method for producing paper, cardboard or cardboard, and uses of ionic polymer and biocide

专利摘要:
METHOD FOR PRODUCTION OF PAPER, CARDBOARD OR CARDBOARD. The invention relates to a method for increasing the benefit of starch in the pulped cellulosic material, preferably repulped in the production of paper or cardboard comprising the steps of (a) pulping a cellulosic material containing starch; (b) treating the cellulosic material containing the starch with one or more biocides, preferably in the thick stock area; and (h) adding an ionic polymer and, preferably, an auxiliary ionic polymer to the cellulosic material; in which the ionic polymer and the optional auxiliary ionic polymer added preferably have a different average molecular weight and, preferably, a different ionicity, in which ionicity is the molar content of ionic monomer units relative to the total amount of monomer units.
公开号:BR112013004430B1
申请号:R112013004430-6
申请日:2011-08-25
公开日:2021-03-02
发明作者:Ludwing Krapsch；Christopher John Mc Gregor；Jean Victor Mallard De La Varende
申请人:Solenis Technologies Cayman, L.P；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[0001] The invention relates to a method for producing pulped paper or paperboard material, preferably repulped. The method increases the benefit of starch in pulped cellulosic material, preferably re-pulped in the production of paper or cardboard by (a) pulping a cellulosic material containing starch, (b) treating the cellulosic material containing the starch with one or more biocides, preferably in the thick stock area, and (h) adding an ionic polymer and, preferably, an auxiliary ionic polymer to the cellulosic material; in which the ionic polymer and the optionally added auxiliary ionic polymer preferably have a different average molecular weight and, preferably, a different ionicity, in which ionicity is the molar content of ionic monomer units relative to the total amount of monomer units. BACKGROUND TECHNIQUE
[0002] Paper production is among the most water intensive industries. In the course of the paper production process, in several stages, substantial amounts of water and aqueous solutions are added to the cellulosic fibers (internal flow stream) and separated from them, respectively (effluent stream). Typically, in the course of the process, a relatively concentrated aqueous slurry of cellulosic material, the so-called "thin stock", is diluted by adding water, thereby producing a relatively diluted aqueous slurry of cellulosic material, the so-called "thin stock".
[0003] As a result of the growth concerning the purity of water resources, and in response to the growth of governmental pressures to maintain the quality of these water resources, the paper industry has been required to investigate and implement methods for reducing chemical pollutants contained in their effluent water streams. The danger of chemical pollution in water is due to the ability of the organic constituents of the effluent currents of paper mills to bind to the dissolved oxygen contained in the water. This connection, whether by chemical reaction or simple chemical interaction, prevents the use of dissolved oxygen for aquatic life. The effect of this bond is commonly referred to as chemical oxygen demand (COD).
[0004] It is well known that the higher the COD of the waste water to be treated, the more ineffective, the more insecure and the more costly these processes are.
[0005] Due to the importance of maintaining adequate levels of dissolved oxygen in water streams, several government agencies have put in place guidelines and test procedures for measuring the COD of effluent streams from paper mills entering rivers and lakes. Several processes have been implemented to improve the quality of the water discharged. Among the proposed methods are (1) evaporation, followed by incineration, (2) chemical treatment to render the organic constituents in the effluent harmless, (3) biological treatment and aeration of effluent collected in holding tanks, and (4) oxidation of the constituents chemicals under restrictive conditions.
[0006] WO 01/36740 discloses papermaking process using enzyme and polymer compositions. Polymer compositions typically contain starch, that is, fresh starch is added to the system. The reference is totally devoid of recycled starch that originates from waste paper. Umbiocide can be added to the treated pulp or pulp. For example, umbiocide can be added to the treated pulp in a mixing box after the pulp has been treated with the enzyme and cationic polymer. Reference teaching is focused on the use of enzymes. It is well known that some biocides interfere with enzymes. The reference does not require the presence of biocide, but merely reveals it as an option to be used in conventional modes for papermaking. There is no collision in the reference that starch degradation can be prevented by the addition of biocide, leaving only that the starch, thus, not degraded, can be fixed to the cellulose fibers of ionic polymers.
[0007] From EP 0 361 736, compositions containing a starch and a flocculating agent intended for use in a paper or cardboard supplier, are known. US 2006/289139 discloses a method of improving retention and drainage in a papermaking process. The method provides for the addition of an associative polymer, starch or a starch derivative, and optionally, a silicon material to the papermaking slip.
[0008] These processes, however, are not satisfactory at all, and thus there is a demand for a method for producing paper, cardboard or cardboard that reduces the COD of the waste water that is produced at the individual stages of the recycling process. papermaking, including the previous stages.
[0009] Starch, particularly non-ionic, anionic, cationic and / or native starch, which is released at the wet end of a papermaking machine by pulping dump or breaking paper, is not attached to the fiber, except through retention natural, and it does not usually contribute to the resistance parameters. In addition, starch degradation usually through microbiological activity causes an increase in the demand for biological oxygen (BOD) and electrical conductivity, and a drop in pH due to the creation of organic acids in the papermaking machine system. This leads to deposition, increased need for microbiological control programs, higher uses of new internal or surface starch to achieve resistance targets and even reduced machine productivity. BOD contributes to COD and gives problems in reaching consensus targets from the effluent installation.
[00010] For the production of uncoated wood-free papers and coated thin papers, up to 40 kg of starch per ton of paper are applied. The packaging paper produced from 100% recovered paper can only be produced economically, and in the quality required by the addition of cost effective biosynthetic starch products. Therefore, these papers are produced with an average starch consumption of 40 kg t-1, mainly by surface application. An additional 25 kg t-1 is applied as an adhesive to the conversion facility. This means that a high amount of starch is typically returned to the production process, via recovered papers, where conventionally it is almost not retained on the paper sheet. Therefore, this quality of uncontrolled starch leads to a considerable load in the white water circuit (usual COD levels of 5,000 to 30,000 mg O2 l-1) and, finally, also in the discharge water (cf. H Holik, Handbook of paper and board, Wiley-VCH Verlag GmbH & Co. KGaA, 1st ed, 2006, Chapter 3.4.3).
[00011] Thus, there is a demand for a method for making paper, cardboard or cardboard that overcomes these problems of the prior art. SUMMARY OF THE INVENTION
[00012] The invention relates to a method for producing paper, cardboard or cardboard comprising the steps of, (a) pulping a cellulosic material containing starch; (b) treating the cellulosic material containing the starch with one or more biocides, preferably in the thick stock area, preferably, thereby preventing microbial degradation of at least a portion of the starch; and, (h) adding an ionic polymer and, preferably, an auxiliary ionic polymer to the cellulosic material, preferably in the thick stock area, where the cellulosic material preferably has a stock consistency of at least 2.0%; or, preferably, in the thin stock area, where the cellulosic material preferably has a stock consistency of less than 2.0%; in which the ionic polymer and the auxiliary ionic polymer preferably have a different average molecular weight and, preferably, a different ionicity, in which ionicity is the molar content of ionic monomer units relative to the total amount of monomer units.
[00013] Preferably, the ionic polymer and the optionally present auxiliary ionic polymer are both cationic.
[00014] Preferably, step (h) comprises the substeps (h1) adding an ionic polymer, preferably a cationic or anionic polymer to the cellulosic material, preferably in the thick stock area, where the cellulosic material preferably has a consistency of the stock of at least 2.0%; or preferably in the thin stock area, where the cellulosic material preferably has a stock consistency of less than 2.0%; and, (h2) preferably, adding an auxiliary ionic polymer, preferably cationic polymer, to the cellulosic material, preferably in the thick stock area where the cellulosic material preferably has a stock consistency of at least 2.0%; or, preferably, in the thin stock area, where the cellulosic material preferably has a stock consistency of less than 2.0% by weight; in which the ionic polymer and the auxiliary ionic polymer preferably have a different average molecular weight and, preferably, a different ionicity, in which ionicity is the molar content of ionic monomer units relative to the total amount of monomer units.
[00015] Additionally, the invention relates to a method for increasing the strength of paper, cardboard or cardboard, comprising steps (a), (b) and (h), in which step (h) can be divided into substep (h1) and substep (h2), as described above. Unless otherwise expressly cited, for the purpose of the specification, any reference to step (h) also independently of another refers to substeps (h1) and (h2). Still further, the invention relates to a method for increasing drainage and / or the rate of production of the papermaking machine comprising steps (a), (b) and (h), as described above. Still further, the invention relates to a method for reducing the effluent COD in the papermaking process comprising steps (a), (b) and (h), as described above.
[00016] Preferably, step (b) is carried out at least partially simultaneously with step (a), or after step (a). Preferably, step (h) is carried out at least partially simultaneously with step (a), or after step (a). Preferably, step (h) is carried out at least partially simultaneously with step (b), or after step (b).
[00017] It has been found that the treatment of dump or break paper, with a sufficient amount of a suitable biocide, for example, an oxidizing and / or non-oxidizing biocide program, during or after pulping, can prevent microbiological degradation of contained starch on the dump or break paper. The fixation, preferably re-fixation, of this non-degraded starch, particularly if it is a nonionic, anionic, cationic and / or native starch, preferably a nonionic, anionic and / or native starch, to cellulosic fibers, can be achieved by adding a cationic polymer, preferably added to the thick stock area, thereby providing reduced white water solids, reduced white water turbidity, increased retention, increased leaf strength, and / or reduced COD. In a preferred embodiment, this effect can be "activated and deactivated", that is, when the ionic polymer, preferably cationic polymer, is employed, the effect is observed after a moment, and when its addition is interrupted, the effect disappears after a time. Additionally, it was surprisingly found that the reduction of starch in the system due to its (re-) fixation to cellulose fibers by means of ionic polymer, also leads to a reduction in nutrients for microorganisms and, therefore, a relative reduction. of biocide demand. BRIEF DESCRIPTION OF THE DRAWINGS
[00018] Figure 1 shows the turbidity of the filtrates of the examples of the invention after being treated with biocide and cationic polymer (0.5, 1.0, 1.5 or 2.0 kg / metric ton), and after being diluted to a thin stock. For comparison also, the turbidity of the corresponding filtrate without cationic polymer is shown. Figure 1 also shows the absorbance of said filtrates at 550 nm after being subjected to an iodine test.
[00019] Figure 2 shows the dehydration impact of the biocide and the cationic polymer by comparing the time to reach the maximum vacuum (break vacuum), and by comparing the difference between the maximum vacuum and the minimum vacuum of the examples of the invention containing different amounts of cationic polymer (0,5,1,0,1,5 and 2,0 kg / metric ton) with the complete experiments.
[00020] Figure 3 shows the drainage rates (time to obtain 100, 200, 300 and 400 ml of filtrate) of the examples of the invention and comparative examples after being subjected to a VDT study.
[00021] Figure 4 shows the dry bone weight depending on the amount of the cationic polymer added.
[00022] Figure 5 shows the turbidity of the filtrates of the examples of the invention after being treated with biocide and cationic polymer, and after being diluted to a thin stock.
[00023] Figure 6 shows the impact of total sample retention depending on the content of the cationic polymer.
[00024] Figure 7 shows the drainage rates (time to obtain 100, 200, 300 and 400 ml of filtrate) of the examples of the invention and comparative examples after being subjected to a VDT study.
[00025] Figure 8 shows the amount of cellulosic material recovered after 40 seconds of drainage time for the examples of the invention and comparative examples.
[00026] Figure 9 shows the amount of water (in%) recovered for the examples of the invention containing the cationic polymer compared to the reference.
[00027] The results shown in Figures 2 - 9 were performed with a thick stock of cellulosic material containing enough biocide to prevent starch degradation.
[00028] Figure 10 shows the necessary biocide dose in order to keep the process parameters of the papermaking process constant with the addition of ionic polymer (inventive) and without the addition of ionic polymer (polymer).
[00029] Figure 11 shows the drainage rates (time to obtain 100, 200, 300 and 400 ml of filtrate) of the examples of the invention and comparative examples after being subjected to a VDT study. DETAILED DESCRIPTION OF THE INVENTION
[00030] The control of microbiological activity in papermaking machines with both oxidizing and non-oxidizing biocides, is well documented. There is also extensive literature on the use of starch as a dry strength aid and the use of synthetic dry strength helpers that can be used, or in addition to the starch applied to both the wet end and the surface of the paper sheet, or as a total or partial replacement of the starch.
[00031] The invention is related to the combined use of an effective biocide, for example, an oxidizing and non-oxidizing microbiological control program, to prevent the degradation of starch (non-ionic / cationic / anionic) present from the pulping of paper dumping or breaking, and the use of an ionic polymer, preferably in combination with an auxiliary ionic polymer in order to fix the now non-degraded starch to the fiber so that it is retained, thereby making it available to provide resistance to final sheet, and removing it from the circulating water. It was surprisingly found that the starch that is released, for example, by pulping the supply of recycled waste, can be reused to provide resistance, considering that degradation (conventionally through microbiological activity) is prevented (amylase control), and, in this way, the non-degraded starch is fixed to the newly formed sheet. This is especially true for nonionic, anionic, cationic and / or native starch, for example, applied to the leaf surface through a size press and partially released from the dump paper during pulping. In conventional processes, this released starch is generally considered to be non-active starch, without the ability to be retained in a substantial amount in order to provide resistance.
[00032] The invention relates to the use of a biocide, for example, an oxidizing and / or non-oxidizing biocide, as the first step in preventing starch degradation by microbiological activity (amylase control), and the use of a polymer ionic, preferably a cationic polymer or anionic polymer, preferably a high molecular weight polymer, high cationic charged polymer, preferably in combination with an auxiliary ionic polymer, preferably cationic or anionic polymer, to fix the starch to the fiber.
[00033] Thus, the method, according to the invention, features a two-step approach: 1.) cancellation of the microbiological degradation of starch carton, or paper-making machine that approaches the flow with 2.) removal of the starch maintained from the white water system of the papermaking machine through fixation, preferably re-fixation to the fiber in order to grant resistance.
[00034] By controlling the microbiological degradation of starch as it is released by the pulping process and the subsequent fixation by the high molecular weight polymer, high charged cationic polymer, DOC and electrical conductivity levels can be reduced, and most importantly less starch fresh is needed to achieve strength specifications. The machine's operability can be improved through improved cleaning. Importantly, COD levels can be reduced by improving the load on the mill effluent installation. Cost savings from increased efficiency of machine additives, less downtime for cleaning, and improved operability are all possible.
[00035] A first aspect of the invention relates to a method - for treating a cellulosic material used for paper production; and / or - for the production of a paper product; and / or - for the production of paper, cardboard or cardboard; and / or - to increase the resistance of paper, cardboard or cardboard; and / or - to increase the drainage and / or production rate of the papermaking machine; and / or - to reduce the effluent COD in the papermaking process; and / or - to reduce the amount of nutrients for microorganisms in the cellulosic material; and / or - to reduce the consumption of fresh starch by recycling the starch that is already contained in the starting material and / or the water circuit of the papermaking facility; -method in each case comprising the steps of (a) pulping a cellulosic material containing starch; (b) treating the cellulosic material containing the starch with one or more biocides, preferably thereby preventing microbial degradation of at least a portion of the starch; (c) optionally, removing paint from the cellulosic material; (d) optionally, mixing the cellulosic material; (e) optionally, bleaching the cellulosic material; (f) optionally, refining the cellulosic material; (g) optionally, screening and / or cleaning the cellulosic material in the thick stock area; (h) adding (h1) an ionic polymer, preferably a cationic polymer and, preferably, (h2) an auxiliary ionic polymer, preferably cationic polymer, to the cellulosic material, preferably in the thick stock area, that is, to the stock thick, where the cellulosic material preferably has a stock consistency of at least 2.0%; or preferably in the thin stock area, that is, in the thin stock, where the cellulosic material preferably has a stock consistency of less than 2.0%; in which the ionic polymer and the optionally added auxiliary ionic polymer preferably has a different average molecular weight and, preferably, a different ionicity, in which ionicity is the molar content of ionic monomer units relative to the total number of monomer units; (i) optionally, screening and / or cleaning the cellulosic material in the thin stock area, that is, after diluting the thick stock in a thin stock; (j) optionally, forming a wet sheet from cellulosic material; (k) optionally, draining the wet leaf; and (l) optionally, drying the drained sheet.
[00036] It has now surprisingly been found that starch, such as non-ionic, cationic and anionic starch, preferably non-ionic, anionic, cationic and / or native starch, if not degraded, can be linked, preferably rewired to cellulose fibers, simply by pulping the cellulosic material containing said starch, and treating the cellulosic material containing the starch with a sufficient amount of a suitable biocide, either during pulping, or shortly thereafter, thereby preventing microbiological degradation of the starch, and adding appropriate amounts of ionic polymer, preferably cationic polymers in order to fix the starch, thus, not degraded, preferably non-ionic, anionic, cationic and / or native non-degraded starch, to the cellulosic fibers.
[00037] For the purpose of the specification, the term "undegraded starch" refers to any type of starch that preferably originates from dump or break paper, and in the course of pulping, it has preferably maintained essentially its molecular structure so that it remains capable of being attached to the fibers. This includes slight degrees of degradation, but compared to conventional processes, the structure of the non-degraded starch preferably does not substantially change (in terms of microbiological degradation) during pulping and papermaking processes.
[00038] In a preferred embodiment, the method, according to the invention, comprises the additional step of adding starch to the cellulosic material. Thus, in this embodiment, the starch, which is processed according to the invention, preferably originates from two sources: the first source is the starting material, for example, waste paper, already containing starch, and the second source is starch that is additionally added to the cellulosic material. The additionally added starch can be any type of starch, that is, native, anionic, cationic, non-ionic, and the like. It can be added to cellulosic material in the thick stock area, or in the thin stock area. When it is added to the thick stock area, it is preferably added to the machine box, more preferably to the machine box discharge. Alternatively, or in addition, the starch can be added to the size press. In a preferred embodiment, the starch is sprayed, for example, in the form of an aqueous solution, between the folds of multi-fold paper, cardboard or paperboard.
[00039] The basic steps of paper production are known to the technician in the subject. In this regard, they can be referred to, for example, in C.J. Biermann, Handbook of Pulping and Papermaking, Academic Press; 2 edition (1996); J.P. Casey, Pulp and Paper, Wiley-Interscience; 3rd edition (1983); and E. Sjõstrõm et al., Analytical Methods in Wood Chemistry, Pulping and Papermaking (Springer Series in Wood Science), Springer; 1 edition (1999).
[00040] The raw material for paper is fiber. For the purpose of the specification, "pulping" is to be related to the process of separation of fibers, suitable for the manufacture of paper, of cellulosic material such as recovered paper (dumping).
[00041] Modern papermaking typically involves seven basic operations: 1) pre-treatment of the fiber; 2) mixing the fiber; 3) provision of cleaning and sieving; 4) distribution and measurement of the slurry; 5) weft formation and water removal by mechanical means; 6) compaction of the web and removal of water by means of heat; and 7) finishing the sheet, through calendering, sizing, coating, enamelling, or paper conversion.
[00042] In practice, there are numerous variants of methods for producing paper, cardboard or cardboard. All of these variants have in common, however, that the total method can be divided into the following sections that will be referred to below to define preferred embodiments of the method according to the invention: (I) measurements that occur before pulping; (II) measures associated with pulping; (III) measures that occur after pulping, but still outside the papermaking machine; (IV) measures that take place inside the papermaking machine; and (V) measurements that take place after the papermaking machine.
[00043] Sections (I) to (II) are typically related to the processing of a thick stock of cellulosic material, so that during section (III), the cellulosic material is converted from a thick stock to a thin stock by dilution with water, and section (IV) is thus related to the processing of a thin stock of cellulosic material. All areas in which measurements that occur prior to dilution, preferably during step (III), are preferably referred to as the "thick stock area", whereby the remainder is preferably referred to as the "thin stock area".
[00044] In a preferred embodiment of the invention, the water used for pulping the cellulosic material containing the starch is brought into contact with at least a part of the biocide, optionally provided as an aqueous composition, in section (I) of the method for the production of that is, before pulping.
[00045] In another preferred embodiment of the invention, the cellulosic material containing the starch is brought into contact with at least part of the biocide, optionally provided as an aqueous composition, in section (II) of the method for the production of paper, that is, in the course of pulping. Section (II) involves step (a) of the method, according to the invention, so the supply of cellulosic material containing the starch in the pulping device (pulper) and its removal from it, are usually not considered to belong to the step pulping per se, but are at least partially involved by section (II) as well.
[00046] In yet another preferred embodiment of the invention, the cellulosic material containing the starch is brought into contact with at least part of the biocide, optionally provided as an aqueous composition, in section (III) of the method for the production of paper, i.e. , after pulping, but still outside the papermaking machine. Preferably, the biocide is added to the cellulosic material containing the starch in the thick stock area.
[00047] Preferably, pulping is the first step in the production of paper where the cellulosic material is brought into contact with substantial amounts of water, thereby generating an aqueous slurry, that is, an aqueous suspension of cellulosic fibers, also referred to like pulp. Said pulp forms an intermediate fibrous material for the production of paper or cardboard.
[00048] The pulping site is referred to as a pulper, that is, a reaction vessel used for the production of an aqueous dispersion or suspension of the cellulosic material. Sometimes, a pulper is also referred to as a hydropower.
[00049] In the case that recovered paper (dump) is used as the starting material for the paper production process, the appropriate recovered paper (dump) is typically directly introduced into the pulper. Dump paper can also be mixed with a quantity of virgin material to improve the quality of the cellulosic material.
[00050] For the purpose of the specification, the term "cellulosic material" refers to any material comprising cellulose including recovered paper (dump). Additionally, the term "cellulosic material" refers to all intermediate and final products during the papermaking process, which originates from recovered paper (dumping), such as dispersions or suspensions of cellulosic material, pulped cellulosic material, cellulosic material without ink, mixed cellulosic material, targeted cellulosic material, refined cellulosic material, sieved cellulosic material and the final paper, cardboard or cardboard. Therefore, the term "cellulosic material" involves pulp, slurry, sludge, stock, and the like.
[00051] The starch contained in the cellulosic material does not necessarily originate from the cellulose starting material (recycled and similar material). It is also possible that the total amount of cellulose starting material is virgin material containing no starch, and that the starch contained in the cellulosic material originates from another source, preferably from a recirculation unit that supplies the pulper with water recycled from the wet end of the papermaking machine.
[00052] In a preferred embodiment, the cellulosic material containing the starch originates from dump or break paper, but can be mixed with, for example, virgin material (=> recycled pulp and mixed pulp, respectively).
[00053] In a preferred embodiment, the starch content of the cellulosic material containing the starch, i.e., the dump or break paper that is used as the starting material, is at least 0.1% by weight, more preferably at least 0.25% by weight, or at least 0.5% by weight, or at least 0.75% by weight, or at least 1.0% by weight, or at least 1.5% by weight, or at least 2.0% by weight, or at least 3.0% by weight, or at least 5.0% by weight, or at least 7.5% by weight, or at least 10% by weight, or at least 15% by weight, based on the weight of dry cellulosic material.
[00054] In another preferred embodiment, the starch is added to the cellulosic material, for example, to the virgin material, in the course of paper production, preferably in the thick stock area. Preferably, a portion of the freshly added starch is attached to the cellulosic fibers before the weft is formed and the water is drained. Due to the recirculation of at least a portion of the water drained from the pulp, another portion of the starch is returned to the beginning of the total process. In this way, the starch does not necessarily originate from waste paper, but can alternatively or additionally also originate from the method itself. This embodiment is particularly preferred when the starch is non-ionic, particularly native starch. Under these circumstances, the freshly added starch is not fixed to the cellulose fibers, but fixed.
[00055] According to the invention, the cellulosic material contains a starch. For the purpose of the specification, the term "starch" refers to any modified or unmodified starch, typically used in paper production. Starch is a carbohydrate polysaccharide consisting of a large number of glucose units joined together by glycosidic bonds. Starch is produced by all green plants as an energy store. Starch is composed of two types of molecules: linear and helical amylose and branched amylopectin. Depending on the origin, native starch usually contains 20 to 25% amylose and 75 to 80% amylopectin. By physical, enzymatic or chemical treatment of native starch, a variety of modified starches can be prepared, including nonionic, anionic and cationic starches.
[00056] Preferably, the starch contained in the cellulosic material has an amylose content within the range of 0.1% by weight to 95% by weight.
[00057] In a preferred embodiment of the invention, the starch contained in the cellulosic material is substantially pure amylose, i.e., it has an amylose content of about 100% by weight. In another preferred embodiment of the invention, the starch contained in the cellulosic material is substantially pure amylopectin, that is, it has an amylopectin content of about 100% by weight. In yet another preferred embodiment, the amylose content is within the range of 22.5 ± 20% by weight, whereby the amylopectin content is preferably within the range of 77.5 ± 20% by weight.
[00058] In a preferred embodiment, the starch is non-ionic, preferably native starch. In another preferred embodiment, the starch is anionic. In yet another preferred embodiment, the starch is cationic. In yet another preferred embodiment, starch contains both anionic as well as cationic charges, so the relative content can be balanced, dominated by anionic charges, or dominated by cationic charges.
[00059] In a preferred embodiment, the starch that is contained in the cellulosic material, preferably before pulping, has an average molecular weight of at least 25,000 g / mol.
[00060] In a preferred embodiment, the relative weight ratio of starch and cellulosic material (solid contents) is within the range of 1: (20 ± 17.5) or 1: (50 ± 40) or 1 :( 100 ± 90) or 1: (200 ± 90) or 1: (400 ± 200) or 1: (600 ± 200) or 1: (800 ± 200).
[00061] A person skilled in the art knows that cellulosic material may contain additional components in addition to cellulose, such as chemicals used for the chemical and semi-chemical step of pulping, dyes, bleaching agents, fillers, etc.
[00062] If not expressly stated otherwise, the percentages based on the cellulosic material are to be listed as being based on the total composition containing the cellulosic material and the starch (solids content).
[00063] If not explicitly mentioned otherwise, for the purpose of the specification, the term "papermaking process" or "method for the production of paper" refers to the production of paper, as well as the production of cardboard and cardboard.
[00064] For the purpose of the specification, cellulosic starting material for the production of paper, cardboard and / or cardboard, which originates from recovered paper (dump), is referred to as "recycled material", so the material fresh starter is referred to as "virgin material". It is also possible for a mixture of virgin material and recycle material to be used as the starting material for the papermaking process, which is referred to herein as "mixing material". In addition, it is also possible that the cellulosic starting material is "broken" or "coated broken" (recessed material) which, for the purpose of the specification, must be surrounded by the term "recycled material".
[00065] For the purpose of the specification, the pulp that originates from virgin material, recycle material, or mixing material, is referred to as "virgin pulp", "recycling pulp" and "mixing pulp", respectively.
[00066] Typically, water is added during and mechanical pulping step to the cellulosic material, that is, to the virgin material, recycling material, or mixing material, to produce the respective cellulosic pulp, that is, virgin pulp, recycling pulp , or mixing pulp. The respective pulp is usually an aqueous fibrous dispersion, or aqueous fibrous suspension of the cellulosic material.
[00067] The mechanical pulping process is typically carried out by exposing the cellulosic material to mechanical force, more specifically, shear force.
[00068] According to the invention, the biocide is present during the pulping step, and / or is added thereafter, preferably shortly thereafter. Microorganisms from the waste paper also play a role in the degradation of starch contained in the waste paper, particularly when the waste paper is stored for days or months, and subjected to the activity of the microorganism during this storage time. The treatment of the dumping paper with biocide during pulping cannot reverse the effects caused by the activity of the microorganism under the starch during the storage of the dumping paper. However, the growth conditions of the microorganism are significantly improved during pulping - when the paper is in contact with the process water - and the inventors have found that it is advantageous to add the biocide at this stage of the process. Since the degradation caused by microorganisms usually takes longer than a few minutes, the inventors have found that it can also be sufficient to add the biocide briefly after pulping.
[00069] For this proposal, the cellulosic material that contains the starch, that is, the virgin material, recycle material, or mixture material, is brought into contact with biocide. If the biocide is added shortly after the pulping step, it is preferably added to the cellulosic material 1 to 60 minutes after the pulping step has been completed.
[00070] In order to treat the cellulosic material containing the starch with biocide according to the invention, it is apparent to a person skilled in the art that at least a part of the total amount (total internal flow) of biocide is added to the cellulosic material containing the starch at any time during the pulping step (a), that is, after pulping has started, or shortly after pulping has been completed. The biocide can be added continuously or discontinuously.
[00071] For the purpose of the specification, the term "continuously" means that the quantity (internal flow) of the biocide for the specific dose is added to the cellulosic material containing the starch without interruption.
[00072] For the purpose of the specification, the term "discontinuously" means here that the addition of the biocide to the cellulosic material containing the starch is carried out by means of pulses of a predetermined length that are interrupted for periods during which no biocide is added at this feed point.
[00073] A person skilled in the art is aware that papermaking processes as such are typically continuous processes. Thus, any "quantity" or "dosage" of biocide, ionic polymer and additional additive, respectively, which is to be added to the cellulosic material, refers to a respective "internal flow" of said biocide, ionic polymer and additional additive, respectively, in order to achieve a desired predetermined local concentration thereof in the cellulosic material stream. This internal flow can be continuous or discontinuous. Consequently, when the "amount" or "dosage" of biocide, ionic polymer and additional additive, respectively, is divided into portions that are added to the cellulosic material at different locations and / or during different process steps, each portion refers to a partial internal flow of said biocide, ionic polymer and additional additive, respectively, in order to achieve a desired predetermined local concentration of it, that is, downstream with respect to its feeding point.
[00074] Typically, water is added to the cellulosic material, that is, to the virgin material, recycle material, or mixing material, before and / or during the pulping step. At least a part of the total amount (total internal flow) of the biocide can be dissolved, dispersed or suspended in said water used to repulp the cellulosic material containing the starch, that is, for the virgin material, recycle material or mixing material.
[00075] In this embodiment, the biocide and water used for pulping can already be brought into contact with each other before pulping is started.
[00076] In a preferred embodiment according to the invention, the biocide is in contact with the water used for pulping at least 10 min before pulping begins, or at least 30 min, or at least 60 min, or at least 120 min, or at least 150 min, or at least 180 min, or at least 210 min, or at least 240 min, or at least 300 min, or at least 360 min, or at least 420 min, or at least 480 min.
[00077] Typically, the pulping step (a) can take from several minutes to several hours. In another preferred embodiment, at least a part of the total amount (total internal flow) of the biocide is added to the cellulosic material during the pulping period.
[00078] For the purpose of the specification, the term "pulping period" is defined as the total time that the pulping step is carried out.
[00079] For example, in the case that the pulping step takes a total time of 1 hour (pulping period), the biocide can be added discontinuously or continuously to the pulper at any point of time or during any interval of time, for example , up to 120 minutes after the pulping step has started.
[00080] In step (b) of the method according to the invention, the cellulosic material containing the starch is treated with one or more biocides, preferably thereby preventing microbial degradation of at least a portion of the starch. In a preferred embodiment, step (b) is at least partially performed simultaneously with step (a) of the method according to the invention, i.e., biocide treatment is carried out during pulping. In another preferred embodiment, step (b) is carried out after step (a) has been completed. One skilled in the art recognizes that any total or partial overlap of steps (a) and (b) is possible, and in accordance with the invention.
[00081] According to the method of the invention, step (b) preferably serves the proposal to avoid degradation of the starch that is contained in the cellulosic material, by eradicating microorganisms that are otherwise capable of degrading the starch (control amylase).
[00082] A wide variety of microorganisms can be found in the pulping process. Each type of pulp has its own microbial characteristics. In general, the microorganisms observed in the production of paper are species of bacteria, yeast and fungus; algae and protozoa exist, but they rarely cause problems. The problems caused by microorganisms can be very different. Very well-known problems are sludge and corrosion.
[00083] The species of the following bacterial genera belong to the usual contaminated pulp: Achromobacter, Actinomycetes, Aerobacter, Alcaligenes, Bacillus, Beggiatoa, Crenothrix, Desulphovibrio, Flavobacterium, Gallionella, Leptothrix, Pseudomonas, Sphearo- tilus, and Thphio- Species of Alcaligenes, Bacillus and Flavobacterium, as well as species of the yeast, Monilia, cause pink mud. Red or brown mud is caused by the bacteria that form ferric hydroxide, namely Crenothrix, Gallionella and Leptothrix. Species of Thiobacillus and Beggiatoa are corrosion bacteria in which they oxidize sulfides to sulfuric acid. Desulphovibrio species are also corrosion bacteria for the opposite reason. Species of the latter genus reduce sulfate to hydrogen sulfite that interact with metal to cause corrosion. Metal sulphites are also black, which is another unwanted effect of sulfate-reducing bacteria.
[00084] Among fungi, species of the following genera are found most often in pulp systems: Aspergillus, Basidiomyces, Cephalosporium, Cladosporium, Endomyces, Endomyopsis, Mucor, Penicillium, and Trichoderma. Blue stain on wood is caused by Cephalosporium and Cladosporium.
[00085] Finally, species of the following yeast genera can be isolated from the pulp: Monilia, Pullularia, Rhodotorula and Saccharomyces. For further details, refer to H.W.Rossmorore, Handbook of Biocide and Preservative Use, Chapter Paper and Pulp, Chapman & Hall, 1995.
[00086] Most prevalent species that express amylase and thereby cause starch degradation, include Actinomycetes, Aerobacter, Bacillus, Beggiatoa, Desulphovibrio, Flavobacterium, Gallionella, Leptothrix, Pseudomonas, Thiobacillus; Aspergillus, Basidiomycetes, Cephalosporium, Endomyces, Endomycopsis, Mucor, Penicillium; Pullularia, and Saccharomyces.
[00087] Thus, the proposal to add biocide according to the invention, essentially serves the proposal to eradicate one or more of the micro-organisms mentioned above, and the biocide dosages are preferably adapted accordingly.
[00088] In a preferred embodiment, the total amount (total internal flow) of biocide is added to the cellulosic material during the pulping step (a) discontinuously or continuously; that is, 100% by weight of the total amount (total internal flow) of the biocide is added to the cellulosic material, that is, to the virgin material, recycle material or mixing material, during the pulping step (a).
[00089] In another preferred method, additional parts of biocide can be added at any time, preferably up to 480 min after the pulping step (a) has been started in any suitable location in order to avoid degradation of the starch. This embodiment includes adding additional parts of the biocide either during the pulping step (a), or, preferably, up to 60 minutes after pulping has been completed. In a preferred embodiment, at least a part of the total amount (total internal flow) of the biocide is added to the cellulosic material containing the starch at any time preferably up to 60 minutes after the pulping step (a) has been completed.
[00090] In a preferred embodiment, one or more biocides are added to the cellulosic material at at least 2 different feed points, more preferably at least 3 different feed points, and even more preferably at least 4 different feed points at the plant. papermaking, where identical or different biocides or combinations of biocides can be added at various feeding points.
[00091] The biocide can be gaseous, solid or liquid; organic or inorganic; oxidizing or non-oxidizing.
[00092] The biocide can be used in substance or in dilution with a suitable solvent, preferably water, in solution or dispersion, suspension or emulsion.
[00093] The biocide can be a one-component biocide, a two-component biocide, or a multi-component biocide.
[00094] The biocide preferably has a comparatively short half-life, that is, it decomposes comparatively quickly, thereby losing its biocidal action. When a combination of two or more biocides is employed, the half-life of at least one biocide within said combination is preferably comparatively short. Preferably, under the conditions of the method according to the invention (temperature, pH and the like), the half-life of the biocide is no more than 24 h, or no more than 18 h, or no more than 12 h, more preferably not more than 10 h, even more preferably not more than 8 h, even more preferably not more than 6 h, more preferably not more than 4 h, in particular, not more than 2 h. The half-life of a given biocide can be easily determined by routine experimentation, preferably under the general conditions of the method according to the invention.
[00095] It has been surprisingly found that biocides having a comparatively short half-life in preventing starch degradation by eradicating microorganisms, would otherwise be broken down into starch, but do not cause problems in the waste water system, which typically also occur in microorganisms that must not be eradicated by the biocide. In addition, it has been surprisingly found that biocides having a comparatively short half-life can be used in comparatively high concentrations without causing substantial problems related to the treatment of wastewater.
[00096] In the United States, biocides to be used in the production of paper and cardboard for use in contact with food must be on the list approved by the US Food and Drug Administration (FDA).
[00097] In a preferred embodiment, the biocide is selected from oxidizing and non-oxidizing biocides.
[00098] Examples of oxidizing biocides include component systems such as ClO2, H2O2 or NaOCl; and two component systems comprising, for example, a nitrogenous compound, preferably an inorganic ammonium salt in combination with an oxidizer, preferably a halogen source, more preferably a chlorine source, more preferably hypochlorous acid or a salt thereof, such as NH4Br / NaOCl or (NH4) 2SO4 / NaOCl; and two component systems comprising, for example, organic biocides in combination with an oxidant, preferably a halogen source, more preferably a chlorine source, more preferably hypochlorous acid or a salt thereof, such as bromochlor-5,5-dimethylimide- zolidine-2,4-dione (BCDMH) / NaOCl, or dimethylhydantoin (DMH) / NaOCl.
[00099] In a particularly preferred embodiment, the biocide is a two-component oxidizing biocide where the first component is a nitrogenous compound, preferably selected from ammonia, amines, inorganic or organic ammonium salts, and inorganic and organic amine salts; and the second component is a source of halogen, preferably a source of chlorine.
[000100] Preferred nitrogenous compounds include ammonia salts, methylamine, dimethylamine, ethanolamine, ethylenediamine, diethanolamine, triethanolamine, dodecylethanolamine, hexdecylethanolamine, oleic acid, ethanolamine, triethylenetetramamine, dibutylamine, tributylamine, glutamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine, dilaurylamine. , n-acetylglucosamine, diphenylamine, ethanolmethylamine, diisopropanolamine, n-methylaniline, n-hexyl-n-methylamine, n-heptyl-n-methylamine, n-octyl-n-methylamine, n-nonyl-n-methylamine, n-decyl -n-methylamine, n-dodecyl-n-methylamine, n-tridecyl-n-methylamine, n-tetra-decyl-n-methylamine, n-benzyl-n-methylamine, n-phenylethyl-n-methylamine, n-phenylpropyl -n-methylamine, n-alkyl-n-ethylamines, n-alkyl-n-hydroxyethylamines, n-alkyl-n-propylamines, n-propylheptyl-n-methylamine, n-ethylhexyl-n-methylamine, n-ethylhexyl-n - butylamine, n-phenylethyl-n-methylamine, n-alkyl-n-hydroxypropylamines, n-alkyl-n-isopropylamines, n-alkyl-n-butylaminase n-alkyl-n-isobutyl-mi nas, n-alkyl-n-hydroxyalkylamines, hydrazine, urea, guanidines, biguanidines, polyamines, primary amines, secondary amines, cyclic amines, bicyclic amines, aminosoligocyclic amines, aliphatic amines, aromatic amines, polymers containing secondary primary nitrogen. Examples of ammonia salts include ammonium bromide, ammonium carbonate, ammonium chloride, ammonium fluoride, ammonium hydroxide, ammonium iodide, ammonium nitrate, ammonium phosphate, and ammonium sulfamate. Preferred nitrogenous compounds are ammonium bromide and ammonium chloride.
[000101] Preferred oxidizers include chlorine, alkaline and alkaline earth hypochlorite salts, hypochlorous acid, chlorinated isocyanurates, bromine, alkaline and alkaline earth hypobromite salts, hypobromous acid, bromine chloride, halogenated hydantoins, such as ozone and peroxide compounds alkaline and alkaline earth perbotate salts, alkaline and earth alkaline percarbonate salts, alkaline and alkaline earth persulfate salts, hydrogen peroxide, percarboxylic acid, and peracetic acid. Particularly preferred sources of halogen include reaction products of a base and a halogen, such as hypochlorous acid and the salts thereof. Preferred salts of hypochlorous acid include LiOCl, NaOCl, KOCl, Ca (OCl) 2 and Mg (OCl) 2, which are preferably provided in aqueous solution. Preferred inorganic salts of ammonia include, but are not limited to, NH4F, NH4Cl, NH4Br, NH4I, NH4HCO3, (NH4) 2CO3, NH4NO3, NH4H2PO2, NH4H2PO4, (NH4) 2HPO4, NH4SO3NH2, NH4IO3, NH4S3, NH4SH, ( , (NH4) 2SO3, NH4HSO4, (NH4) 2SO4, and (NH4) 2S2O3. Preferred organic ammonium salts include, but are not limited to, NH4OCONH2, CH3CO2NH4 and HCO2NH4. The amine can be a primary or secondary amine, or the amine portion of an amide; for example, urea, or alkyl derivatives thereof, such as N-N'-dimethyl urea, or N'-N'-dimethylurea. The combination of NH4Br and NaOCl is particularly preferred and known, for example, from US 7,008,545, EP-A 517 102, EP 785 908, EP 1 293 482 and EP 1 734 009. Preferably, the relative molar ratio of said first component and said second component is within the range of 100: 1 to 1: 100, more preferably 50: 1 to 1:50, even more preferably 1:20 to 20: 1, even more preferably 1:10 to 10: 1, more preferably 1: 5 to 5: 1 and, in particular, 1: 2 to 2: 1.
[000102] Compared to strong oxidizers, biocides of this type, that is, combinations of ammonia salts with hypochlorite acid or salts thereof, have particular advantages.
[000103] For a number of years, strong oxidizers have been used to control microbial populations in the papermaking industry. Maintaining an effective oxidant level is not always easy, or economically viable, because paper process currents exhibit high and variable "demand" in the oxidizer. This demand is caused by the presence of organic materials, such as fiber, starch, and other colloidal or particulate organic materials in the process. These organic materials react with and consume the oxidant, making it much less effective in controlling microbial populations. In order to achieve an effective residual oxidant in high-demand systems, such as paper-making machines, the oxidant must be overfed to exceed the demand in the system. Overfeeding strong oxidants not only leads to higher treatment costs, but can also cause adverse side effects in the papermaking system. These side effects include increased consumption of dyes and other costly wet end additives (eg, optical brighteners and sizing agents), increased corrosion rates, and reduced felt life. Some oxidants also contribute greatly to the amount of halogenated organic compounds (AOX) produced in the papermaking process. In addition, excessive residues of certain oxidants may be suitable for controlling microbial populations in the mass fluid, but they are ineffective in controlling biopellicle due to limited penetration into the biopellicle matrix.
[000104] In contrast to strong oxidizers, biocides produced by mixing ammonia salts, such as ammonia bromide solution, with, for example, sodium hypochlorite and fresh mill water, under specific reaction conditions, can be described as a weak oxidizer. The biocide is produced on the spot and immediately dosed to the paper system. The required dosage depends on several factors, including use of fresh water, water recycling, and the presence of reducing agents. Biocides of this type, therefore, have a comparatively short half-life, and therefore do not accumulate, which could cause problems with wastewater treatment. In addition, they are not very aggressive, that is, they do not oxidize the other constituents of the cellulosic material, but are comparatively selective for microorganisms.
[000105] Oxidation of one-component biocides or two-component biocides of this type can be employed alone, or, preferably, particularly when the starting material comprises recycled pulp, in combination with non-oxidizing biocides.
[000106] Examples of non-oxidizing biocides include, but are not limited to, quaternary ammonia compounds, benzyl-C12-16-alkyldimethyl chlorides (ADBAC), polyhexamethylenebiguanide (biguanide), 1,2-benzisothiazole-3 (2H) -one (BIT), bronopol (BNPD), bis (trichloromethyl) sulfone, diiodomethyl-p-tolylsulfone, sulfone, bronopol / quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (BNPD / ADBAC), bronopol / didecyldimethylammonium chloride (BNPD / DDAC), bronopol / 5-chloro-2-methyl-2H-isothiazol-3-one / 2-methyl-2H-isothiazole-3-one (BNPD / Iso), NABAM / sodium dimethyldithiocarbamate, sodium dimethyldithiocarbamate- N, N-dithiocarbamate (NABAM), sodium methyldithiocarbamate, sodium dimethyldithiocarbamate, 5-chloro-2-methyl-4-isothiazolin-3-one (CMIT), 2,2-dibromo-2-cyanoacetamide ( DBNPA), DBNPA / bronopol / iso (DBNPA / BNPD / Iso), 4,5-dichloro-2-n-octyl-3-isothiazolin-3-one (DCOIT), didecyldimethylammonium chloride (DDAC), didecyldimethylammonium chloride, dimethylbenzylammonium alkyl chloride (DDAC / ADBAC) , dodecylguanidine monohydrochloride / quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (DGH / ADBAC), dodecylguanidine / methylene dithocyanate monohydrate (DGH / MBT), gluteraldehyde (glut), gluteraldehyde / compounds quaternary / benzylcoconut alkyldimethyl chlorides (Glut / coconut), gluteraldehyde / didecyldimethylammonium chloride (Glut / DDAC), gluteraldehyde / 5-chloro-2-methyl-2H-isothiazole-3-one / 2-methyl-2H-isothiazol-3- one (Glut / Iso), gluteraldehyde / methylene dithocyanate (Glut / MBT), 5-chloro-2-methyl-2H-isothiazol-3-one / 2-methyl-2H-isothiazole-3-one (Iso), methylene dithocyanate (MBT), 2-methyl-4-isothiazolin-3-one (MIT), methane oxirane (metamine oxirane), sodium bromide (NaBr), nitromethylidinetrimethanol, 2-n-octyl-3-isothiazolin-3-one (OIT ), bis (trichloromethyl) sulfone / quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (sulfone / ADBAC), simclosene, terbuthylazine, dazomet (thione), tetracis (hydroxymethyl) phosphonium sulfate (2: 1) ( THPS) and p- [(di-iodomethyl) south fonyl] toluene (tolyl sulfone), and mixtures thereof.
[000107] A person skilled in the art knows that a simple biocide or a simple multicomponent biocide can be employed, or a combination of different biocides.
[000108] In a particularly preferred embodiment of the invention, preferably when the starting material comprises recycle pulp, the biocide is a biocide system, preferably comprising a first biocide composed of an inorganic ammonium salt in combination with a halogen source, preferably a source of chlorine, more preferably hypochlorous acid or a salt thereof, and an additional biocide, preferably selected from non-oxidizing biocides and / or organic biocides, preferably non-oxidizing organic biocides. For the purpose of the specification, unless otherwise expressly cited, the one or more biocides referred to in step (b) may involve said additional biocide, if present.
[000109] In a preferred embodiment, the non-oxidizing biocide comprises bronopol (BNPD) and at least one isothiazolone compound selected from the group consisting of 1,2-benzisothiazole-3 (2H) -one (BIT), 5-chlorine -2-methyl-4-isothiazolin-3-one (CMIT), 4,5-dichloro-2-n-octyl-3-isothiazolin-3-one (DCOIT), methyl-4-isothiazolin-3-one (MIT ), 2-n-octyl-3-isothiazolin-3-one (OIT); and / or a sulfone selected from bis (trichloromethyl) sulfone and diiodomethyl-p-tolylsulfone. In another preferred embodiment, the non-oxidizing biocide comprises compounds that support quaternary ammonium and bronopol ions (BNPD), or a sulfone selected from bis (trichloromethyl) sulfone and diiodomethyl-p-tolylsulfone. The biocide system, preferably comprising an oxidizing biocide and a non-oxidizing biocide, is particularly preferred when the residence time of the biocide in the thick stock is comparatively long, that is, the time from the point in time when the biocide is added to the cellulosic material until the point in time when the cellulosic material enters the paper-making machine. In a preferred embodiment, the above biocide system comprising a first and an additional biocide is employed when said residence time is at least 1 h, or at least 2 h, or at least 4 h, or at least 6 h, or at least at least 8 h, or at least 10 h.
[000110] Said biocide system is particularly preferred when the starting material comprises recycled pulp. When the starting material essentially consists of virgin pulp, however, the addition of an additional biocide is preferably omitted.
[000111] When such a combination of biocides is employed, at least a portion of the first biocide is preferably added to the dilution water of the pulper, while the additional biocide is preferably added to the discharge of the pulper and / or to the admission of the clarification of the fiber.
[000112] The dosage of one or more biocides depends on its antimicrobial effectiveness. Typically, the biocide is dosed in an amount sufficient to prevent substantial degradation of the starch contained in the cellulosic material. The appropriate dosages for a given biocide can be determined by routine experimentation, or by comparing the number of microorganisms before and after adding the biocide (taking into account that biocides typically require some time in order to eradicate microorganisms) .
[000113] The addition of biocides during the papermaking process has been known for many years. The presence of microorganisms in the pulp and papermaking process is inevitable, and, therefore, steps are taken to control its growth and numbers. It would be unrealistic to try to kill all microorganisms. Instead, the goal is typically to control, or suppress, the multiplication of microorganisms and thereby restrict their metabolic activities.
[000114] In conventional methods for producing paper, cardboard or cardboard, the composition of mud is one of the most important indicators that microbial growth and microbial activities should be restricted. In conventional methods for the production of paper, cardboard or cardboard, the biocide is typically added for the conventional proposal of preventing the formation of mud, corrosion and / or wet end breaks, controlling the terminal wet deposition, or for odor control, but not for the proposal to avoid microbial degradation of the starch, which is contained in the cellulosic material, by eradicating the microorganisms that are otherwise capable of degrading the starch with the intention of (re) fixing this starch later with polymers as described hereinafter.
[000115] The conventional proposals above require comparatively low amounts of biocides maintaining only relatively small sections of the total antimicrobially controlled papermaking facility. In contrast, the cancellation of starch degradation according to the invention, that is, the partial or total eradication of microorganisms that are capable of degrading starch (amylase control), typically requires substantially higher amounts / concentrations of biocide . As additionally shown in the experimental section, the amount of biocide that is preferably employed according to the invention in order to avoid starch degradation, is at least 2 times, preferably at least 3 times higher than the amount of biocide conventionally employed in papermaking processes for conventional proposal. In addition, the distribution of the biocide which is preferably achieved by dosing the biocide at various feeding points located in various sections of the papermaking facility in the method according to the invention in order to avoid starch degradation in any location is not conventional. For example, according to the product specification of aqueous ammonium bromide compositions currently marketed as a precursor to microbiological control agent for paper production, the recommended dosage ranges from merely 150 - 600 g / t of dry fiber to an active content 35%, which corresponds to a maximum dosage of only 210 g of ammonia bromide per ton of dry fiber. However, by such conventional biocide treatment, that is, by 210 g / t of dry fiber, and without adding additional biocide at additional locations, the starch that is contained in the rest of the papermaking facility is still substantially degraded.
[000116] In a preferred embodiment of the method according to the invention, step (b) involves reducing the content of microorganisms that are contained in the cellulosic material and are able to degrade starch by treating the cellulosic material containing the starch with a sufficient amount of a suitable biocide.
[000117] In another preferred embodiment of the method according to the invention, step (b) involves the partial or total nullification, prevention, suppression or reduction of starch degradation by microorganisms that are contained in the cellulosic material, and which are capable of degrading starch by treating the cellulosic material containing the starch with a sufficient amount of a suitable biocide.
[000118] In another preferred embodiment of the method according to the invention, step (b) involves the partial or total preservation of starch against degradation by microorganisms that are contained in the cellulosic material, and which are able to degrade starch by treatment of the cellulosic material containing the starch with a sufficient amount of a suitable biocide.
[000119] The degradation of the starch contained in the cellulosic material can be monitored by measuring several parameters, for example, pH value, electrical conductivity, ATP (adenosine triphosphate) content, redox potential, and extinction. The microbiological activity needs to be significantly reduced in the total system, compared to conventional biocide treatments. In this way, the effectiveness of a given biocide in a given amount with respect to its effect in preventing starch degradation can be investigated by routine experimentation, that is, by monitoring the pH value, electrical conductivity, ATP content, potential -redox, and / or extinction (iodine test), and comparison of the situation without biocide treatment to the situation with biocide treatment after a sufficient equilibrium period (typically at least 3 days, preferably 1 week, or 1 month).
[000120] A person skilled in the art is fully aware that the papermaking facilities comprise a water circuit to which more or less fresh water is added (open system and closed system, respectively). The cellulosic material is brought into contact with the process water in, or before, the pulping step (a), it is further diluted by the addition of process water when the thick stock is converted into thin stock, and is separated from the stock water. process in the paper making machine where sheet formation occurs. Process water is returned (recycled) through the water circuit in order to reduce the consumption of fresh water. The process water parameters in the water circuit are typically balanced, the balance being influenced by the size of the system, added amount of fresh water, properties of the starting material, nature and quantity of additives, and the like.
[000121] When changing the process conditions according to the invention, for example, by adding higher amounts of biocide in various locations, some parameters change spontaneously locally and reach an equilibrium in the total system within hours or days, for example example, redox potential, ATP level and oxygen reduction potential (ORP), so other parameters typically require more time to balance, for example, pH value and electrical conductivity.
[000122] Typically, unwanted starch degradation leads to a decrease in the pH value of the aqueous cellulosic material. In this way, efficient prevention of starch degradation by eradicating microorganisms due to biocide treatment can be monitored by measuring the pH value of the aqueous phase of the cellulosic material. Preferably, in step (b) of the method according to the invention, the one or more biocides are continuously or discontinuously added to the cellulosic material in such a way that after 1 month of treatment, preferably after two months of treatment in a manufacturing plant of continuously operating paper, the pH value of the aqueous phase of the cellulosic material has been increased by at least 0.2 pH unit, or by at least 0.4 pH unit, or by at least 0.6 pH unit, or at least 0.8 pH units, or at least 1.0 pH units, or at least 1.2 pH units, or at least 1.4 pH units, or at least 1, 6 pH units, or at least 1.8 pH units, or at least 2.0 pH units, or at least 2.2 pH units, or at least 2.4 pH units, compared to the pH value that was measured, preferably at the same location, preferably at the wet end of the papermaking machine immediately before the biocide is added for the first time, or before the addition of higher amounts of biocide than conventionally employed is initiated, that is, compared to a situation where microorganisms were degrading the starch, thereby causing a decrease in the value of pH. Preferably, in step (b) of the method according to the invention, the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that after 1 month of treatment, preferably after two months of treatment in a manufacturing facility of continuously operating paper, the pH value of the aqueous phase of the cellulosic material measured at the wet end entrance of the papermaking machine has been decreased by no more than 2.4 pH units, or by no more than 2.2 pH units, or by not more than 2.0 pH units, or by not more than 1.8 pH units, or by not more than 1.6 pH units, or by not more than 1 , 4 pH unit, or by not more than 1,2 pH unit, or by not more than 1,0 pH unit, or by not more than 0,8 pH unit, or by not more than than 0.6 pH unit, or by not more than 0.4 pH unit, or by not more than 0.2 pH unit, compared to the pH value of a composition o containing the starting material (virgin pulp and recycle pulp, respectively), as well as all additives that were added to the cellulosic material in the corresponding concentrations until it reaches the wet terminal entrance of the papermaking machine.
[000123] Typically, unwanted starch degradation also leads to an increase in electrical conductivity of the aqueous cellulosic material. In this way, efficient prevention of starch degradation by eradicating microorganisms due to biocide treatment, can be monitored by measuring the electrical conductivity of the aqueous phase of the cellulosic material. Preferably, in step (b) of the method according to the invention, the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that after 1 month of treatment, preferably after two months of treatment in a manufacturing facility of paper that operates continuously, the electrical conductivity of the aqueous phase of the cellulosic material has been decreased by at least 5%, or by at least 10%, or by at least 15%, or by at least 20%, or by at least 25% , or by at least 30%, or by at least 35%, or by at least 40%, or by at least 45%, or by at least 50%, or by at least 55%, or by at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, compared to the electrical conductivity that was measured, preferably at the same location, preferably at the wet end entrance of the machine papermaking just before the biocide is added for the first time, or before the addition of higher amounts of biocide than conventionally employed is initiated, that is, compared to a situation where microorganisms were degrading the starch, thereby causing an increase in electrical conductivity. Preferably, in step (b) of the method according to the invention, the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that after 1 month of treatment, preferably after two months of treatment in a manufacturing facility of continuously operating paper, the electrical conductivity of the aqueous phase of the cellulosic material measured at the wet end entrance of the papermaking machine has been increased by at least 80%, or at least 75%, or at least 70%, or at least 60%, or at least 55%, ou at least 50%, or at least 45%, or at least 40%, or at least 30%, or at least 25%, or at least 20%, or at least 15%, or at least 10%, or at least 10%, or at least 5%, compared to the electrical conductivity of a composition containing the starting material (virgin pulp and recycle pulp, respectively), as well as all additives that were added to the cellulosic material in the corresponding concentrations until it reach the wet end entrance of the papermaking machine.
[000124] Preferably, in step (b) of the method according to the invention, the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that, preferably after 1 month of treatment, more preferably after two months of treatment. treatment in a paper-making plant that operates continuously, the electrical conductivity of the aqueous phase of the cellulosic material is at least 7000 μS / cm, or at least 6500 μS / cm, or at least 6000 μS / cm, or at least 5500 μS / cm, or at least 5000 μS / cm, or at least 4500 μS / cm, or at least 4000 μS / cm, or at least 3500 μS / cm, or at least 3000 μS / cm, or at least 2500 μS / cm , or at least 2000 μS / cm, or at least 1500 μS / cm, or at least 1000 μS / cm.
[000125] Typically, unwanted starch degradation also leads to a decrease in extinction when the aqueous cellulosic material is subjected to an iodine test. In this way, efficient prevention of starch degradation by eradicating microorganisms due to biocide treatment can be monitored by measuring the extinction of the starch that is contained in the aqueous phase of the cellulosic material by means of iodine testing. Preferably, in step (b) of the method according to the invention, the one or more biocides are continuously or discontinuously added to the cellulosic material in such a way that after 8 hours, preferably after 2 days, more preferably after 3 days of treatment, more preferably after 1 week of treatment, in a paper-making plant that operates continuously, the extinction of the starch contained in the aqueous phase of the cellulosic material has been increased by at least 5%, or by at least 10%, or by at least 15 %, or by at least 20%, or by at least 25%, or by at least 30%, or by at least 35%, or by at least 40%, or by at least 45%, or by at least 50% , or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, compared to the extinction that was measured, preferably in the same location, preferably at the wet end entrance of the papermaking machine immediately before the biocide is added for the first time, or before the addition of higher amounts of biocide than conventionally employed is initiated, that is, compared to a situation where microorganisms were degrading the starch, thereby causing a extinction decrease. In a preferred embodiment, the extinction of native starch is monitored. This can be done at a particular wavelength (for details, refer to the experimental section). According to the invention, the increase in starch content can be higher. For example, depending on the composition of the starting material, the starch content at the beginning, that is, when the biocide treatment begins, can be about zero.
[000126] In a preferred embodiment, the starch that is contained in the cellulosic material, preferably after the pulping step has been completed, has an average molecular weight of at least 25,000 g / mol.
[000127] In a preferred embodiment, the one or more biocides are dosed in an amount so that after 60 minutes, the microorganism (MO) content in [cfu / mL] in the cellulosic material containing the starch is at least 1 , 0x107, or at least 5.0x106, or at least 1.0x106; or at least 7.5x105, or at least 5.0x105; or at least 2.5x105, or at least 1.0x105, or at least 7.5x104; or at least 5.0x104, or at least 2.5x104, or at least 1.0x104; or at least 7.5x103, or at least 5.0x103, or at least 4.0x103; or at least 3.0x103, or at least 2.0x103, or at least 1.0x103. In another preferred embodiment, the biocide is dosed in an amount so that after 60 minutes, the microorganism (MO) content in [cfu / mL] in the cellulosic material containing the starch is at least 9.0x102, or at least 8.0x102, or at least 7.0x102; or at least 6.0x102, or at least 5.0x102, or at least 4.0x102; or at least 3.0x102, or at least 2.0x102, or at least 1.0x102; or at least 9.0x101, or at least 8.0x101, or at least 7.0x101; or at least 6.0x101, or at least 5.0x101, or at least 4.0x101; or at least 3.0x101, or at least 2.0x101, or at least 1.0x101.
[000128] In a preferred embodiment, the one or more biocides are dosed to the cellulosic material at a feed rate related to the finally produced paper of at least 5 g / metric ton (= 5 ppm), preferably within the range of 10 g / metric ton to 5000 g / metric ton, more preferably from 20 g / metric ton to 4000 g / metric ton, even more preferably from 50 g / metric ton to 3000 g / metric ton, even more preferably from 100 g / metric ton to 2500 g / metric ton, more preferably from 200 g / metric ton to 2250 g / metric ton, and in particular, from 250 g / metric ton to 2000 g / metric ton, based on the paper finally produced.
[000129] In a preferred embodiment, the one or more biocides comprises a two-component system comprising an inorganic ammonium salt and a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt thereof, in which the ratio The molar ratio of inorganic ammonia salt to hypochlorous acid or its salt is within the range of 2: 1 to 1: 2. Under these circumstances, preferably when the starting material of the process according to the invention comprises recycled pulp, said two-component system is preferably dosed to the cellulosic material at a feed rate related to the finally produced paper of at least 175 g / tonne metric, or at least 200 g / metric ton, or at least 250 g / metric ton, or at least 300 g / metric ton; or at least 350 g / metric ton, or at least 400 g / metric ton, or at least 450 g / metric ton, at least 500 g / metric ton, or at least 550 g / metric ton; more preferably at least 600 g / metric ton, or at least 650 g / metric ton, or at least 700 g / metric ton, or at least 750 g / metric ton, or at least 800 g / metric ton, or at least 850 g / metric ton, or at least 900 g / metric ton, or at least 950 g / metric ton, or at least 1000 g / metric ton; or at least 1100 g / metric ton, or at least 1200 g / metric ton, or at least 1300 g / metric ton, or at least 1400 g / metric ton, or at least 1500 g / metric ton; or at least 1750 g / metric ton, or at least 2000 g / metric ton; in each case based on the weight of the inorganic ammonia salt and relative to the paper finally produced. Under these circumstances, preferably when the starting material of the process according to the invention does not comprise recycled pulp, that is, it essentially consists of virgin pulp, said two-component system is preferably dosed to the cellulosic material at a feed rate related to the finally produced paper of either at least 50 g / metric ton, or at least 100 g / metric ton, or at least 150 g / metric ton, or at least 200 g / metric ton, or at least 250 g / metric ton, or at least 300 g / metric ton, or at least 350 g / metric ton, or at least 400 g / metric ton, or at least 450 g / metric ton, or at least 500 g / metric ton, or at least 550 g / metric ton, or at least 600 g / metric ton, or at least 650 g / metric ton; or at least 700 g / metric ton, or at least 750 g / metric ton, or at least 800 g / metric ton, or at least 850 g / metric ton, or at least 900 g / metric ton; or at least 950 g / metric ton, or at least 1000 g / metric ton; in each case based on the weight of the inorganic ammonia salt and relative to the paper finally produced.
[000130] In a preferred embodiment, the one or more biocides are discontinuously added to the cellulosic material in a papermaking facility that operates continuously. The one or more biocides are preferably added by means of pulsed feed rates, that is, peaks in the local concentration of the biocide in the cellulosic material reaching the critical local concentration that is necessary in order to eradicate microorganisms, thereby preventing effectively, the starch from being degraded. In other words, the cellulosic material that passes through the biocide feed point (s) is transiently locally enriched by biocide at predetermined intervals (biocide intervals), which are interrupted at intervals during which no biocide is added locally ( passive intervals).
[000131] Preferably, a biocide interval typically lasts at least about 2 minutes, but it can also last, for example, up to about 120 minutes. Preferably, the biocide is added to the cellulosic material in a papermaking facility that operates continuously for 24 h through at least 4, 8, 12, 16, 20, 30, 40, 50, 60, 70 or more biocides that are separated from each other by a respective number of passive intervals, in which during each biocide interval, the desired and predetermined local concentration of the biocide in the cellulosic material is achieved.
[000132] In another preferred embodiment, the one or more biocides are continuously added to the cellulosic material in a papermaking facility that operates continuously.
[000133] Preferably, the biocide is added to the cellulosic material at at least two feeding points, which are located downstream from each other. For example, the biocide is added at a first feed point and at a second feed point being located downstream from the first feed point. Depending on the half-life and distribution of the biocide in the cellulosic material, the cellulosic material that passes through the second feed point may already contain biocide that has been added to it at the first feed point. In this way, the amount of biocide locally added at the second feed point may be lower than the amount locally added at the first feed point in order to achieve the same desired and predetermined local concentration of the biocide in the cellulosic material that is needed so. to eradicate microorganisms, thereby effectively preventing starch from being degraded.
[000134] Preferably, biocide, more preferably a two-component oxidizing biocide, is added in section (I) and / or (II); and optionally also in section (III) and / or (IV) of the papermaking facility; more preferably in section (I) and / or (II); as well as in section (IV) of a papermaking facility comprising a papermaking machine, in which section (I) includes measurements that occur before pulping; section (II) includes measures associated with pulping; section (III) includes measures that occur after pulping, but still outside the papermaking machine; and section (IV) includes measurements that occur within the papermaking machine.
[000135] In a preferred embodiment, particularly when the biocide is oxidizing, for example, a two component system comprising an ammonia salt and a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt thereof. , biocide is dosed to the cellulosic material at a concentration of active substance that is equivalent to elemental chlorine at a concentration within the range of 0.005 to 0.500% of active substance such as Cl2 per ton of paper produced, more preferably from 0.010 to 0.500% of substance active as Cl2 per ton of paper produced, even more preferably from 0.020 to 0.500% of active substance as Cl2 per ton of paper produced, even more preferably from 0.030 to 0.500% of active substance as Cl2 per ton of paper produced, more preferably- 0.040 to 0.500%, and in particular 0.050 to 0.500% of active substance such as Cl2 per ton of paper produced.
[000136] In another preferred embodiment, particularly when the biocide is oxidizing, for example, a two component system comprising an ammonia salt and a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt thereof. , the biocide is dosed to the cellulosic material at a concentration of active substance that is equivalent to elemental chlorine at a concentration within the range of 0.005 to 0.100% of active substance such as Cl2 per ton of paper produced, more preferably from 0.010 to 0.100% of active substance like Cl2 per ton of paper produced, even more preferably from 0.020 to 0.100% of active substance like Cl2 per ton of paper produced, even more preferably from 0.030 to 0.100% of active substance like Cl2 per ton of paper produced, more preferably from 0.040 to 0.100% of active substance as Cl2 per ton of paper produced, and, in particular, from 0.050 to 0.100% of active substance as Cl2 per ton of paper produced.
[000137] In yet another preferred embodiment, particularly when the biocide is oxidizing, for example, a two-component system comprising an ammonia salt and a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt thereof, the biocide is dosed to the cellulosic material at a concentration of active substance that is equivalent to elemental chlorine at a concentration within the range of 0.010 to 0.080% of active substance as Cl2 per ton of paper produced, more preferably from 0.015 to 0.080% of substance active as Cl2 per ton of paper produced, even more preferably from 0.020 to 0.080% of active substance as Cl2 per ton of paper produced, even more preferably from 0.030 to 0.080%, more preferably from 0.040 to 0.080% of active substance as Cl2 per ton of paper produced, and, in particular, from 0.050 to 0.080% of active substance such as Cl2 per ton of paper produced.
[000138] Concentrations above the biocide are expressed as equivalent concentrations of elemental chlorine. The determination of the concentration of a biocide (based on the active substance) that is equivalent to a particular concentration of elemental chlorine is known to the person skilled in the art.
[000139] The particularly preferred embodiments A1 to A6 concerning the biocide added in step (b) of the method according to the invention (first biocide) and the additional organic biocide (additional biocide) are summarized in Table 1 here below: Table 1:
in which sections (I) to (IV) refer to the sections of a papermaking facility comprising a papermaking machine, in which section (I) includes measurements that occur prior to pulping; section (II) includes measures associated with pulping; section (III) includes measures that occur after pulping, but still outside the papermaking machine; and section (IV) includes measurements that occur within the papermaking machine.
[000140] In a preferred embodiment, the stock consistency of cellulosic material in the pulping step (a) is within the range of 3.0 to 6.0%, or 3.3 to 5.5%, or 3 , 6 to 5.1%, or 3.9 to 4.8%, or 4.2 to 4.6%. In another preferred embodiment, the consistency of the stock of cellulosic material in the pulping step (a) is within the range of 10 to 25%, or 12 to 23%, or 13 to 22%, or 14 to 21%, or 15 to 20%. Suitable methods for measuring the consistency of the stock of cellulosic materials are known to the person skilled in the art. In this regard, it may refer to, for example, M.H. Waller, Measurement and Control of Paper Stock Consistency, Instrumentation Systems &, 1983; H. Holik, Handbook of Paper and Board, Wiley-VCH, 2006.
[000141] Preferably, the redox potential of the cellulosic material is increased by adding the biocide to a value within the range of -500 mV to +500 mV, or from -150 mV to +500 mV, or from -450 mV to +450 mV , or from -100 mV to +450 mV, or from -50 mV to +400 mV, or from -25 mV to +350 mV, or from 0 mV to +300 mV. For example, before the biocide is added, the redox potential of the cellulosic material can be -400 mV, and after adding the biocide, it is increased to a value, for example, -100 mV to +200 mV.
[000142] A positive value of the redox potential indicates an oxidative system, so a negative redox potential indicates a reductive system. Suitable methods for measuring the redox potential are known to the person skilled in the art. In this regard, one can refer, for example, to H. Holik, Handbook of Paper and Board, Wiley-VCH, 2006.
[000143] Preferably, the level of the ATP (adenosine triphosphate) of the cellulosic material, expressed in RLU (relative light units), decreases by the addition of biocide to a value within the range of 500 to 400,000 RLU, or from 600 to 350,000 RLU, or from 750 to 300,000 RLU, or from 1,000 to 200,000 RLU, or from 5,000 to 100,000 RLU. For example, before the biocide is added, the ATP level can exceed 400,000 RLU, and after adding the biocide, it is increased to a value of, for example, 5,000 to 100,000 RLU. In a preferred embodiment, the level of ATP (adenosine triphosphate) of the cellulosic material, expressed in RLU (relative light units), decreases by adding biocide to a value within the range of 5000 to 500,000 RLU, more preferably 5000 to 25,000 RLU .
[000144] ATP detection using bioluminescence provides another method for determining the level of microbial contamination. Suitable methods for detecting ATP using bioluminescence are known to those skilled in the art.
[000145] The pulping step (a) can be performed at ambient conditions.
[000146] In a preferred embodiment, the pulping step (a) is carried out at elevated temperature. Preferably, the pulping step (a) is carried out at an elevated temperature within the range of 20 ° C to 90 ° C, more preferably from 20 ° C to 50 ° C.
[000147] In a preferred embodiment, the pulping step (a) is carried out at a pH value of 5 to 13, or from 5 to 12, or from 6 to 11, or from 6 to 10, or from 7 to 9 The desired pH value can be adjusted by adding acids and bases, respectively.
[000148] In a preferred embodiment according to the invention, the pulping step (a) is carried out in the presence of one or more additional biocides and auxiliaries. Such additional auxiliaries comprise, but are not limited to, inorganic materials, such as talc, or other additives.
[000149] Typically, the pulped cellulosic material containing the starch (not degraded), that is, virgin pulp, recycle pulp, or mixing pulp, can be subjected to additional process steps all of which are involved by section (III) of the method for the production of paper, cardboard or cardboard, which follows the pulping step (a) of section (II). These steps may comprise, but are not limited to (c) removing paint from the cellulosic material; and / or (d) mixing the cellulosic material; and / or (e) bleaching of cellulosic material; and / or (f) refining the cellulosic material; and / or (g) screening and / or cleaning the cellulosic material in the thick stock area; and / or (h) adding (h1) an ionic polymer, preferably a cationic polymer or anionic polymer, and preferably (h2) an auxiliary ionic polymer, preferably cationic polymer, to the cellulosic material, preferably in the thick stock area, that is it is, to the thick stock, where the cellulosic material preferably has a stock consistency of at least 2.0%; or preferably in the thin stock area, that is, in the thin stock, where the cellulosic material preferably has a stock consistency of less than 2.0%; in which the ionic polymer and the optionally added auxiliary ionic polymer preferably has a different average molecular weight and, preferably, a different ionicity, in which ionicity is the molar content of ionic monomer units relative to the total number of monomer units; and / or (i) screening and / or cleaning the cellulosic material in the thin stock area, that is, after diluting the thick stock in a thin stock.
[000150] In this regard, it should be emphasized that steps (c) to (g) and (i) mentioned above are optional only, meaning that any one, any two, any three or any four of steps (c) a (g ) and (i) can be omitted. It is also possible that the six steps (c) to (g) and (i) are omitted during the papermaking process. According to the invention, step (b), the treatment of the cellulosic material containing the starch with one or more biocides, is mandatory, and can be carried out, either during the pulping step (a) and / or after the step of pulping (a). Provided that step (b), the treatment of the cellulosic material containing the starch with one or more biocides, is at least partially carried out after the pulping step (a), it can either be carried out before step (c), or at any time during steps (c) to (g) mentioned above. Preferably, however, step (b) is carried out before the cellulosic material containing the starch is diluted from a thick stock (being processed in the thick stock area) to a thin stock (being further processed in the thin stock area), i.e. , before step (i).
[000151] Devices that are suitable for the subsequent steps after the pulping step (a) are known to the person skilled in the art. For example, the cellulosic material containing the starch (not degraded) can be pumped from the pulper into a stock barrel, a mixing barrel and / or a machine barrel before it is delivered to the papermaking machine (ie , the so-called "constant part" of the paper-making machine).
[000152] The time sequence of steps (c) to (g) can be freely chosen, meaning that the time sequence of steps (c) to (g) does not necessarily follow the alphabetical order as indicated. Preferably, however, the order is alphabetical.
[000153] Additional process steps, such as storing cellulosic material in storage tanks or additional washing and / or sieving steps, can be incorporated after any of the process steps (a) to (g).
[000154] In a preferred embodiment, the time sequence of the process steps is selected from the group consisting of (a) ^ (g); (a) ^ (c) ^ (g); (a) ^ (d) ^ (g); (aHθHg); (a) ^ (f) ^ (g); (a) ^ (c) ^ (d) ^ (g); (a) ^ (c) ^ (e) ^ (g); (a) ^ (c) ^ (f) ^ (g); (a) ^ (d) ^ (e) ^ (g); (a) ^ (d) ^ (f) ^ (g); (a) ^ (e) ^ (f) ^ (g); (a) ^ (c) ^ (d) ^ (e) ^ (g); (aH (cH (dH (f) ^ (g); (aH (cH (eH (fH (g); (a) ^ (d) ^ (e) ^ (f) ^ (g); e (a) ^ (c) ^ (d) ^ (e) ^ (f) ^ (g); in which, for the purpose of the specification, the symbol "^" means "followed by"; and additional process steps, such as storage of cellulosic material in storage tanks, or additional washing and / or sieving steps can be incorporated after any of the process steps (a) to (g). Step (b), the treatment of the cellulosic material containing the starch with the biocide it can also be incorporated after any of the process steps (a) to (g).
[000155] At least part of the biocide is preferably added during the pulping step (a), or shortly thereafter. Provided that the biocide that was initially added during the pulping step (a) is not completely removed or consumed in subsequent steps, the biocide is also present in process steps (c), (d), (e), (f) and (g), if any, which follows the pulping step (a).
[000156] In a preferred embodiment, at least a part of the remainder of the total amount (total internal flow) of the biocide is added to the cellulosic material during any of the steps (c), (d), (e), (f) and / or (g). For example, 50% by weight of the total amount (total internal flow) of the biocide can be added continuously or discontinuously, before and / or during the pulping step (a), and the remaining 50% by weight of the total amount (flow) total internal) of the biocide can be added continuously or discontinuously, before, during and / or after the process steps (c), (d), (e), (f) and / or (g).
[000157] A person skilled in the art is aware that after each of the process steps (a) to (g), the mixture comprising the cellulosic material and the biocide can be supplied to the storage tanks, before it is reintroduced in the additional steps of papermaking process.
[000158] It is also apparent to a person skilled in the art that at least a part of the remainder of the total amount (total internal flow) of the biocide can be added to the cellulosic material, when it is stored in storage tanks after any of the process steps ( a), (c), (d), (e), (f) and (g).
[000159] In general, the pulping step (a) is carried out before the cellulosic material containing the starch (not degraded) enters the paper-making machine. In a preferred embodiment, at least a part of the biocide is added to the water used for pulping before or during the pulping step for the cellulosic material, that is, for the virgin material, recycle material, or mixing material. Said addition preferably occurs at least 5 minutes, or at least 10 minutes, or at least 20 minutes, or at least 30 minutes, or at least 40 minutes before the cellulosic material is supplied to the wet end of the papermaking machine, for example , through flow box.
[000160] In a preferred embodiment, said addition preferably occurs at least 360 minutes, or at least 300 minutes, or at least 240 minutes, or at least 180 minutes, or at least 120 minutes, or at least 60 minutes before the cellulosic material be supplied to the wet end of the papermaking machine, for example, through a flow box.
[000161] Preferably, the period of time during which the cellulosic material is in contact with the biocide is within the range of 10 minutes to 3 days.
[000162] In a preferred embodiment of the method according to the invention, the period of time during which the cellulosic material is in contact with the biocide is at least 10 minutes, or at least 30 minutes, or at least 60 minutes, or at least 80 minutes, or at least 120 minutes.
[000163] In a preferred embodiment of the method according to the invention, the period of time during which the cellulosic material is in contact with the biocide is preferably within the range of 12 ± 10 hours, or 24 ± 10 hours, or 48 ± 12 hours, or 72 ± 12.
[000164] The duration of the pulping step (a) is not critical to the invention. After the pulping step, the pulp according to the invention can be subjected to an ink removal step (c), in which the virgin pulp, recycle pulp, or mixing pulp is preferably devoid of ink in the presence of the biocide.
[000165] After the pulping step, the pulp, according to the invention, can be subjected to a mixing step (d). Mixture (d), also referred to as stock preparation, is typically carried out in a so-called mixing box, that is, a reaction vessel in which additives, such as dyes, fillers (for example, talc or clay), and dimensioning agents (for example, rosin, wax, additional starch, glue) are added to the pulped cellulosic material, preferably to the virgin pulp, recycle pulp, or mixing pulp, preferably in the presence of the biocide. Loads are preferably added to improve printing properties, smoothness, gloss, and opacity. Sizing agents typically improve the water resistance and printability of the final paper, cardboard and / or cardboard. The sizing can also be performed on the papermaking machine, by superficial application on the sheet.
[000166] After the pulping step, the pulp, according to the invention, can be subjected to a bleaching step (e). Typically, bleaching (e) is performed to bleach pulped cellulosic material, preferably in the presence of the biocide. In said bleaching process, chemical bleaches, such as hydrogen peroxide, sodium bisulfite or sodium hydrosulfite, are typically added to the pulped cellulosic material to remove the color.
[000167] After the pulping step, the pulp, according to the invention, can be subjected to a refining step (f). The refine (f) is preferably carried out in a so-called pulp shaker or refiner by fibrillation of the fibers of the cellulosic material, preferably in the presence of the biocide. The proposal is preferably to brush and raise the fibrils from the fiber surfaces to better bond with each other during sheet formation resulting in stronger paper. Process batches in pulp agitators (eg Hollander agitator, Jones-Bertram agitator, etc.) of pulp, while refiners (eg Chaflin refiner, Jordan refiner, single or double disc refiners, etc.) process the pulp continuously.
[000168] After the pulping step, the pulp, according to the invention, can be subjected to a sieving step (g). The sieve (g) is preferably applied to remove unwanted fibrous and non-fibrous material from the cellulosic material, preferably in the presence of the biocide, preferably by the use of rotating screens and centrifugal cleaners.
[000169] Before the cellulosic material enters the papermaking machine, the cellulosic material that is present as a "thick stock" is diluted with water to "thin the stock". After dilution, the pulp, according to the invention, can be subjected to an additional sieving and / or cleaning step (i).
[000170] Then, typically near the end of the papermaking process, the cellulosic material is supplied to a papermaking machine, where it typically enters the wet end of the papermaking machine.
[000171] This is where section (IV) of the total method for the production of paper, cardboard or cardboard, begins.
[000172] For the purpose of the specification, the term "papermaking machine" preferably refers to any device or component thereof that basically serves to form sheets from an aqueous suspension of the cellulosic material. For example, the pulper is not to be listed as a component of the papermaking machine.
[000173] Typically, the papermaking machine has a wet end comprising a connecting section and a press section, and a dry end comprising a first drying section, a size press, a second drying section, a calender, and "jumbo" spools.
[000174] The first section of the wet end of the papermaking machine is typically the binding section, where cellulosic material is supplied through a flow box to the binding section, and evenly distributed over the entire width of the papermaking machine. papermaking, and a significant amount of water from the aqueous dispersion or aqueous suspension of the cellulosic material is drained. The bonding section, also called the forming section, can comprise a layer or multi-layer, in which multi preferably means 2, 3, 4, 5, 6, 7, 8 or 9 layers (folds). Subsequently, the cellulosic material preferably enters the press section of the papermaking machine where the remaining water is squeezed out of the cellulosic material, which forms a web of cellulosic material, which then in turn is preferably supplied to the dry end of the paper-making machine.
[000175] The so-called dry end of the papermaking machine preferably comprises a first drying section, optionally a size press, a second drying section, a calender, and "jumbo" spools. The first and second drying sections preferably comprise a number of heat-heated drying cylinders, where synthetic drying fabrics can carry the cellulosic material web around the cylinders until the cellulosic web has a water content of approximately 4 to 12%. An aqueous solution of starch can be added to the surface of the cellulosic material web in order to optimize the surface for the printing proposal, or for strength properties. Preferably, the web of cellulosic material is then subjected to a calender, where it is smoothed and polished. Subsequently, the cellulosic material is typically wrapped in the so-called "jumbo" spool section.
[000176] In a preferred embodiment, the method according to the invention is carried out in a papermaking facility that can be related to having an open water supply, and thus an open water circuit. Paper-making facilities of this type are typically characterized by an effluent installation, that is, by an effluent stream through which an aqueous composition is continuously removed from the system.
[000177] In another preferred embodiment, the method according to the invention is carried out in a papermaking facility that can be related as having a closed water recycling loop. Paper-making facilities of this type are typically characterized by not retaining any effluent installation, that is, there is no effluent stream through which an aqueous composition is continuously removed from the system, while the paper, of course, contains some moisture residual. All papermaking facilities (closed and open systems) typically allow water (gaseous) to evaporate, so closed systems do not allow liquid effluent currents. It has been surprisingly found that the method according to the invention is of particular advantage in such a closed recycling loop of water. Without the method according to the invention, the starch in the liquid phase would concentrate from the recycle step to the recycle step, and finally end up in a highly viscous pasty composition not useful for any paper production. By means of the method according to the invention, however, the starch is fixed, preferably fixed to the fibers, thereby avoiding any concentration effect from the recycling step to the recycling step.
[000178] In a preferred embodiment, at least 50% by weight of the biocide that is present during step (b), is still present when the cellulosic material containing the starch (not degraded) enters the wet end of the papermaking machine . In the event that the loss of biocide during the papermaking process is very high, additional parts of the biocide can be added during any of the process steps (c), (d), (e), (f) and / or ( g).
[000179] In another preferred embodiment, at least 50% by weight of the biocide, which is present during step (b), is still present when the cellulosic material containing the (non-degraded) starch enters the papermaking machine.
[000180] An additional one or two component biocide (additional biocide) that differs in nature from the biocide of step (b) (first biocide), can also be added to the cellulosic material containing the starch (not degraded) before, during or after process steps (c) to (g) and / or after the cellulosic material has been supplied to the papermaking machine.
[000181] Provided that the biocide that was added during step (b) and, optionally, in process steps (c), (d), (e), (f), and (g), if any, which follows the pulping step (a), is not completely removed in the subsequent steps, said biocide is also present in the papermaking machine.
[000182] In a preferred embodiment, at least part of the remainder of the total amount (total internal flow) of the biocide (first biocide), and / or another biocide (additional biocide), is added to the cellulosic material subsequent to any of the steps ( c), (d), (e), (f) and / or (g), that is, in the paper-making machine. For example, 50% by weight of the total amount (total internal flow) of the first biocide, can be added discontinuously or continuously before, and / or during, the pulping step (a), and / or after the process steps ( c), (d), (e), (f) and / or (g), and the remaining 50% by weight of the total amount (total internal flow) of the first biocide, can be added discontinuously or continuously, in the papermaking.
[000183] In a preferred embodiment, the additional biocide (i.e., another portion of the first biocide and / or an additional biocide differing in nature from the first biocide) is added to the cellulosic material containing the (non-degraded) starch at the wet end of the machine paper making process, preferably in the connecting section. In a preferred embodiment, said additional biocide is added in the machine box or mixing box, or in the regulation box, or in a constant part of the papermaking machine. In a preferred embodiment, at least a portion of said additional biocide is added to one or more water streams from the papermaking facility selected from the group consisting of pulper dilution water, white water (such as white water 1 and / or white water 2), clear shower water, clear filtrate, and clarification admission. In addition, at least a portion of said biocide additional to the pulper dilution water is particularly preferred.
[000184] According to the invention, step (h) comprises the addition of an ionic polymer, preferably a cationic polymer and, preferably, an auxiliary ionic polymer, preferably an auxiliary cationic polymer, preferably to a thick stock of the material cellulosic, preferably having a stock consistency of at least 2.0%; or to a thin stock of cellulosic material, preferably having a stock consistency of less than 2.0%; in which the ionic polymer and the optionally present auxiliary ionic polymer preferably have a different average molecular weight and, preferably, a different ionicity, in which ionicity is the molar content of ionic monomer units relative to the total amount of monomer units.
[000185] The ionic polymer and the auxiliary ionic polymer, according to the invention, differ from each other. If the ionic polymer and the auxiliary ionic polymer are derived from the same monomer units, both polymers are further characterized by the characteristics according to which a person skilled in the art can clearly recognize that the two polymers differ from each other, taking into account account the statistical nature of many polymerization reactions, for example, due to significantly different average molecular weight weights, and / or significantly different cationicity.
[000186] As the ionic polymer and the optionally present auxiliary ionic polymer preferably have a different ionicity, in which the ionicity is the molar content of ionic monomer units relative to the total amount of monomer units, at least one of the polymers is a copolymer comprising ionic monomer units, as well as non-ionic monomer units. In a preferred embodiment, the ionic polymer is a homopolymer of ionic monomer units and the auxiliary ionic polymer is a copolymer comprising ionic monomer units and nonionic monomer units. In another preferred embodiment, the ionic polymer is a copolymer comprising ionic monomer units and non-ionic monomer units, and the auxiliary ionic polymer is a homopolymer of ionic monomer units. In yet another embodiment, the ionic polymer, as well as the auxiliary ionic polymer, is a copolymer each comprising units of ionic monomer and units of nonionic monomer.
[000187] Preferably, step (h) comprises substeps (h1) adding an ionic polymer, preferably a cationic polymer to the cellulosic material, preferably in the thick stock area, where the cellulosic material preferably has a stock consistency of at least 2.0%, or preferably in the thin stock area, where the cellulosic material preferably has a stock consistency of less than 2.0%; and, (h2) preferably, adding an auxiliary ionic polymer, preferably cationic polymer, to the cellulosic material, preferably in the thick stock area where the cellulosic material preferably has a stock consistency of at least 2.0%, or preferably in the thin stock area, where the cellulosic material preferably has a stock consistency of less than 2.0% by weight; in which the ionic polymer and the auxiliary ionic polymer preferably have a different average molecular weight and, preferably, a different ionicity, in which ionicity is the molar content of ionic monomer units relative to the total number of monomer units.
[000188] The substep (h1) can be performed before the substep (h2), simultaneously with the substep (h2), or after the substep (h2). Any partial overlap is also possible. In a preferred embodiment, step (b) is performed at least partially before substeps (h1) and (h2), and substep (h2), in turn, is preferably performed at least partially before substep (h1). In other words, preferably a feed point for at least part of the total amount of biocide that is added in step (b) is located in the upstream papermaking facility with respect to the feed points for the ionic polymer and the polymer auxiliary ionic, and a feed point for at least part of the total amount of auxiliary ionic polymer that is added in step (h2) is located in the upstream papermaking facility with respect to the feed point for the ionic polymer added in substep (h1).
[000189] A person skilled in the art recognizes that the ionic polymer and the auxiliary ionic polymer can, independently of each other, be directly added to a location of the installation, that is, the total installation for processing cellulosic material, where thick stock is processed as such, and where the thin stock is processed as such, respectively. In this regard, direct addition may mean adding a solid or liquid material containing the polymer to the stock. One skilled in the art also recognizes that alternatively, the polymer can be added to a location in that facility where no stock is processed as such, but where another solid, liquid or gaseous material is processed which, in turn, is subsequently added to the stock , that is, mixed with thick stock or thin stock (indirect addition). In this regard, indirect addition can also mean adding a solid or liquid material containing the polymer to the other solid, liquid or gaseous material which, in turn, is subsequently added to the thick stock and the thin stock, respectively.
[000190] A proposal to add the ionic polymer, preferably cationic polymer and the optionally added auxiliary ionic polymer, preferably cationic polymer, is fixation, preferably re-fixation of non-ionic (non-degraded) starch, preferably non-ionic (non-degraded) starch , anionic, cationic and / or native, particularly nonionic, anionic and / or native starch, to cellulosic fibers, thereby preferably reducing the starch content in white water.
[000191] Cationic polymers are particularly useful for fixing nonionic, native, zwitterionic or anionic starches, while anionic polymers are particularly useful for fixing nonionic, native, zwitterionic or cationic starches.
[000192] The ionic polymer, preferably cationic polymer and auxiliary ionic polymer, preferably cationic polymer, can independently be added to the cellulosic material containing the starch at any stage of paper production in the thick stock area, in pulping or after pulping; or at any stage of paper production in the thin stock area. It is apparent to a person skilled in the art that at least a part of the total amount (total internal flow) of the polymer can be added to the cellulosic material, i.e., virgin material, recycle material, or mixing material, during or after the step pulping (a).
[000193] For the purpose of the specification, the term "thick stock area" refers to any paper production stage where cellulosic material is present as "thick stock". Similarly, the term "thin stock area" refers to any stage of paper production where cellulosic material is present as thin stock. Typically, the thick stock is processed in any conventional process steps for the production of paper or cardboard that occurs before step (i). The terms "thick stock" and "thin stock" are known to the person skilled in the art. Typically, in the papermaking machine, the thick stock is diluted before step (i), thereby producing thin stock. For the purpose of the specification, "thick stock" preferably has a solids content (= stock consistency) of at least 2.0% by weight, preferably at least 2.1% by weight, more preferably at least 2.2 % by weight, even more preferably at least 2.3% by weight, even more preferably at least 2.4% by weight, and, more preferably, at least 2.5% by weight. Thus, for the purpose of the specification, cellulosic material having the solids content above is preferably to be listed as thick stock, so cellulosic material having a lower solids content is to be listed as thin stock.
[000194] In a preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer are, independently of each other, added to the cellulosic material containing the (non-degraded) starch during any of the steps, (a), (c), (d ), (e), (f) or (g), that is, before the cellulosic material containing the (non-degraded) starch is diluted to a "thin stock", and before the cellulosic material containing the (non-degraded) starch enters in the paper-making machine. If the method according to the invention comprises one or more of steps (c) to (g), this does not mean that step (h) and its substeps (h1) and (h2), respectively, are carried out in alphabetical order, that is, after all other steps. Preferably, for example, it is possible that after step (a), the ionic polymer is added in step (h1), and that then any of steps (c) to (g) is performed, followed by the addition of the polymer auxiliary ion in step (h2). Preferably, however, the steps of the method according to the invention are carried out in alphabetical order.
[000195] In a preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer are added to the cellulosic material containing the starch before the biocide is added to the cellulosic material containing the starch.
[000196] In this particular, at least a part of the total amount (total internal flow) of the ionic polymer and / or the auxiliary ionic polymer can be added directly at the beginning of the pulping step, that is, directly after the virgin material, recycle, or mixing material, to be supplied to the pulper. Additionally, at least a part of the ionic polymer and / or the auxiliary ionic polymer can be added to the cellulosic material at any time during the pulping step, that is, after the pulping has started, but before the recovery of the pulped cellulosic material from of the pulper. When pulping is carried out continuously, the ionic polymer and / or the auxiliary ionic polymer can be added continuously as well.
[000197] In another preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer is added to the cellulosic material containing the starch after the biocide has been added. It is also possible that the biocide and the ionic polymer and / or the auxiliary ionic polymer are added simultaneously to the cellulosic material containing the starch. In addition, it is possible that a first part of the ionic polymer and / or the auxiliary ionic polymer is added to the cellulosic material containing the starch before a first part of the biocide is added, and subsequently a second part of the ionic polymer and / or the ionic polymer auxiliary be added, or vice versa.
[000198] In another preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer is added before or subsequently with the biocide during the pulping step (a).
[000199] In a preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer is added to the cellulosic material containing the starch after the pulping step has been completed.
[000200] It is apparent to a person skilled in the art that the amount (internal flow) of ionic polymer and / or auxiliary ionic polymer can be added continuously (uninterruptedly) or discontinuously (interruptedly) with respect to a supply point. In addition, the total amount (total internal flow) of polymer can be divided into at least two parts, of which at least one part is continuously or discontinuously added to the cellulosic material containing the starch during or after the pulping step (a), and the other part is continuously or discontinuously added anywhere, that is, at one or more other feeding points.
[000201] In a preferred embodiment, the total amount (total internal flow) of ionic polymer and / or auxiliary ionic polymer is added to the cellulosic material during the pulping step (a) continuously or discontinuously, that is, 100% by weight of the total amount (total internal flow) of the ionic polymer and / or the auxiliary ionic polymer is added to the cellulosic material, that is, to the virgin material, recycle material, or mixing material, during or after the pulping step (a) .
[000202] Provided that the ionic polymer and / or the auxiliary ionic polymer that was added during step (a) and, optionally, in process steps (c), (d), (e), (f) and (g ), if any, which follows the pulping step (a), is not completely removed in the subsequent steps, the ionic polymer and / or the auxiliary ionic polymer are also present in the papermaking machine.
[000203] In a preferred embodiment, at least a part of the remainder of the total amount (total internal flow) of the ionic polymer and / or the auxiliary ionic polymer is added to the subsequent cellulosic material at any of the steps (c), (d ), (e), (f) and / or (g). For example, 50% by weight of the total amount (total internal flow) of the ionic polymer and / or the auxiliary ionic polymer can be added continuously or discontinuously, during the pulping step (a), and the remaining 50% by weight of the total amount (total internal flow) of the ionic polymer and / or the auxiliary ionic polymer can be added continuously or discontinuously, in any other processing step, for example, within the thick stock area.
[000204] In a preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer is added in the machine box or mixing box, or in the regulation box. In a preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer is added to the intake of the machine housing.
[000205] According to the method of the invention, the addition of the ionic polymer and optionally added auxiliary ionic polymer to the cellulosic material, serves the proposal of (re-) fixing the starch to the cellulose fibers of the cellulose material, thereby reducing thus substantially the content of free starch (i.e., unbound or dissolved or dispersed starch) in the cellulosic material. In this regard, for the proposal of the specification, "(re-) fixation" of starch can mean both refixation of undegraded starch and / or fixation of starch recently added to cellulose fibers.
[000206] (Re-) starch fixation to cellulose fibers leads to a decrease in extinction when subjecting the aqueous phase of the cellulosic material to an iodine test. In this way, efficient (re-) fixation of starch by means of the ionic polymer and / or the auxiliary ionic polymer can be monitored by measuring the extinction of the starch that is contained in the aqueous phase of the cellulosic material by means of the iodine test.
[000207] Preferably, in step (h) of the method according to the invention, the ionic polymer and / or the auxiliary ionic polymer, independently of each other, is continuously or discontinuously added to the cellulosic material in quantities so that after 3 treatment days, preferably after 1 week of treatment in a paper-making plant that operates continuously, the extinction of the starch contained in the aqueous phase of the cellulosic material has been reduced by at least 5%, or by at least 10%, or by at least at least 15%, or by at least 20%, or by at least 25%, or by at least 30%, or by at least 35%, or by at least 40%, or by at least 45%, or by at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, compared to the extinction that was measured, preferably in the same location, preferably at the wet end entrance of the papermaking machine immediately at before the polymer is added for the first time, or before the addition of higher amounts of biocide than conventionally employed is initiated, that is, compared to a situation where micro-organisms had been prevented from degrading the starch by means of the biocide added in the step (b), but in the absence of ionic polymer and / or auxiliary ionic polymer. In a preferred embodiment, the extinction of native starch is monitored. This can be done at a particular wavelength, typically at 550 nm (for details, refer to the experimental section).
[000208] Thus, according to the content of free starch in the aqueous phase of the cellulosic material, the steps (b) and (h) of the method according to the invention have opposite effects: While step (b) prevents the starch from being degraded by microorganisms and thereby increases the free starch content, step (h) causes (re-) fixation, that is, starch deposition and thereby decreases the free starch content. These opposite effects of the method according to the invention can easily be demonstrated by experiments where a conventional, balanced method for producing paper, cardboard or cardboard, is first modified by step (b) only, thereby leading to a substantial increase in the free starch content in the aqueous phase of the cellulosic material (which can be monitored, for example, by the iodine test), and then, once the method thus modified has been balanced, secondly, additionally modifying the method as well step (h), thereby leading to a substantial decrease in the free starch content in the aqueous phase of the cellulosic material (which can also be monitored, for example, by the iodine test).
[000209] As the starch is (re-) attached to cellulose fibers, the strength of paper, cardboard or cardboard is increased. Thus, another aspect of the invention relates to a method for increasing the strength of paper, cardboard or cardboard, comprising the method for producing paper, cardboard or cardboard, according to the invention.
[000210] Additionally, as the starch is (re-) attached to the cellulose fibers, the drainage and / or production rate of the papermaking machine can be increased. Thus, another aspect of the invention relates to a method for increasing the drainage and / or production rate of the papermaking machine, comprising the method for producing paper, cardboard or cardboard, according to the invention.
[000211] Still additionally, as the starch is (re-) fixed to the cellulose fibers, the COD effluent in the papermaking process can be reduced. Thus, another aspect of the invention relates to a method for reducing effluent COD in the papermaking process comprising the method for producing paper, cardboard or cardboard, according to the invention.
[000212] In a preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer, independently of each other, is dosed to the cellulosic material containing the starch during or after the pulping step (a) at a final concentration of at least 50 g / metric ton, or at least 100 g / metric ton, or at least 250 g / metric ton, or at least 500 g / metric ton, or at least 750 g / metric ton, or at least 1,000 g / metric ton, or at least 1,250 g / metric ton, or at least 1,500 g / metric ton, in which metric tons are preferably based on the total composition containing the cellulosic material, and the grams are preferably based on the ionic polymer as such (active content) . More preferably, the ionic polymer, preferably cationic polymer, is dosed to the cellulosic material during or after the pulping step (a) at a final concentration of 100 to 2,500 g / metric ton, or 200 to 2,250 g / metric ton, or from 250 to 2,000 g / metric ton, or from 300 to 1,000 g / metric ton, in which metric tons are preferably based on the total composition containing the cellulosic material, and the grams are preferably based on the ionic polymer and the ionic polymer auxiliary, respectively, as such (active content).
[000213] In a preferred embodiment, preferably when the ionic polymer and / or the ionic auxiliary polymer is employed in the solid state, for example, as a granular material, the ionic polymer and / or the ionic auxiliary polymer, independently of each other, is dosed to cellulosic material at a concentration of 1,500 ± 750 g / metric ton, or 1,500 ± 500g / metric ton, or 1,500 ± 400 g / metric ton, or 1,500 ± 300g / metric ton, or 1,500 ± 200 g / metric ton, or1. 500 ± 100g / metric ton, based on the total composition containing the cellulosic material. In another preferred embodiment, preferably when the ionic polymer and / or the auxiliary ionic polymer, independently of each other, is employed in the emulsified state, for example, as a water-in-oil emulsion, the ionic polymer and / or the ionic polymer auxiliary, independently of each other, is dosed to cellulosic material at a concentration of 2,500 ± 750 g / metric ton, or 2,500 ± 500 g / metric ton, or 2,500 ± 400 g / metric ton, or 2,500 ± 300 g / metric ton, or 2,500 ± 200 g / metric ton, or 2,500 ± 100 g / metric ton, based on the total composition containing the cellulosic material and related to the polymer content, that is, not to the water and oil content of the water-in emulsion. -oil.
[000214] It has been found that the biocide and the ionic polymer, and the optionally added auxiliary ionic polymer, not only reduce the COD of the resulting effluents such as waste water, but can also improve the strength properties of the final paper products. This indicates that the ionic polymer and the optionally added auxiliary ionic polymer are stable through the entire papermaking process.
[000215] In a preferred embodiment, the combined treatment of the cellulosic material containing the starch with the biocide and the ionic polymer and the optionally added auxiliary ionic polymer in the thick stock or thin stock area, according to the invention, results in a decrease the COD value of the waste water of at least 3.0%, or at least 5.0%, or at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, when compared to the COD of dump water, which is obtained when cellulosic material is processed in the absence of the biocide , and when no polymer is added. The COD value is preferably measured according to ASTM D1252 or ASTM D6697.
[000216] In an additionally preferred embodiment, the combined treatment of the cellulosic material containing the starch with the biocide and the ionic polymer, and the optionally added auxiliary ionic polymer, results in a reduction in turbidity of at least 5.0%, or at least at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least 35%, or at least 40%, or at least 50%, or at least 60 %, or at least 70%, or at least 80%, or at least 90%, when compared to the measured turbidity for the final paper product produced from cellulosic material that has not been treated with the biocide and the polymer during pulping, or shortly after. Turbidity is preferably measured according to ASTM D7315 - 07a.
[000217] In another preferred embodiment, the combined treatment of the cellulosic material containing the starch with the biocide and the ionic polymer, and the optionally added auxiliary ionic polymer, results in an increase in the Scott Bond value of the final paper product of at least 2.0%, or at least 5.0%, or at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, when compared to the Scott Bond value measured for the final paper product produced from cellulosic material that was not treated with the biocide and the polymer during pulping, or shortly after. The Scott Bond value is preferably measured according to TAPPI T 833 pm-94.
[000218] In yet another preferred embodiment, the combined treatment of the cellulosic material containing the starch with the biocide and the ionic polymer, and the optionally added auxiliary ionic polymer, results in an increase in the CMT value of the final paper product of at least 2.0%, or at least 5.0%, or at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, when compared to the measured CMT value for the final paper product produced from cellulosic material that was not treated with the biocide and the polymer during pulping, or shortly after . The CMT value is preferably measured according to DIN EN ISO 7236 or TAPPI method T 809.
[000219] In yet another preferred embodiment, the combined treatment of the cellulosic material containing the starch with the biocide and the ionic polymer, and the optionally added auxiliary ionic polymer, results in an increase in the SCT value of the final paper product of at least 2.0%, or at least 5.0%, or at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least 40%, or at least 50%, or at least 60% or at least 70%, when compared to the SCT value measured for the final paper product produced from cellulosic material that was not treated with the biocide and the polymer during pulping, or shortly after . The SCT value is preferably measured according to DIN 54 518 or TAPPI method T 826.
[000220] In an additionally preferred embodiment, the combined treatment of the cellulosic material containing the starch with the biocide and the ionic polymer, and the optionally added auxiliary ionic polymer, results in an increase in the breaking strength (Mullen's bursting resistance) of the product paper end of at least 2.0%, or at least 5.0%, or at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, when compared to the bursting resistance measured for the final paper product produced from cellulosic material that has not been treated with the biocide and the polymer during pulping, or shortly after. The breaking strength is preferably measured according to TAPPI 403os-76 or ASTM D774.
[000221] In an additionally preferred embodiment, the combined treatment of the cellulosic material containing the starch with the biocide and the ionic polymer, and the optionally added auxiliary ionic polymer, results in an increase in the breaking length of the final paper product of at least 2.0%, or at least 5.0%, or at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, when compared to the measured break length for the final paper product produced from cellulosic material that has not been treated with the biocide and the polymer during pulping, or shortly after . The break length is preferably measured according to TAPPI Method T 404 cm-92.
[000222] For the purpose of the specification, the term "cationic polymer" preferably refers to water-soluble and / or water-swellable polymers, which have a positive net charge. Cationic polymers can be branched or unbranched, cross-linked or non-cross-linked, grafted or non-grafted. The cationic polymers, according to the invention, are preferably neither branched, nor cross-linked, nor grafted.
[000223] For the purpose of the specification, the term "anionic polymer" preferably refers to water-soluble and / or water-swellable, which have a negative net charge. Anionic polymers can be branched or unbranched, cross-linked or non-cross-linked, grafted or non-grafted. The cationic polymers, according to the invention, are preferably neither branched, nor cross-linked, nor grafted.
[000224] A person skilled in the art knows the meaning of the terms "branched polymer", "unbranched polymer", "crosslinked polymer" and "graft polymer". Definitions for these terms can be found preferably in A. D. Jenkins et al. Glossary of Basic Terms in Polymer Science. Pure & Applied Chemistry 1996, 68, 22872311.
[000225] For the purpose of the specification, the term "swellable in water" preferably refers to the increase in the volume of polymer particles associated with the entry of water (cf. DH Everett. Manual of Symbols and Terminology for Physicochemical Quantities and Units Appendix II, Part I: Definitions, Terminology and Symbols in Colloid and Surface Chemistry. Pure & Applied Chemistry 1972, 31, 579638). The swelling behavior of the polymer can be measured at different temperatures and pH values in water. The swelling weights of the polymers are determined at intervals, after removing water from the surface, until equilibrium swelling is achieved. The swelling percentage is preferably calculated using the following equation:% swelling = 100 x [(Wt - W0) / W0], where W0 is the initial weight and Wt the final weight of the gel at time t (cf. IM El-Sherbiny et al. Preparation, characterization, swelling and in vitro drug release behavior of poli [N-acryloylglycine-chitosan] interpolymeric pH and thermally-responsive hydrogels. European Polymer Journal 2005, 41, 2584-2591).
[000226] Water-swellable ionic polymers and / or auxiliary ionic polymers, according to the invention, can preferably yield a swelling% of at least 2.5%, or at least 5.0%, or at least 7 , 5%, or at least 10%, or at least 15%, or at least 20% measured in demineralized water at 20 ° C and pH 7.4 in phosphate buffer after equilibrium swelling is achieved.
[000227] For the purpose of the specification, the term "polymer" preferably refers to a material composed of macromolecules containing> 10 units of monomer (cf. GP Moss et al. Glossary of Class Names of Organic Compounds and Reactive Intermediates Based on Structure, Pure & Applied Chemistry 1995, 67, 1307-1375).
[000228] The ionic polymer and / or the auxiliary ionic polymer, independently of each other, can each consist of a simple type of ionic polymer, preferably cationic polymer, or can be contained in a composition comprising a different ionic polymer, preferably cationic polymers.
[000229] Ionic polymers and / or auxiliary ionic polymers, independently of each other, can be homopolymers, which preferably comprise ionic monomer units, preferably cationic monomer units as the only monomer component. In addition, ionic polymers and / or auxiliary ionic polymers, independently of each other, can also be copolymers, i.e., bipolymers, terpolymers, quaterpolymers, etc., which comprise, for example, different ionic monomer units, preferably monomer units cationic; or ionic monomer units, preferably cationic, as well as nonionic monomer units.
[000230] For the purpose of the specification, the term "homopolymer" preferably refers to a polymer derived from a species of monomer, and the term "copolymer" preferably refers to a polymer derived from more than one species of monomer. Copolymers that are obtained by copolymerization of two species of monomer are called bipolymers, those obtained from three monomers, terpolymers, those obtained from four monomers, quaterpolymers, etc. (cf. A. D. Jenkins et al. Glossary of Basic Terms in Polymer Science. Pure & Applied Chemistry 1996, 68, 2287-2311).
[000231] In the event that the ionic polymer and / or the auxiliary ionic polymer is a copolymer, it is preferably independently random copolymer, a statistical copolymer, a block copolymer, a periodic copolymer, or an alternative copolymer, more preferably one random copolymer. In a particularly preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer, independently of each other, is a copolymer with one of the comonomers being acrylamide.
[000232] One skilled in the art knows the meaning of the terms "random copolymer", "statistical copolymer", "periodic copolymer", "block copolymer" and "alternative copolymer". Definitions for these terms can be found preferably in A. D. Jenkins et al. Glossary of Basic Terms in Polymer Science. Pure & Applied Chemistry 1996, 68, 2287-2311.
[000233] For the purpose of the specification, the expression "at least two different ionic polymers" refers to a mixture (blend) of ionic polymers comprising more than one, preferably two, three or four ionic polymers that differ from each other in its monomer units, molecular weight, polydispersity and / or tacticity, etc. Different polymers can also differ in their ionicity, that is, one ionic polymer can be cationic, another anionic.
[000234] For the purpose of the specification, the term "ionicity" can refer to the net charge of a polymer, as well as its quantity, preferably molar content of ionic monomer units based on the total content of monomer units, preferably expressed in mole%.
[000235] Preferably, the ionic polymer and / or the auxiliary ionic polymer, independently of each other, comprise monomer units that are derived from radically polymerizable, ethylenically unsaturated monomers. Therefore, in a preferred embodiment, the polymer support of the ionic polymer and / or the auxiliary ionic polymer, independently of each other, is a carbon chain that is not interrupted by heteroatoms, such as nitrogen or oxygen.
[000236] Preferably, the ionic polymer and / or the auxiliary ionic polymer, independently of each other, is derived from ethylenically unsaturated monomers which are preferably radically polymerizable.
[000237] In a preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer, independently of each other, is derived from (meth) acrylic acid derivatives, such as (meth) acrylic acid esters, (meth) acrylic acid amides, acrylonitrile, and the like. Preferably, the ionic polymer and / or the auxiliary ionic polymer, independently of one another, is a derivative of a poly (meth) acrylate. For the purpose of the specification, the term "(meth) acryl" must refer to methacryl, as well as to acryl.
[000238] Preferably, the degree of polymerization of the ionic polymer and / or the auxiliary ionic polymer, independently of each other, is at least 90%, more preferably at least 95%, even more preferably at least 99%, even more preferably at least 99.9%, more preferably at least 99.95% and, in particular, at least 99.99%.
[000239] Preferably, the ionic polymer, preferably cationic polymer, or anionic polymer, has a comparatively high average molecular weight that is preferably higher than that of the optionally present auxiliary ionic polymer. Preferably, the weight average molecular weight Mw of the ionic polymer, preferably cationic polymer, or anionic polymer, which can be measured, for example, by GPC, is at least 100,000 g / mol, or at least 250,000 g / mol, more preferably at least 500,000 g / mol, or at least 750,000 g / mol, even more preferably at least 1,000,000 g / mol, or at least 1,250,000 g / mol, even more preferably at least 1,500,000 g / mol, or at least 2,000,000 g / mol, more preferably at least 2,500,000 g / mol, or at least 3,000,000 g / mol, and in particular, within the range of 1,000,000 g / mol to 10,000,000 g / mol, or within the range of 5,000,000 g / mol to 25,000,000 g / mol.
[000240] Preferably, the molecular weight dispersion (average molecular weight weight: Mw) / (average molecular weight number: Mn) of the ionic polymer, preferably cationic polymer, or anionic polymer is within the range of 1.0 to 4 , 0, more preferably 1.5 to 3.5 and, in particular, 1.8 to 3.2.
[000241] The average molecular weight and molecular weight distribution of the ionic polymer, preferably cationic polymer, or anionic polymer, can be measured by a well-known method using gel permeation chromatography. An average number of molecular weight and average molecular weight of weight can be calculated using these values, and the ratio (Mw / Mn) can also be calculated.
[000242] The average molecular weight (Mn) number of the ionic polymer, preferably cationic polymer, or anionic polymer is preferably 1,000,000-50,000,000 g / mol and, more preferably, 5,000,000-25,000,000 g / mol .
[000243] In a preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer, independently of each other, is a cationic polymer.
[000244] In a preferred embodiment, the cationic polymer and / or the auxiliary cationic polymer, independently of one another, is derived from vinyl amine or vinyl amine derivatives, such as vinylamides, for example, vinyl formamide or vinyl acetamide.
[000245] In another preferred embodiment, the cationic polymer and / or the auxiliary cationic polymer, independently of one another, is derived from quaternized ammonia compounds comprising radically polymerizable groups such as allyl or acryl groups.
[000246] The cationic polymer and / or the auxiliary cationic polymer, independently of each other, can also be derived from several of the above monomers, for example, acrylic acid derivatives, as well as vinyl amine or vinyl amine derivatives.
[000247] In a preferred embodiment, the cationic polymer and / or the auxiliary cationic polymer, independently of each other, is a positively charged material composed of macromolecules containing> 10 monomer units, in which at least one monomer is a cationic monomer of formula general (I) as defined below.
[000248] The compounds of the following general formula (I) can be used as cationic monomers for the production of the water-soluble cationic polymer or water-swellable cationic polymer and / or the auxiliary cationic polymer, independently of each other, according to the invention:
in which R1 supports hydrogen or methyl, Z1 supports O, NH or NR4, in which R4 supports alkyl with 1 to 4 carbon atoms; preferably Z1 supports NH; and Y supports one of the groups
in which Y0 and Y1 supports alkylene with 2 to 6 carbon atoms, optionally substituted with hydroxy groups, Y2, Y3, Y4, Y5, and Y6, independently of each other, support alkyl with 1 to 6 carbon atoms, and Z "supports halide, pseudohalide, acetate or methyl sulfate.
[000249] For the purpose of the specification, the term "pseudohalide" preferably refers to certain ions such as azide, thiocyanate, and cyanide, which resemble halide ions in their chemistry (cf. GP Moss et al. Glossary of Class Names of Organic Compounds and Reactive Intermediates Based on Structure. Pure & Applied Chemistry 1995, 67, 1307-1375). downstreamchlorhydratochlorhydratochlorhydratochlorhydrate
[000250] Protonated or quaternized dialkylaminoalkyl (meth) acrylates (e.g. trialkylammonalkyl (meth) acrylates) or dialkylaminoalkyl (meth) acrylated protonated or quaternized (e.g. trialkylammonalkyl (meth) acrylamides with C1-C3 alkyls or C1-C3 alkyl groups alkylene are preferred. Methyl halide-quaternized, ethyl halide-quaternized, propyl halide-quaternized, or isopropyl halide-quaternized ammonia salts of N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminomethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (met) acrylamide / ouN, N-dimethylaminopropyl (met) acrylamide, are more preferred. As preferred alkyl halides, alkyl chlorides are used for quaternization. Instead of the alkyl chlorides (i.e., methyl chloride, ethyl chloride, propyl chloride, and isopropyl chloride), the corresponding bromides, iodides, sulfates, etc., can also be used for the quaternization of said N, N-dialkylaminoalkyl (methyl ) acrylate and N, N-dialkylaminoalkyl (meth) acrylamide derivatives.
[000251] Additionally, the cationic monomer DADMAC (diallyldimethyl ammonium chloride) can be used for the preparation of the cationic polymer and / or the auxiliary cationic polymer, according to the invention.
[000252] In a preferred embodiment of the invention, the cationic polymer and / or the auxiliary ionic polymer, independently of each other, contain cationic monomer units selected from the group consisting of quaternized ADAME-Quat (N, N-dimethylaminoethyl acrylate) ; for example, N, N, N-trimethylammonethyl acrylate), DIMAPA-Quat (N, N-N-dimethylaminopropyl acrylamide; for example, N, N, N-trimethylammonylpropyl acrylamide), and DADMAC (diallyldimethyl ammonium chloride), as well as units of nonionic monomer selected from the group consisting of acrylamide, methacrylamide and vinylamide and vinylamine, respectively.
[000253] Quaternized dialkylaminoalkyl (meth) acrylates with C1 to C6-alkyl groups, preferably C1 to C3-alkyl, or C1 to C6-alkylene, preferably C1 to C3-alkylene groups (N, N, N-trialkylamoniaalkyl (meth) acrylates ); preferably N, N, N-trialkylammonylalkyl (meth) acrylate, more preferably N, N, N-trimethylammonylalkyl (meth) acrylate, even more preferably N, N, N-trimethylammonethyl (meth) acrylate, in each case with counter anions suitable compounds such as halogens are particularly preferred as cationic monomers for the production of water-soluble polymers or water-swellable polymers according to the invention, especially the ionic polymer.
[000254] In a preferred embodiment of the invention, the cationic polymer and / or auxiliary cationic polymer, independently of each other, is the reaction product (preferably Michael's adduct) of a polyvinylamine totally or partially hydrolyzed and protonated or quaternized N, N -dialkylaminoalkyl acrylamide, preferably DIMAPA-Quat. (N, N-N-dimethylaminopropyl acrylamide; for example, N, N, N-trimethylammoniapropyl acrylamide) or other cationic, anionic and / or non-ionic monomers. Polymers of this type comprise the following structural element:
in which R is H (in the case of the protonated form) or alkyl (in the case of the quaternized form) and X- is a counter anion, such as halogen, HSO4- and the like.
[000255] Quaternized dialkylaminoalkyl (meth) acrylamides with C1 to C6-alkyl groups, preferably C1 to C3-alkyl or C1 to C6-alkylene, preferably C1 to C3-alkylene (N, N, N-trialkyl-ammoniaalkyl (met) groups acrylamide, in which "(meth) acrylamide" supports "methacrylamide or acrylamide"); preferably N, N, N-trialkylammonalkyl (meth) acrylamide, more preferably N, N, N-trimethylammonalkyl (meth) acrylamide, even more preferably N, N, N-trimethylammonpropyl (meth) acrylamide, in each case with suitable counter anions, such as halide are particularly preferred as cationic monomers for the production of water-soluble polymers or water-swellable polymers according to the invention, especially the ionic polymer and / or the ionic auxiliary polymer.
[000256] For the preparation of cationic polymers and / or auxiliary cationic polymers, independently of one another, a monomer composition is preferably used which comprises one or more cationic monomers. Most preferably, the preparation of cationic polymer and / or auxiliary cationic polymer is carried out using a mixture of one or more nonionic monomers, preferably acrylamide, and one or more cationic monomers, in particular, any of the cationic monomers as described above.
[000257] In another preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer, independently of each other, is an anionic polymer.
[000258] In a preferred embodiment, the anionic polymer and / or the auxiliary anionic polymer, independently of each other, is a negatively charged material composed of macromolecules containing> 10 monomer units, in which at least one monomer is an anionic monomer as defined bellow.
[000259] The anionic monomers that can be used or selected by way of example, according to the invention, are those listed below: a.) Olefinically unsaturated carboxylic acids and anhydride carboxylic acids, in particular acrylic acid, methacrylic acid, itaconic, crotonic acid, glutaconic acid, maleic acid, maleic anhydride, fumaric acid, and their water-soluble alkali metal salts, their alkaline earth metal salts, and their ammonium salts; b.) olefinically unsaturated sulfonic acids, in particular, aliphatic and / or aromatic vinyl sulfonic acids, for example, vinyl sulfonic acid, allylsulfonic acid, styrenesulfonic acid, acrylic and methacrylic sulfonic acids, in particular sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-methacryloxypropyl sulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid, and the water-soluble alkali metal salts thereof, alkaline earth metal salts thereof, and ammonium salts thereof; c.) olefinically unsaturated phosphonic acids, in particular, for example, vinyl- and allyl-phosphonic acid, and their water-soluble alkali metal salts, their alkaline earth metal salts, and their ammonium salts; d.) sulfomethylated and / or phosphonomethylated acrylamides and the water-soluble alkali metal salts thereof, alkaline earth metal salts thereof, and ammonium salts thereof.
[000260] Preferably, olefinically instilled carboxylic acids and anhydride carboxylic acid, in particular acrylic acid, methacrylic acid, itaconic acid, crotonic acid, glutaconic acid, maleic acid, maleic anhydride, fumaric acid, and the water-soluble alkali metal salts of these, alkaline earth metal salts of these, and ammonium salts of these, are used as anionic monomers, the alkali metal salts soluble in water of acrylic acid, in particular, their sodium salts and potassium salts, and their ammonia salts , being particularly preferred.
[000261] For the preparation of anionic polymers and / or auxiliary anionic polymers, independently of one another, a monomer composition is preferably used that consists of 0 to 100% by weight, preferably from 5 to 70% by weight, and, more preferably , from 5 to 40% by weight, of anionic monomers, in each case based on the total monomer weight. Most preferably, the preparation of anionic polymer and / or auxiliary anionic polymer, independently of each other, is carried out using a mixture of nonionic monomers, preferably acrylamide, and anionic monomers, in particular, olefinically unsaturated carboxylic acids, and anhydride carboxylic acid, preferably acrylic acid, methacrylic acid, itaconic acid, crotonic acid, glutaconic acid, maleic acid, maleic anhydride, fumaric acid, and their water-soluble alkali metal salts, their alkaline earth metal salts, and their ammonium salts, acrylic acid being particularly preferred as the anionic monomer. A mixture of acrylic acid with alkyl (meth) acrylates and / or alkyl (meth) acrylamides is also preferred. In such monomer compositions, the amount of anionic monomers is preferably at least 5% by weight.
[000262] The ionic polymer, preferably cationic polymer, or anionic polymers and / or auxiliary ionic polymers, independently of each other, can also be copolymers, i.e., bipolymers, terpolymers, quaterpolymers, etc., which comprise, for example , at least two different ionic monomer units, preferably cationic monomer unit or monomer units or ionic monomer unit, preferably cationic monomer unit, or anionic monomer unit, as well as nonionic monomer units, and / or units of amphiphilic monomer.
[000263] It is also possible that the ionic polymer and / or the auxiliary ionic polymer, independently of each other, is a copolymer of cationic monomers, anionic monomers, and, optionally, nonionic monomers, so that ionicity is dominated by cationic monomers of so that the total net charge is positive, making the polymer cationic. Alternatively, the ionic polymer and / or the auxiliary ionic polymer, independently of each other, can also be a cationic, anionic, and optionally non-ionic monomer copolymer, whereby ionicity is dominated by the anionic monomers so that the net charge total is negative, making the ionic polymer anionic.
[000264] For the purpose of the specification, the term "nonionic monomer units" preferably refers to the monomers of the general formula (II):
in which R1 supports hydrogen or methyl, and R2 and R3 independently support hydrogen, alkyl with 1 to 5 carbon atoms, or hydroxyalkyl with 1 to 5 carbon atoms.
[000265] Nonionic monomers (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, or N, N substituted (meth) acrylamides, such as N, N, -dimethyl (meth) acrylamide , N, N-diethyl (meth) acrylamide, N-methyl-N-ethyl (meth) acrylamide, or N-hydroxyethyl (meth) acrylamide, are preferably used as comonomers for the production of water-soluble or swellable ionic polymers in water, preferably cationic polymers or anionic polymers and / or auxiliary ionic polymers, according to the invention. The nonionic monomer acrylamide or methacrylamide is most preferably used.
[000266] For the purpose of the specification, the term "amphiphilic monomer units" preferably refers to monomers of the general formula (III) and (IV):
in which Z1 supports O, NH or NR4, in which R4 supports hydrogen or methyl, R1 supports hydrogen or methyl, R5 and R6 independently supports alkyl with 1 to 6 carbon atoms, R7 supports alkyl, aryl and / or aralkyl with 8 to 32 carbon atoms, R8 supports alkylene with 1 to 6 carbon atoms, and Z "supports halogen, pseudohalide ions, methyl sulfate or acetate; Or
in which Z1 supports O, NH or NR4, in which R4 supports alkyl with 1 to 4 carbon atoms, R1 supports hydrogen or methyl, R8 supports alkylene with 1 to 6 carbon atoms, R9 supports alkylene with 2 to 6 carbon atoms , and R10 supports hydrogen, alkyl, aryl, and / or aralkyl with 8 to 32 carbon atoms, and n supports an integer between 1 to 50.
[000267] Conversion products of (meth) acrylic acid or (meth) acrylamide with polyethylene glycols (10 to 40 ethylene oxide units) that have been etherified with fatty alcohol are preferably used as amphiphilic monomers for the production of the ionic polymer soluble in water, or water-swellable ionic polymer, and / or the auxiliary ionic polymer according to the invention.
[000268] For the purpose of the specification, the term "amphiphilic monomer units" preferably refers to charged, preferably positively charged, or uncharged monomers, which both have a hydrophilic group and a hydrophobic group (cf. DH Everett. Manual of Symbols and Terminology for Physicochemical Quantities and Units. Appendix II, Part I: Definitions, Terminology and Symbols in Colloid and Surface Chemistry. Pure & Applied Chemistry 1972, 31, 579-638).
[000269] In a preferred embodiment, the ionic polymer, preferably cationic polymer, or anionic polymer, contains at least 10% by weight, or at least 25% by weight, or at least 50% by weight, or at least 75% by weight. weight, or about 100% by weight of ionic monomer units, preferably cationic monomer units, or ionic monomer units. More preferably, the ionic polymer, preferably cationic polymer, or anionic polymer, contains 10-100% by weight, or 15-90% by weight, or 20-80% by weight, or 25-70% by weight, or 30- 60% by weight of ionic monomer units, preferably cationic monomer units, or ionic monomer units.
[000270] In another preferred embodiment, the ionic polymer, preferably cationic polymer, or anionic polymer, contains at least 1.0 mol%, or at least 2.5 mol%, or at least 5.0 mol%, or at least 7.5 mol%, or at least 10 mol% of cationic monomer units. More preferably, the ionic polymer, preferably cationic polymer, or anionic polymer, contains 2.5-40 mol%, or 5.0-30 mol%, or 7.5-25 mol%, or 8.0- 22 mol%, or 9.0-20 mol% of ionic monomer units, preferably cationic monomer units, or ionic monomer units.
[000271] Preferably, the ionic polymer, preferably cationic polymer, or anionic polymer, contains 15.5 ± 15 mol%, 16 ± 15 mol%, 16.5 ± 15 mol%, 17 ± 15 mol%, 17.5 ± 15 mol%, 18 ± 15 mol%, 18.5 ± 15 mol%, 19 ± 15 mol%, 19.5 ± 15 mol%, 20 ± 15 mol%, 20, 5 ± 15 mol%, 21 ± 15 mol%, 21.5 ± 15 mol%, 22 ± 15 mol%, 22.5 ± 15 mol%, 23 ± 15 mol%, 23.5 ± 15 mol%, 24 ± 15 mol%, 24.5 ± 15 mol%, 25 ± 15 mol%, 25.5 ± 15 mol%, 26 ± 15 mol%, 26.5 ± 15% mol, 27 ± 15 mol%, 27.5 ± 15 mol%, 28 ± 15 mol%, 28.5 ± 15 mol%, 29 ± 15 mol%, 29.5 ± 15 mol% , 30 ± 15 mol%, 30.5 ± 15 mol%, 31 ± 15 mol%, 31.5 ± 15 mol%, 32 ± 15 mol%, 32.5 ± 15 mol%, 33 ± 15 mol%, 33.5 ± 15 mol%, 34 ± 15 mol%, 34.5 ± 15 mol%, 35 ± 15 mol%, 35.5 ± 15 mol%, 36 ± 15 mol%, 36.5 ± 15 mol%, 37 ± 15 mol%, 37.5 ± 15 mol%, 38 ± 15 mol%, 38.5 ± 15 mol%, 39 ± 15% mol mol, 39.5 ± 15 mol%, or 40 ± 15 mol% of ion monomer units, preferably cationic monomer units, or joined ionic monomer requirements, based on the total number of monomer units.
[000272] Preferably, the ionic polymer, preferably cationic polymer, or anionic polymer, contains 8.0 ± 7.5 mol%, 8.5 ± 7.5 mol%, 9.0 ± 7.5 mol% , 9.5 ± 7.5 mol%, 10 ± 7.5 mol%, 10.5 ± 7.5 mol%, 11 ± 7.5 mol%, 11.5 ± 7.5% mol mol, 12 ± 7.5 mol%, 12.5 ± 7.5 mol%, 13 ± 7.5 mol%, 13.5 ± 7.5 mol%, 14 ± 7.5 mol% , 14.5 ± 7.5 mol%, 15 ± 7.5 mol%, 15.5 ± 7.5 mol%, 16 ± 7.5 mol%, 16.5 ± 7.5% mol mol, 17 ± 7.5 mol%, 17.5 ± 7.5 mol%, 18 ± 7.5 mol%, 18.5 ± 7.5 mol%, 19 ± 7.5 mol% , 19.5 ± 7.5 mol%, 20 ± 7.5 mol%, 20.5 ± 7.5 mol%, 21 ± 7.5 mol%, 21.5 ± 7.5% mol mol, 22 ± 7.5 mol%, 22.5 ± 7.5 mol%, 23 ± 7.5 mol%, 23.5 ± 7.5 mol%, 24 ± 7.5 mol% , 24.5 ± 7.5 mol%, 25 ± 7.5 mol%, 25.5 ± 7.5 mol%, 26 ± 7.5 mol%, 26.5 ± 7.5% mol mol, 27 ± 7.5 mol%, 27.5 ± 7.5 mol%, 28 ± 7.5 mol%, 28.5 ± 7.5 mol%, 29 ± 7.5 mol% , 29.5 ± 7.5 mol%, 30 ± 7.5 mol%, 30.5 ± 7.5 mol%, 31 ± 7.5 mol%, 31.5 ± 7.5% mol mol, 32 ± 7.5 mol%, 32.5 ± 7.5 mol%, 33 ± 7.5 mol%, 33.5 ± 7.5 mol%, 34 ± 7.5 mol%, 34.5 ± 7.5 mol%, 35 ± 7.5 mol%, 35.5 ± 7.5 mol%, 36 ± 7.5 mol%, 36.5 ± 7, 5 mol%, 37 ± 7.5 mol%, 37.5 ± 7.5 mol%, 38 ± 7.5 mol%, 38.5 ± 7.5 mol%, 39 ± 7.5 mol%, 39.5 ± 7.5 mol%, or 40 ± 7.5 mol% of ionic monomer units, preferably cationic monomer units, or ionic monomer units, based on the total amount of units of monomer.
[000273] In yet another preferred embodiment, the ionic polymer, preferably cationic polymer, or anionic polymer, contains 1550 mol%, or 20-45% mol, or 25-40% mol, or 25.5-38% in mol, or 26-36 mol% of ionic monomer units, preferably cationic monomer units, or ionic monomer units.
[000274] In a particularly preferred embodiment, the ionic polymer is a cationic polymer which is a copolymer of acrylamide or methacrylamide with dialkylaminoalkyl (meth) acrylates, quaternized dialkylaminoalkyl (meth) acrylamides, or diallylalkyl ammonium halides; more preferably a copolymer of acrylamide with ADAME-Quat (N, N-N-dimethylaminoethyl acrylate, i.e., trimethylammonethyl acrylate), DIMAPA-Quat (N, N-dimethylaminopropyl acrylamide, quaternized amylethyl acrylate amide or diallylamide) or ); in which the cationic monomer content is preferably within the range of 5 to 99% by weight, more preferably 7.5 to 90% by weight, even more preferably 10 to 80% by weight, more preferably 15 to 60% by weight, and, in particular, 20 to 45% by weight, based on the total weight of the cationic polymer.
[000275] Preferably, the cationic polymer and / or the auxiliary cationic polymer, independently of each other, is derived from identical or different monomers according to the general formula (V),
in which R1 supports -H or -CH3, and R11 supports -H or -C2-C6-alkylene-N + (C1-C3-alkyl) 3 X-, where X- is a suitable anion, such as Cl-, Br- , SO42-, and the like.
[000276] Preferably, the cationic polymer and / or auxiliary cationic polymer does not contain any vinylamine units, or derivatives thereof, such as acylates (e.g., vinylamine, mono- or di-N-alkylvinylamine, quaternized N-alkyl vinylamine, N-formyl vinylamine, N-acetyl vinylamine, and the like).
[000277] Quaternized dialkylaminoalkyl (meth) acrylamide homopolymers, or quaternized dialkylaminoalkyl (meth) acrylamides and (meth) acrylamides are preferably employed as cationic polymers and / or auxiliary cationic polymers.
[000278] In a particularly preferred embodiment, the ionic polymer and / or the auxiliary ionic polymer, independently of each other, in each case, may be contained in a cationic or anionic polymer composition that contains at least one anionic polymer A and / or at least one cationic polymer or anionic polymer B as defined here below. Preferably, ionic polymer A and ionic polymer B have the same charge, that is, they are either both anionic, or both cationic.
[000279] The cationic polymer or anionic polymer A is preferably high molecular with an average molecular weight (Mw) of - 1.0 * 106 g / mol, as measured by the GPC method. The cationic polymer or anionic polymer B is preferably a low molecular polymer with an average molecular weight (Mw) of at least 500,000 g / mol, or at least 400,000 g / mol, or at least 300,000 g / mol, or at least 200,000 g / mol, as measured by the GPC method.
[000280] Thus, it is preferred that the average molecular weight of the cationic polymer or anionic polymer A is greater than the average molecular weight of the cationic polymer or anionic polymer B. The ratio of the average molecular weights of cationic polymer or anionic polymer A to cationic polymer or anionic polymer B can be at least 4.0, or at least 10, or at least 20, or at least 25, or at least 30, or at least 40.
[000281] In a particularly preferred embodiment, the ionic polymer, preferably cationic polymer or anionic polymer and / or the auxiliary ionic polymer, preferably cationic polymer or anionic polymer, independently of each other, in each case, comprises at least one cationic polymer or polymer water-soluble or water-swellable anionic, and / or at least one cationic polymer or water-soluble or water-swellable anionic polymer, as the only polymer components.
[000282] The preparation of the cationic polymer or water-soluble and water-swellable anionic polymer is known to the person skilled in the art. For example, the polymers according to the invention can be prepared by polymerization techniques according to the procedures described in WO 2005/092954, WO 2006/072295, and WO 2006/072294.
[000283] According to a preferred embodiment of the method according to the invention, step (h) involves the addition of two different ionic polymers, preferably cationic polymers or anionic polymers to the cellulosic material, in which the second ionic polymer (ionic polymer) auxiliary) is preferably added in the thick stock area, where the cellulosic material preferably has a stock consistency of at least 2.0%; or in the thin stock area, where the cellulosic material preferably has a stock consistency of less than 2.0%.
[000284] It has been surprisingly found that two different ionic polymers referred to can act synergistically, particularly with regard to (re-) fixation of starch to cellulose fibers. This synergism is particularly pronounced when both polymers have different average molecular weights and / or ionicities.
[000285] For the purpose of the specification, one of the said two different ionic polymers is to be related as the "ionic polymer", so the other of said two different ionic polymers, according to the invention, in the following, will be referred to as "auxiliary ionic polymer".
[000286] Thus, preferably step (h) of the method according to the invention comprises - sub-step (h1) concerning the addition of the ionic polymer, preferably cationic polymer or anionic polymer, according to the invention, to the cellulosic material in the area thick stock, or in the thin stock area; and sub-step (h2) concerning the addition of the auxiliary ionic polymer, preferably cationic polymer or anionic polymer, according to the invention, to the cellulosic material, preferably in the thick stock area, or in the thin stock area.
[000287] The auxiliary ionic polymer and the ionic polymer can be added to the cellulosic material, preferably to the thick stock, or to the thin stock, simultaneously or subsequently, continuously or discontinuously. Preferably, both polymers are added continuously.
[000288] The auxiliary ionic polymer and the ionic polymer can be added to the cellulosic material at the same feed point, or at different feed points. When both polymers are added at the same feed point, they can be added in the form of a simple composition containing the auxiliary ionic polymer and the ionic polymer, or in the form of different compositions, one containing the auxiliary ionic polymer, the other containing the ionic polymer. One skilled in the art recognizes that mixed variants are also possible, for example, one composition may contain a mixture of the auxiliary ionic polymer and the ionic polymer, whereby the other composition may contain pure auxiliary ionic polymer, pure ionic polymer, or both, this that is, the auxiliary ionic polymer and the ionic polymer in another mixing ratio.
[000289] In a preferred embodiment, the auxiliary ionic polymer is added to the intake of the mixing box and / or on top of the machine box.
[000290] Preferably, the ionic polymer and the auxiliary ionic polymer are added at locations other than the papermaking facility. In a preferred embodiment, the feed point for the ionic polymer is located upstream with respect to the feed point for the auxiliary ionic polymer. In another preferred embodiment, the supply point for the ionic polymer is located downstream with respect to the supply point for the auxiliary ionic polymer.
[000291] In a preferred embodiment, at least a portion of the ionic polymer and at least a portion of the auxiliary ionic polymer is added to the thick stock. In another preferred embodiment, at least a portion of the ionic polymer and at least a portion of the auxiliary ionic polymer is added to the thin stock. In yet another preferred embodiment, at least a portion of the ionic polymer is added to the thick stock, and at least a portion of the auxiliary ionic polymer is added to the thin stock. In yet another preferred embodiment, at least a portion of the ionic polymer is added to the thin stock, whereby at least a portion of the auxiliary ionic polymer is added to the thick stock.
[000292] Particularly preferred embodiments B1 to B2 concerning preferred ionic polymer feed points, preferably cationic polymer, or anionic polymer, and the auxiliary ionic polymer, preferably cationic polymer or anionic polymer, according to the invention, are summarized in the Table 2 here below: Table 2:
in which sections (II) to (IV) refer to the sections of a papermaking facility comprising a papermaking machine, in which section (II) includes measures associated with pulping; section (III) includes measures that occur after pulping, but still outside the papermaking machine; and section (IV) includes measurements that occur within the papermaking machine.
[000293] Particularly preferred embodiments of the method according to the invention relate to combinations of any of the embodiments A1 to A6 as summarized in Table 1 with any of the embodiments B1 to B2 as summarized in Table 2; particularly A1 + B1, A1 + B2; A2 + B1, A2 + B2; A3 + B1, A3 + B2; A4 + B1, A4 + B2; A5 + B1, A5 + B2; A6 + B1, A6 + B2.
[000294] When the auxiliary ionic polymer and the ionic polymer are contained in different compositions, said compositions may, independently of each other, be liquid or solid. Preferably, the composition containing the auxiliary ionic polymer is liquid and the composition containing the ionic polymer is solid.
[000295] The auxiliary ionic polymer can be cationic or anionic. Preferably, it has the same charge as the ionic polymer, that is, either the ionic polymer, as well as the auxiliary ionic polymer are either both cationic or both anionic.
[000296] In principle, the preferred properties, such as chemical composition (e.g., monomers, comonomers, molecular weight, and the like) of the ionic polymer according to the invention, which have been described above, also apply fully to the ionic polymer auxiliary, according to the invention. Thus, for the purpose of the specification, the above definitions referring to the ionic polymer, preferably cationic polymer or anionic polymer, according to the invention, must also refer to the auxiliary ionic polymer, according to the invention, and therefore they are not explicitly repeated from now on. For example, when the auxiliary ionic polymer is cationic, it is preferably derived from a monomer composition containing cationic monomers of the general formula (I).
[000297] In a preferred embodiment, the auxiliary ionic polymer is a homopolymer of cationic monomers. In another preferred embodiment, the auxiliary ionic polymer is a copolymer of cationic and non-ionic monomers.
[000298] Preferably, the auxiliary ionic polymer is a copolymer of cationic monomers and, optionally, nonionic monomers, and anionic comonomers, so that the ionicity is dominated by the cationic monomers so that the total net charge is positive, making the ionic polymer cationic auxiliary. In this embodiment, the auxiliary ionic polymer preferably contains at least 20% by weight, or at least 17.5% by weight, or at least 15% by weight, or at least 12.5% by weight, or at least 10% by weight. weight, or at least 7.5% by weight, or at least 6.0% by weight, or at least 5.0% by weight of ionic monomer units.
[000299] Preferably, the auxiliary ionic polymer contains at least 50% by weight, or at least 60% by weight, or at least 70% by weight, or at least 80% by weight, or at least 90% by weight, or at least 95% by weight, or about 100% by weight, of ionic monomer units, preferably cationic monomer units, or ionic monomer units.
[000300] Preferably, the average molecular weight of Mw of the auxiliary ionic polymer, which can be measured, for example, by GPC, is at least 5,000,000 g / mol, or at least 4,000,000 g / mol, or at least minus 3,000,000 g / mol, or at least 2,500,000 g / mol, or at least 2,000,000, or at least 1,750,000 g / mol, or within the range of 500,000 g / mol to 1,500,000 g / mol mol.
[000301] Preferably, the average molecular weight of Mw weight of the auxiliary ionic polymer is within the range of 500,000 ± 300,000 g / mol, 600,000 ± 300,000 g / mol, 700,000 ± 300,000 g / mol, 800,000 ± 300,000


[000302] Preferably, the ionic polymer and the auxiliary ionic polymer have a different ionicity (i.e., the content of ionic monomer units relative to the total number of monomer units), and / or average molecular weight.
[000303] In a preferred embodiment, the ionicity of the auxiliary ionic polymer is higher than the ionicity of the ionic polymer, that is, the content of ionic monomer units relative to the total number of monomeric units of the auxiliary ionic polymer is higher than that of the ionic polymer.
[000304] In a preferred embodiment, the relative difference between the ionicity (i.e., the content of ionic monomer units relative to the total number of monomer units) of the auxiliary ionic polymer and the ionicity of the ionic polymer is at least 5% in mol, or at least 10 mol%, or at least 15 mol%, or at least 20 mol%, or at least 25 mol%, or at least 30 mol%, or at least 35 mol%, or at least 40 mol%, or at least 45 mol%, or at least 50 mol%, or at least 55 mol%, or at least 60 mol%, or at least 65 mol%, or at least at least 70 mol%, or at least 75 mol%. For example, when the difference above amounts to at least 40 mol% and the ionic polymer has an ionicity of, for example, 30 mol%, then the ionicity of the auxiliary ionic polymer is at least 70 mol%.
[000305] In a preferred embodiment, the ionic polymer and the auxiliary ionic polymer, according to the invention, are derived from the same monomers and comonomers. For example, when the ionic polymer and the auxiliary anionic polymer are both cationic, they are preferably derived from monomer compositions containing the same cationic monomers, and, optionally, the same comonomers. Typically, however, the absolute content, as well as the weight ratio relative to the comonomers contained in said monomer compositions, differ from each other.
[000306] In a preferred embodiment, the weight average molecular weight of the ionic polymer is higher than the weight average molecular weight of the auxiliary ionic polymer.
[000307] Preferably, the average molecular weight of the ionic polymer is at least twice as high as the average molecular weight of the auxiliary ionic polymer, more preferably at least three times, even more preferably at least four times, even more preferably at least five times, more preferably at least six times, and particularly at least seven times as high as the weight average molecular weight of the auxiliary ionic polymer.
[000308] Preferably, the relative ratio of the weight average molecular weight of the auxiliary ionic polymer to the weight average molecular weight of the ionic polymer is within the range of 1: 2 to 1: 106, or 1: 3 to 1: 105, or 1: 4 to 1: 104, or 1: 5 to 1: 1000, or 1: 6 to 1: 500, or 1: 7 to 1: 400.
[000309] In a preferred embodiment, the relative ratio of the weight average molecular weight of the auxiliary ionic polymer to the weight average molecular weight of the ionic polymer is within the range of 1: (7 ± 6), or 1: (10 ± 6), or 1: (13 ± 6), or 1: (16 ± 6), or 1: (19 ± 6) or 1: (22 ± 6), or 1: (25 ± 6), or 1: (28 ± 6).
[000310] In a particularly preferred embodiment, (i) the ionic polymer is a cationic polymer comprising cationic monomer units derived from N, N, N-trialkylammonylalkyl (meth) acrylate with a counter anion, preferably N, N, N -trimethylamoniaalkyl (meth) acrylate, more preferably N, N, N-trimethylammonethyl (meth) acrylate; or N, N, N-trialkylammonylalkyl (meth) acrylamide with a counter anion, preferably N, N, N-trimethylammonylalkyl (meth) acrylamide, more preferably N, N, N-trimethylammonpropyl (meth) acrylamide; or diallyldialkyl ammonium halide, preferably diallyldimethyl ammonium halide; and (ii) the auxiliary ionic polymer is a cationic polymer comprising monomer units derived from N, N, N-trialkyl-moniaalkyl (meth) acrylamide with a counter anion, preferably N, N, N-trimethylammonalkyl (meth) acrylamide, more preferably N, N, N-trimethylamoniapropyl (meth) acrylamide.
[000311] Preferably, (i) the ionic polymer has an ionicity within the range of 20 to 45 mol%, more preferably 30.5 ± 15 mol%, more preferably 30.5 ± 7.5 mol%; and (ii) the auxiliary ionic polymer has an ionicity of at least 80 mol%, more preferably at least 85 mol%, even more preferably at least 90 mol% and, in particular, at least 95 mol%.
[000312] The auxiliary ionic polymer and the ionic polymer can be added to the thick stock in different or identical dosages.
[000313] In a preferred embodiment, (i) the ionic polymer, preferably cationic polymer is added to the thick stock at a dosage of 50 to 6000 g / t, or 100 to 5000 g / t, or 200 to 4000 g / t, or 300 to 3000 g / t, or 400 to 2000 g / t, or 450 to 1500 g / t or 500 to 1000 g / t, based on the total composition containing the cellulosic material; and (ii) the auxiliary ionic polymer, preferably cationic polymer, is added to the thick stock at a dosage of 10 to 400 g / t, or 20 to 300 g / t, or 30 to 250 g / t, or 40 to 200 g / t, or 50 to 175 g / t, or 60 to 150 g / t, or 75 to 125 g / t, based on the dry weight of the auxiliary ionic polymer and the weight of the total composition containing the cellulosic material.
[000314] The particularly preferred embodiments E1 to E6 concerning the ionic polymer and the auxiliary ionic polymer, according to the invention, are summarized in Table 3 here below: Table 3:

1 trimethylammoniapropylacrylamide 2 trimethylammonia ethylacrylate
[000315] Particularly preferred embodiments of the method according to the invention relate to combinations of any of the embodiments A1 to A6 as summarized in Table 1 with any of the embodiments E1 to E6 as summarized in Table 3; particularly A1 + E1, A1 + E2, A1 + E3, A1 + E4, A1 + E5, A1 + E6; A2 + E1, A2 + E2, A2 + E3, A2 + E4, A2 + E5, A2 + E6; A3 + E1, A3 + E2, A3 + E3, A3 + E4, A3 + E5, A3 + E6; A4 + E1, A4 + E2, A4 + E3, A4 + E4, A4 + E5, A4 + E6; A5 + E1, A5 + E2, A5 + E3, A5 + E4, A5 + E5, A5 + E6; A6 + E1, A6 + E2, A6 + E3, A6 + E4, A6 + E5, or A6 + E6.
[000316] Depending on the procedure used for the preparation of the ionic polymer and the auxiliary ionic polymer, according to the invention, the respective polymer products may additionally comprise substances such as polyfunctional alcohols, water-soluble salts, chelating agents, initiators of free radical and / or their respective degradation products, reducing agents and / or their respective degradation products, oxidants and / or their respective degradation products, etc.
[000317] The ionic polymer and the auxiliary ionic polymer, according to the invention, can be solid, in the form of a solution, dispersion, emulsion or suspension.
[000318] For the purpose of the specification, the term "dispersion" preferably comprises aqueous dispersions, water-in-oil dispersions and oil-in-water dispersions. A technician in the field knows the meaning of these terms; in this regard, it can also refer to EP 1 833 913, WO 02/46275 and WO 02/16446.
[000319] Preferably, the ionic polymer and the auxiliary ionic polymer, according to the invention, is dissolved, dispersed, emulsified or suspended in a suitable solvent. The solvent can be water, an organic solvent, a mixture of water with at least one organic solvent or a mixture of organic solvents.
[000320] In another preferred embodiment, the ionic polymer and the auxiliary ionic polymer, according to the invention, independently of each other, is in the form of a solution, in which the polymer is dissolved in water with the only solvent or in a mixture comprising water and at least one organic solvent.
[000321] More preferably, the ionic polymer and the auxiliary ionic polymer, according to the invention, independently of each other, is in the form of a dispersion, an emulsion or a suspension, in which the polymer is dispersed, emulsified or suspended in a mixture comprising water and at least one organic solvent. Preferably, the polymer is in the form of a dispersion, an emulsion or a suspension, in which the polymer is dispersed, emulsified or suspended in water as the only solvent, that is, no organic solvent is present. In another preferred embodiment of the invention, the ionic polymer and the auxiliary ionic polymer, according to the invention, independently of each other, is in the form of a dispersion, in which the polymer is dispersed in water as the only solvent, or in a mixture comprising water and at least one organic solvent. It is especially preferred that the ionic polymer, preferably dispersion of cationic polymer or anionic polymer, according to the invention, is substantially oil-free.
[000322] In a preferred embodiment, the content of the ionic polymer and the auxiliary ionic polymer, according to the invention, independently of each other, in the solution, dispersion, emulsion or suspension is at least 50% by weight, or at least 40% by weight, or at least 30% by weight, or at least 20% by weight, or at least 10% by weight based on the total weight of the solution, dispersion, emulsion or suspension.
[000323] Suitable organic solvents are preferably low molecular weight alcohols (e.g., methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, etc.), ethers low molecular weight (e.g., dimethylether, diethylether, di-n-propylether, diisopropylether, etc.), low molecular weight ketones (e.g. acetone, butan-2-one, pentane-2-one, pentane-3-one, etc.), low molecular weight hydrocarbons (for example, n-pentane, n-hexane, petroleum ether, ligroin, benzene, etc.) or low molecular weight halogenated hydrocarbons (for example, chloride methylene, chloroform, etc.) or mixtures thereof.
[000324] When the polymer is used in the form of a dispersion, the ionic polymer, preferably dispersion of cationic polymer or anionic polymer, which is preferably substantially oil-free, has a density of 550 to 2,000 kg / m3, or 650 to 1,800 kg / m3, or from 750 to 1,600 kg / m3, or from 850 to 1,400 kg / m3, or from 950 to 1,200 kg / m3.
[000325] In a preferred embodiment, the ionic polymer, preferably dispersion of cationic polymer or anionic polymer, according to the invention, which is preferably substantially oil-free, has a product viscosity of 1,000 to 20,000 mPa s, or 3,000 at 18,000 mPa s, or from 5,000 to 15,000 mPa s, or from 8,000 to 12,000 mPa s, or from 9,000 to 11,000 mPa s.
[000326] When the ionic polymer, preferably cationic polymer or anionic polymer is employed in the form of a polymer solution, the ionic polymer, preferably solution of cationic polymer or anionic polymer preferably has a density of 550 to 2,000 kg / m3, or from 650 to 1,800 kg / m3, or from 750 to 1,600 kg / m3, or from 850 to 1,400 kg / m3, or from 950 to 1,100 kg / m3.
[000327] In a preferred embodiment, the ionic polymer, preferably solution of cationic polymer or anionic polymer has a product viscosity of 300 to 3,000 mPa s, or 500 to 2,750 mPa s, or 1,000 to 2,500 mPa s, or from 1,500 to 2,250 mPa s, or from 1,900 to 2,100 mPa s.
[000328] When the ionic polymer, preferably cationic polymer or anionic polymer is employed in the form of a polymer emulsion, the ionic polymer, preferably emulsion of cationic polymer or anionic polymer preferably has a density of 550 to 2,000 kg / m3, or from 650 to 1,800 kg / m3, or from 750 to 1,600 kg / m3, or from 850 to 1,400 kg / m3, or from 900 to 1,300 kg / m3.
[000329] In a preferred embodiment, the ionic polymer, preferably emulsion of cationic polymer or anionic polymer has a product viscosity of 1,000 to 3,500 mPa s, or 1,200 to 3,250 mPa s, or 1,400 to 3,000 mPa s, or from 1,600 to 2,700 mPa s, or from 1,800 to 2,200 mPa s.
[000330] The ionic polymer, preferably cationic polymer or anionic polymer, according to the invention, can also be a solid, that is, in particulate form, such as in the form of granules, pellets or powders.
[000331] Preferably, the ionic polymer, preferably granules of cationic polymer or anionic polymer has a mass density of 100 to 1,000 kg / m3, or 200 to 900 kg / m3, or 300 to 800 kg / m3, or 450 to 700 kg / m3, or 550 to 675 kg / m3.
[000332] Preferably, the solid ionic polymer, preferably particles of cationic polymer or anionic polymer (i.e., granules, pellets, dust particles, etc.) has an average diameter of 100 to 5,000 μm, or 100 to 4,000 μm, or from 100 to 3,000 μm, or from 100 to 2,000 μm, or from 100 to 1,000 μm.
[000333] The ionic polymer, preferably cationic polymer or anionic polymer in the form of a solution, dispersion, emulsion, suspension, granulate, pellet, or powder, is preferably dispersed, emulsified, suspended, dissolved or diluted in a suitable solvent, such as water, an organic solvent, a mixture of water with at least one organic solvent, or a mixture of at least two organic solvents, before being added to the cellulosic material.
[000334] In a particularly preferred embodiment of the method according to the invention, the biocide comprises an inorganic ammonium salt in combination with a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt thereof; preferably NH4Br / NaOCl; which is preferably added before or during pulping; and - the ionic polymer is a cationic polymer which in turn is a copolymer derived from acrylamide and dialkylaminoalkyl (meth) acrylates or dialkylaminoalkyl (meth) quaternized acrylamides; preferably quaternized dialkylaminoalkyl (meth) acrylamides (i.e., trialkylammonylalkyl (meth) acrylamides); which is preferably added to the cellulosic material in the thick stock area.
[000335] The method according to the invention is suitable for the production of paper, cardboard or cardboard. Preferably, paper, cardboard or cardboard has an area weight of less than 150 g / m2, from 150 g / m2 to 600 g / m2, or more than 600 g / m2. In a preferred embodiment, the area weight is within the range of 15 ± 10 g / m2, or 30 ± 20 g / m2, or 50 ± 30 g / m2, or 70 ± 35 g / m2, or 150 ± 50 g / m2.
[000336] In a preferred embodiment, starch is added to the cellulosic material in the paper-making machine. Due to the unexpected advantages of the invention, the amount of starch that needs to be added in order to achieve the desired properties is reduced, as the non-degraded starch, which was originally contained in the cellulosic material, has been fixed to the cellulosic fibers by means of the cationic polymer, at least to a certain extent, whereby the starch that is optionally added to the cellulosic material in the papermaking machine is also attached to the cellulosic fibers by means of the cationic polymer, at least to a certain extent.
[000337] For the purpose of the specification, the term "fixed" and "fixation" must involve both the fixation of freshly added starch, as well as the fixation of starch that is already contained in the system ("refixation"), for example , originates from the discharge water.
[000338] It is known to one skilled in the art that a compound that has three properties can be referred to as a "retention aid".
[000339] The ionic polymer, preferably cationic polymer or anionic polymer, according to the invention, and the auxiliary ionic polymer, according to the invention, can be used in combination with an additional retention aid. The term "retention aid", as used here, refers to one or more components that, when applied to a stock of cellulosic material, improve retention compared to a stock of cellulosic material in which no retention aid is present. Suitable retention aids that can be used in combination with the ionic polymer, preferably cationic polymer or anionic polymer, according to the invention, are preferably anionic microparticulate materials, including anionic inorganic particles, anionic organic particles, soluble anionic vinyl addition polymers in water, aluminum compounds, and combinations thereof.
[000340] Inorganic anionic particles that can be used in combination with the ionic polymer, preferably cationic polymer or anionic polymer, according to the invention, include anionic silica-based particles and smectite clays.
[000341] Anionic silica-based particles, i.e. particles based on SiO2 or silicic acid, include colloidal silica, different types of polysilisic acid, modified colloidal aluminum silica, aluminum silicates, and mixtures thereof. Anionic silica-based particles are usually supplied in the form of aqueous colloidal dispersions, so called suns.
[000342] Smectite clays that are suitable for use in combination with the ionic polymer, preferably cationic polymer or anionic polymer, according to the invention, include montmorillonite / bentonite, hectorite, beidelite, nontronite and saponite, preferably bentonite.
[000343] Anionic organic particles which are preferably used in combination with the ionic polymer, preferably cationic polymer or anionic polymer, according to the invention, include crosslinked anionic vinyl addition polymers and copolymers derivable from an anionic monomer, such as acrylic acid , methacrylic acid and sulphonated vinyl addition monomers, which can be copolymerized with nonionic monomers, such as (meth) acrylamide or alkyl (meth) acrylates; and anionic condensation polymers, such as melamine-sulfonic acid sols.
[000344] Aluminum compounds which are preferably employed with the cationic polymer according to the invention include alum, aluminates, such as sodium aluminate, aluminum chloride, aluminum nitrate and polyaluminium compounds. Suitable polyaluminium compounds are, for example, polyaluminium chlorides, polyaluminium sulphates, polyaluminium compounds containing both chloride and sulphate ions, polyaluminium silicate, polyaluminium compounds and mixtures thereof. Polyaluminium compounds can also contain other anions, including anions derived from phosphoric acid, sulfuric acid, citric acid and oxalic acid.
[000345] Preferably, the ionic polymer, preferably cationic polymer or anionic polymer, and the additional retention aid, are employed in such a way that the retention is improved compared to the cellulosic material containing, or the ionic polymer alone, or the retention aid additional alone.
[000346] In a preferred embodiment of the invention, the method comprises the additional step of (j) employing an auxiliary additive typically used in the production of paper.
[000347] The invention can be used in combination with other compositions in order to further improve the strength properties of the paper product. The compositions that can be used in combination with the invention can be a cationic polymer, or an anionic polymer, or an amphoteric polymer, or a synthetic non-ionic polymer, or a natural polymer, or combinations thereof. For example, the invention can be used in conjunction with a cationic starch or an amphoteric starch.
[000348] In a preferred embodiment, the method according to the invention does not involve the addition of cellulosic enzymes to the cellulosic material, preferably not the introduction of at least one cellulosic enzyme composition, and at least one cationic polymer composition to a pulp papermaking process at about the same time to form a treated pulp.
[000349] In particularly preferred embodiments of the method according to the invention, (i) in step (b), the one or more biocides are continuously or discontinuously added to the cellulosic material in quantities so that -after 1 month of treatment in a papermaking facility that operates continuously, the pH value of the aqueous phase of the cellulosic material has been increased by at least 0.2 pH units, compared to the pH value that has been measured, preferably at the same location, preferably at the end entrance wetting of the paper-making machine immediately before the biocide was added for the first time, or before the addition of higher amounts of biocide than conventionally employed was initiated, that is, compared to a situation where micro-organisms were degrading starch ; and / or - after 1 month of treatment in a paper-making plant that operates continuously, the electrical conductivity of the aqueous phase of the cellulosic material has been decreased by at least 5%, preferably at least 20%, more preferably at least 50%, compared to the electrical conductivity that was measured, preferably at the same location, preferably at the wet end entrance of the papermaking machine immediately before the biocide was added for the first time, or before the addition of higher amounts of biocide than conventionally employed. initiated, that is, compared to a situation where microorganisms were degrading starch; and / or -after 48 hours, preferably after 8 hours in a paper-making plant that operates continuously, the extinction of the starch (corresponding to the use of the free starch concentration) contained in the aqueous phase of the cellulosic material has been increased by at least 5 %, compared to the extinction that was measured, preferably at the same location, preferably at the wet end entrance of the papermaking machine just before the biocide was added for the first time, or before the addition of higher amounts of biocide than conventionally employed be initiated, that is, compared to a situation where microorganisms were degrading starch; and / or -after 48 hours, preferably after 8 hours in a paper-making plant that operates continuously, the concentration of ATP in the aqueous phase of the cellulosic material has been decreased by at least 5%, compared to the concentration of ATP that has been measured, preferably at the same location, preferably at the entrance to the wet end of the papermaking machine immediately before the biocide is added for the first time, or before the addition of higher amounts of biocide than conventionally employed is initiated, i.e. , compared to a situation where microorganisms were degrading starch; and / or -after 48 hours, preferably after 8 hours in a paper-making plant that operates continuously, the redox potential of the aqueous phase of the cellulosic material has been increased to an absolute value of at least -75 mV; and / or (ii) the one or more biocides comprise an ammonia salt; preferably NH4Br in combination with a halogen source, preferably a chlorine source, more preferably hypochlorous acid or a salt thereof; and / or the one or more biocides comprise an ammonia salt, preferably NH4Br in combination with hypochlorous acid or a salt thereof, as the first biocide and an organic biocide, preferably non-oxidizing biocide as an additional biocide; (iii) the one or more biocides comprise an oxidizing biocide which is used at a concentration equivalent to a concentration of at least 0.005% of active substance as Cl2 per ton of paper produced, more preferably at least 0.010% of active substance as Cl2 per ton of paper produced; and / or (iv) the one or more biocides are added to the thick stock, preferably at least a portion of it is added to the dilution water for the pulper; and / or (v) the ionic polymer is added in combination with an auxiliary ionic polymer; and / or (vi) the ionic polymer and / or the auxiliary ionic polymer are cationic; preferably independently of one another, trialkylammonylalkyl (meth) acrylamide derivatives and / or (vii) the starting material comprises virgin pulp or recycle pulp.
[000350] In a papermaking facility that operates continuously, in which paper production can optionally be transiently stopped for maintenance purposes, a preferred embodiment of the invention includes the steps: (A) measuring a property of the aqueous phase of the cellulosic material selected from the group consisting of electrical conductivity, redox potential, pH, ATP concentration and free starch concentration; in a predetermined location of the papermaking facility, preferably in a location in the thick stock area, or in the thin stock area; (B) production of paper, cardboard or cardboard, by the method according to the invention comprising steps (a), (b), (h1) and, optionally, (h2); (C) measurement of the same property as measured in step (A), preferably at the same location, preferably at the entrance to the wet end of the papermaking machine of the papermaking facility as in step (A), after time Δt, preferably after 1, 2, 3, 4, 5, 10, 14, 21 or 28 days, and comparing the value measured in step (C) with the value measured in step (A); and (D) regulation, preferably optimizing the biocide dosage added in step (b), and / or the ionic polymer dosage added in step (h1), and / or the auxiliary ionic polymer dosage optionally added in step (h2) depending on the result of the comparison made in step (C).
[000351] For the proposal of the specification, optimization preferably means that in the minimized consumption of biocide, the ionic polymer and the auxiliary ionic polymer, respectively, the substantial change of the measured value (m2 vs. m1) is prevented.
[000352] Another aspect of the invention relates to a method as described above for (re-) fixing starch to cellulosic material, preferably to cellulose fibers. This method, according to the invention, serves the proposal of refixing the starch that is originally contained in the starting material (for example, virgin pulp) and / or fixing the starch that has been added anywhere to the cellulosic material, preferably to the fibers of cellulose, thus resulting in a recycling of the starch. All preferred embodiments that have been described above in conjunction with the method according to the invention also apply to this aspect of the invention and, therefore, are not repeated hereinafter.
[000353] Yet another aspect of the invention relates to the use of the ionic polymer, preferably cationic polymer or anionic polymer, as defined above, or the combination of the ionic polymer, preferably cationic polymer or anionic polymer, with the auxiliary ionic polymer, preferably cationic polymer or anionic polymer as defined above, in the method for producing paper, cardboard or cardboard, to increase the strength of paper, cardboard or cardboard, to increase drainage and / or production rate of the papermaking machine, and / or to reduce the effluent COD in the papermaking process, as described above, and / or for (re-) fixing starch to the cellulosic material, preferably to the cellulose fibers. All of the preferred embodiments that have been described above, together with the methods according to the invention, also apply to this aspect of the invention and, therefore, are not repeated hereinafter.
[000354] Yet another aspect of the invention relates to the use of the biocide as defined above in the method for producing paper, cardboard or cardboard, to increase the strength of paper, cardboard or cardboard, to increase drainage and / or production rate of papermaking machine, and / or to reduce the effluent COD in the papermaking process as described above, and / or for (re-) fixing the starch to the cellulosic material, preferably to the cellulose fibers. All of the preferred embodiments that have been described above in conjunction with the methods according to the invention, also apply to this aspect of the invention and, therefore, are not repeated hereinafter.
[000355] Another aspect of the invention relates to the use of the auxiliary additive, as defined above, in the method for the production of paper, cardboard or cardboard, to increase the resistance of paper, cardboard or cardboard, to increase drainage and / or rate for the production of the papermaking machine, and / or to reduce the effluent COD in the papermaking process, as described above, and / or for (re-) fixing starch to the cellulosic material, preferably to the cellulose fibers. All preferred embodiments that have been described above in conjunction with the methods according to the invention also apply to this aspect of the invention and, therefore, are not repeated hereinafter. EXAMPLES
[000356] The following experiments were operated on different commercially used paper mills across Europe. Examples 1 and 4 were operated in a closed system, so the other Examples were operated in an open system. The starting material in each case was 100% recycled paper.
[000357] The following biocides and polymers were used in the following dosages and feeding points are summarized in Table 4 below: Table 4:

CEPI - Confederation of European Paper Industries
[000358] For a comparative proposal, it should be noted that the ammonia bromide biocide is conventionally used in the dosages of 0.005 to 0.008% of active substance as Cl2 per ton of paper produced, that is, the dosage used in the experiments according to the invention is 2 to 10 times higher than the conventional dosage. Example 1 - Use of fit A (experiments showing the effects on microbial degradation and starch fixation in cellulose when using (a) Aux. Poly A, but no biocides or Poly A; (b) Aux. Poly A and biocides, but no Poly A; and (c) Poly A, Biocidal and Poly A Aids:
[000359] The positive impact of the combined use of a biocide and a cationic polymer, according to the invention, was studied by the following experiment.
[000360] The biocide employed was a combination of a two-component oxidizing biocide comprising (a) 35% NH4Br and 13% NaOCl as an inorganic biocide, prepared in situ according to EP-A 517 102, EP 785 908 , EP 1 293 482 and EP 1 734 009; and (b) bronopol / 5-chloro-2-methyl-2H-isothiazole-3-one / 2-methyl.2H-isothiazole-3-one (BNPD / Iso) as an organic biocide.
[000361] The cationic polymer employed was an acrylic amide copolymer (approx. 69 mol%) and NN-dimethylaminopropyl quaternized acrylamide (DIMAPA-Quat.) (Approximately 31 mol%), having a molecular weight of approximately 10,000,000 - 20,000,000 g / mol, in the following also referred to as "Poly A" or "Polymer A".
[000362] As revealed in Table 4 above, all examples use an auxiliary cationic polymer in addition to Poly A, which, for convenience, will be described here. The auxiliary cationic polymer is a homopolymer of DIMAPA-Quat. (100 mol%), having a molecular weight of> 100,000 g / mol, in the following also referred to as "Aux. Poly A", or "Auxiliary polymer A".
[000363] First, a thick stock of recycled fibers having a consistency of 35 to 45 g / L (corresponding to 3.5 to 4.5% consistency) cepi 1.04 reference compound was subjected to a pulping step.
[000364] By means of a comparative cone laying study using an Imhoff funnel, the positive impact of the biocide and the cationic polymer on the remaining starch can then be made visible. The clear filtrate of a polydisk fiber recovery device was taken under 3 different conditions as described below.
[000365] Experiment a: The filtrate was treated with Aux. poly A, but none with a biocide, nor with Poly A. As a result, the filtrate has a high turbidity, containing lots of degradation products.
[000366] Experiment b: The filtrate was treated with biocide and Aux. poly A, but not with Poly A. As a result, the starch was prevented from microbiological degradation and settled at the bottom of the funnel.
[000367] Experiment c: The filtrate was treated with biocide, Poli A and Aux. poly A, according to the invention. As a result, the starch has been prevented from microbiological degradation and can therefore be attached to the thick stock in its original properties. The starch was therefore not present in the filtrate, and the filtrate was thus determined with low consistency.
[000368] The test by means of the polydisk fiber recovery device revealed that only in the experiment and the total solution was removed, that is, the starch can be prevented from being degraded, and be effectively fixed to the cellulose fibers. In experiment a (absence of biocide and Poli A), however, the total solution exhibited substantial turbidity, indicating several degradation products that cannot be effectively filtered by the polydisk fiber recovery device. In experiment b (absence of Poli A), there is a starch settlement indicating that the starch can be prevented from being degraded; however, it cannot be effectively fixed on cellulose fibers.
[000369] Experiments (a), (b) and (c) illustrate the importance of using everyone, the biocide, Poli A and Aux. poly A, in order to prevent microbiological degradation and fix and / or fix the starch to the cellulose fibers of the thick stock. Example 2 - Use of adjustment A (experiments showing effects of starch fixation, turbidity and drainage when using various amounts of Poly A in conjunction with constant amounts of Poly Aids and biocide):
[000370] In the following experiment, the biocide and the cationic polymer, according to Example 1, were applied to a papermaking process as follows:
[000371] A thick stock of recycled fibers having a consistency of 35 to 45 g / L composed of, any reference cepi 1.04 or 4.01, was subjected to a pulping step before being treated with biocide in order to prevent starch degradation.
[000372] Poli A, as well as Aux. poly A, was then added to the thick stock of the recycled pulp and mixed with said pulp to simulate the addition of the machine's box. Then, the sample was diluted, either with tap water, or white water, to a thin stock of material having a concentration of 7 to 9 g / L. A standard auxiliary retention program was then added, and the sample was placed on a VDT device (vacuum drainage test), or on a DFR device for analysis (DFR = Freeness Retention Drainage). A DFR device simulates the retention and drainage conditions that prevail in a papermaking machine just before and during sheet formation.
[000373] The VDT is a cushion-forming device, meaning that the pulp is drained under vacuum on filter paper, resulting in the formation of a cushion. The VDT used here consists of a Büchner funnel (diameter: 15 mm) that is placed in a vacuum flask connected to a vacuum pump (LABOPORT, type N820 AN 18). For VDT experiments, the thin pulp is transferred to the Büchner funnel and subsequently transferred by gravity to the vacuum dehydration chamber. The drainage rate (in seconds) was calculated by determining the time required to collect 100, 200, 300 and 400 mL of filtrate, or white water. Additionally, the vacuum was determined using a vacuum measuring device, and the filtrate was used to determine turbidity, evolution of starch concentration (iodine test) and ionic demand.
[000374] For the starch concentration test, 10 mL of the filtrate was mixed with 5 mL of tap water, and 10 mL of acetic acid, and placed in a spectrometer (HACH DR 2010). For measurements, a wavelength of 550 nm was selected and the absorbance was adjusted to zero%. To the sample, 100 μL of an N / 10 iodine solution was added and the resulting solution was mixed.
[000375] A positive starch test shows a range of color from blue to purple. A negative starch test shows a yellowish color. Up to an absorbency of 1.5, the color intensity is directly proportional to the starch concentration. Amylose is the portion of starch that is responsible for the formation of the deep blue color in the presence of iodine. In contrast, amylopectin starch does not give a blue color. Native starch usually has its maximum absorbance at 550 nm, and cationic starch at 620 nm.
[000376] According to the procedure as described above, a variety of experiments were conducted with varying amounts of Poli A in each case in combination with constant amounts of Aux. poly A, using batches other than thick stock (composed of any reference cepi 1.04 or 4.01, and having been treated with either biocide a, or biocide b). For each batch, a comparative experiment (bench test) was conducted, in which treatment with Poli A was omitted (ref. 1-7), but treatment with Aux. poly A was continued. This example was performed using adjustment A. As shown in Table 4 above, auxiliary polymer A (Aux. Poly A) was dosed at 400 g / ton of paper, and its dose was kept constant. The dose of Poli A was varied within the range of 600 to 1000 g / ton of paper, as additionally specified (expressed in kg) in Table 5.
[000377] The results of the VDT tests (vacuum drainage tests) are represented in Figures 1-5 and summarized in Table 5 here below: Table 5 (1st part):

Table 5 (2nd part):

Table 5 (3rd part):


[000378] If the comparative examples (ref. 4, ref. 5 and ref. 6) (biocide + Aux. Poly A, but no Poly A) are compared with the examples of the invention containing different amounts of Poly A (0.5 , 1.0, 1.5 and 2.0 kg / metric ton) (biocide + Aux. Poly A + Poly A), it is clear that the concentration of starch in the filtrate was significantly reduced by the presence of Poli A. For example, with 1.0 kg / metric ton of Poly A, the starch concentration was reduced by 50-65%. The starch concentration is reduced with an increased amount of Poli A. As can be seen from a comparison of the examples of the invention, the optimum dose for Poli A in this embodiment is about 1.0 kg / metric ton. When Poli A was applied to the cellulosic material in an amount of 0.5 kg / metric ton, a small positive effect can still be observed.
[000379] Apparently, part of the starch had not been released into the solution, but had been retained in the fiber, or had been refixed to the fiber instead.
[000380] The results of the turbidity studies are shown in Figure 1 and Table 5.
[000381] If the comparative examples (ref. 1-7) (biocide + Aux. Poly A, but no Poly A) are compared to the examples of the invention containing different amounts of Poly A (0.5, 1.0, 1, 5 and 2.0 kg / metric ton) (biocide + Aux. Poly A + Poly A), it is clear that due to the presence of Poly A, the turbidity of the solution is reduced. In the case of the batch of day 3 (cepi 4.01), for example, with 1.0 kg / metric ton of Poly A, the starch concentration had been reduced from 200 NTU to 24.5 NTU. Except for one case, turbidity had been reduced by more than 67%.
[000382] Both tests imply that the residual starches are attached to the fibers, which results in an improvement of medium strength for the paper, and in clear water more removed.
[000383] Regarding the VDT studies, Table 5 shows the drainage rate (time to obtain 100, 200, 300 and 400 mL of filtrate) and the time to reach the maximum vacuum for the pulp. The drainage curves are additionally shown in Figure 2. Generally, the time to reach the maximum vacuum has been significantly reduced in the presence of the cationic Poly A polymer, resulting in a higher average vacuum, and a reduced drainage rate.
[000384] During the drainage process, the maximum vacuum and minimum vacuum are measured, and the difference is calculated as an indication for the floc size, higher floc size will mean a degraded formation. After the drainage procedure, the wet weight of the resulting pad is determined before it is dried for 2 hours in an oven set at 105 ° C and the dry weight is determined. The higher the dry bone value (percentage of dry pad vs. wet pad: The highest average drying pad), the drier the pad will leave the drainage process, and the drier a corresponding sheet would reach the press section of the process. corresponding papermaking process. The results of the floc size and dry bone weight studies, depending on the Poly A content, are shown in Table 5 and Figure 4.
[000385] If the comparative examples (ref. 1-7) (biocide + Aux. Poly A, but no Poly A) are compared to the examples of the invention containing different amounts of Poly A (0.5, 1.0, 1, 5 and 2.0 kg / metric ton) (biocide + Aux. Poly A + Poly A), it is clear that by increasing the level of Poli A, all parameters related to drainage: Drainage curves - "Water Line" - Bone drying reflects the positive trend (Figures 3-5). Regarding the VDT results, it is clear that Poli A improves the VDT in all parameters. Example 3 - Use of adjustment A (laboratory simulation experiments showing the effects on drainage, retention and turbidity when using Poly A / Poly Aids and no Poly A / Poly A Aids, respectively):
[000386] Four thin stocks of cellulosic material containing different amounts of Poli A (0,5,1,0,1,5 or 2,0 kg / metric ton), Aux. poly A and the standard retention aid, were prepared and analyzed according to Example 2, that is, the polymers were dosed to the thick stock which was subsequently diluted to produce thin stock. Additionally, a comparative experiment (bench test) was conducted, in which the treatment with Poli A and Aux. poly A has been omitted.
[000387] The data from the DFR experiments are represented in Figures 6 to 10 and summarized in Table 6 here below: Table 6:


[000388] The results of the turbidity study show that turbidity is already reduced with 0.5 kg / metric ton of Poly A (Table 4 and Figure 5), which is again an indication for effective starch fixation.
[000389] Regarding the DFR results, it is clear that the retention and drainage were also improved by the presence of Poli A (Table 4 and Figures 7-10). The extent to which both retention and drainage have been improved depends on the amount of Poly A added.
[000390] Altogether, the tests carried out indicate that Poli A in combination with Aux. poly A improves the fixation of undegraded starch when added to the thick stock of recycled fiber treated with a biocide. This effect is expected to translate into an improvement in the strength of the final paper.
[000391] The following examples were operated on paper-making machines, not in the laboratory, in order to demonstrate that the invention also operates under real conditions. This is important, since it is known to the technician on the subject that in the production of paper, laboratory results cannot always be transferred to industrial scale processes. Example 4 - Use of adjustment A (experiments showing effect on starch reduction in white water when using biocide in combination with only Poly Aids, but in the absence of Poly A, and biocide in combination with Poly A and Poly Aids. ):
[000392] In the following comparative experiment, the combined use of the biocide, the cationic polymer Poly A and the auxiliary cationic polymer Aux. poly A, according to Example 1, was compared to the use of biocide and Aux. poly A only.
[000393] The comparative experiment was operated on a paper-making machine equipped with a closed water recycling circuit, and the paper-making process was monitored for 92 consecutive days.
[000394] In the papermaking process, a thick stock of recycled fibers having a consistency of 35 to 45 g / L made up of mixed supplies was subjected to a pulping step before being treated with the biocide in order to prevent degradation of starch.
[000395] Two conditions were tested within the test period:
[000396] Experiment a) Aux. poly A was added to the thick stock of cellulosic material in the machine box.
[000397] Experiment b) Poli A and Aux. poly A were added to the thick stock of cellulosic material in the machine box.
[000398] A comparative cone nesting study was then conducted. For this study, a filtrate taken from the process water was transferred to a conical glass (Imhof funnel), and the amount of starch sitting at the bottom of the funnel was measured relative to the total volume of the suspension.
[000399] The results of this test are shown in Table 7 below: Table 7:

[000400] It is clear from the table above that the amount of starch in white water solids is reduced by the combined use of biocide, Poli A and Aux. poly A, compared to the use of only the biocide and Aux. poly A. It is also clear that this effect can be "enabled and disabled". Example 5 - Use of D adjustment (experiments showing starch reduction effect in white water when both biocide and Poly A are used in the absence of Poly Aids; and when biocide, Poly A and Poly Aids are used):
[000401] In this experiment, the combined use of the biocide, the cationic polymer Poly A and the auxiliary cationic polymer Aux. poly A, according to Example 1, was compared to the use of the biocide and Poli A only.
[000402] The comparative experiment was operated on a papermaking machine equipped with an open water circuit, and the papermaking process was operated continuously during the full test period. In the papermaking process, a thick stock of recycled fibers having a consistency of 35 to 45 g / L made up of mixed supplies, was subjected to a pulping step before treated with the biocide in order to prevent starch degradation. For this proposal, the white water of the papermaking machine was analyzed using the starch concentration test as revealed in Example 1. During day 1, the cellulosic material was treated with the biocide after the pulping step, and the Poly A cationic polymer was added to the thick stock of cellulosic material in the machine box. In the following days, the auxiliary cationic polymer Aux. poly A was additionally added to the thick stock of cellulosic material in the machine box. The white water of the papermaking machine was analyzed at different times according to the starch concentration test according to Example 1.
[000403] The results of this test are shown in Table 8 here below: Table 8:

[000404] It is apparent from these results that the amount of starch in white water (expressed as iodine absorption) is further reduced when a combination of Poly A and Aux. poly A is applied to the papermaking process. Example 6 - Use of adjustment A (experiments showing the effects on dry resistance in different types of paper when using a combination of biocide, Poly A, and Aux. Poly A):
[000405] The results of the resistance are summarized in Table 9 here below: Table 9:

CMT - Flat Crush of Corrugated Medium Test (measure for corrugated edge flat crush resistance) SCT - Short Span Compression Test (measure for paper compression resistance)
[000406] It is clear from the above experimental results that the method according to the invention substantially increases the dry strength of paper, cardboard and cardboard, in a reduced dosage of dry surface starch. Example 7: - Use of adjustment B (experiments showing that the effects on dry resistance at different base weights when using a combination of biocide, Poly A, and Aux. Poly A):
[000407] The base weight refers to the density of the paper mass (as weight) per number of sheets. The experimental details are contained in Table 13.
[000408] The results of resistance for base weights of 100, 110 and 120 are summarized in Table 10 here below: Table 10:
Example 8 - Use of adjustment C (experiments showing the effects on dry resistance at different base weights when using a combination of biocide, Poly A, and Aux. Poly A):
[000409] The experimental details are contained in Table 13.
[000410] The results of the resistance are summarized in Table 11 below: Table 11:

Example 9 - Use of setting D (experiments showing the effects on dry resistance at different base weights when using a combination of biocide, Poly A, and Aux. Poly A):
[000411] The details of experiments are contained in Table 13.
[000412] The resistance results are summarized in Table 12 below: Table 12:


[000413] It is clear from the above experimental results that the method according to the invention substantially increases the dry strength of paper, cardboard and cardboard. Consequently, the amount of fresh starch applied in the size can be reduced and in the strength maintained, additional synthetic dry strength agents can be omitted altogether, or at least their amount can be reduced.
[000414] Some additional experimental results that were observed during machine operations using Settings A to D are summarized in Table 13 below: Table 13:

1 organic biotin in conventional amounts, absence of NH4Br biocide 2 NH4Br biocide in conventional amounts, absence of organic biocide 3combination of NH4Br biocide with organic biocide in increased amounts as shown in Table 4 Example 10 - Use of adjustment A (experiments showing effect on biocide dosage when Poly A and Poly Aids are used and when Poly A Aids are used
[000415] The role of the ionic polymer in the combination of biocide and auxiliary ionic polymer according to the invention was investigated. For this proposal, the biocide was added in quantities that were sufficient under the given conditions to keep the process parameters below a limit value.
[000416] At the beginning of the experiment, the biocide was used in combination with Poli A and Aux. poly A (where "+" indicates addition). After about a month, however, the addition of Poli A was interrupted (where "-" indicates interruption), while the addition of Aux. poly A was continued, and it was investigated whether the dose of biocide needs to be adapted in order to satisfy the predetermined limit requirement. The results are summarized in Table 14 here below and represented in Figure 10: Table 14:

* expressed as chlorine equivalent concentration in% of active substance as Cl2 per ton of paper produced.
[000417] It is clear from the data above that in the absence of ionic polymer according to the invention, the dose of the biocide must be increased by about 40% (from 0.020 to 0.027) in order to keep the process stable. It appears that in the absence of ionic polymer, the system is enriched with starch, which in turn is a nutrient for microorganisms. Consequently, more biocide is needed in this period in order to suppress microbiological degradation of starch. Example 11 - (laboratory simulation experiments showing the effects on drainage, starch retention and turbidity when using Poly Aids in combination with Poly A, Poly Aids always being added to the thick stock and Poly A being added or in different thick stock locations, or thin stock):
[000418] Four thick stocks (3.5%) of recycled cellulosic material containing biocide, but no polymers have been prepared. All samples were shaken for 50 seconds as thick stock before being diluted in thin stock with clear filtrate to achieve the same similar consistency in the main box of the papermaking machine (0.89%). The supply to the bench remained without any chemicals.
[000419] Samples 2, 3 and 4 were all treated with 300 g / t of Aux. poly A after 5 out of 50 seconds to simulate a previous application of thick stock. Samples 2, 3 and 4 were additionally treated with Poli A (0.6 kg / metric ton for all samples). Sample 2 was treated with Poli A after 10 out of 50 seconds which corresponds to the previous addition of thick stock. Sample 3 was treated with Poli A after 30 out of 50 seconds to simulate the subsequent application of thick stock. Sample 4 was treated with Poli A in thin stock, that is, after dilution, to demonstrate a very late dosage in thin stock.
[000420] The experimental results are summarized in Table 15 below and shown in Figure 11: Table 15:

[000421] The results of the turbidity study show that the turbidity and starch concentration in white water is also reduced when Poli A is added to the slender stock at 0.6 kg / metric ton, which is an indication of an effective starch refixation .
[000422] Regarding the DFR results, it is clear that the retention and drainage were also improved by the presence of Poli A (Table 2 and Figures 7-10). The extent to which both retention and drainage have been improved depends on the feeding point where Poli A was added.
[000423] Altogether, the tests carried out indicate that Poli A, particularly in combination with Aux. Poli A, improves the fixation of non-degraded starch when added to thick stock later, or thin stock of recycled fiber treated with a biocide. This effect is expected to translate into an improvement in the strength of the final paper.

权利要求:
Claims (25)
[0001]
1. Method for the production of paper, cardboard or cardboard, characterized by the fact that it comprises the steps of: (a) pulping a cellulosic material containing starch; (b) treating the cellulosic material containing the starch with one or more biocides; and (h) adding an ionic polymer and an auxiliary ionic polymer to the cellulosic material; the ionic polymer, as well as the auxiliary ionic polymer, is cationic; the ionic polymer having a higher average molecular weight than the auxiliary ionic polymer; the relative difference between the ionicity of the auxiliary ionic polymer and the ionicity of the ionic polymer is at least 5 mol%; where ionicity is the molar content of ionic monomer units relative to the total number of monomer units; the cationic polymer comprising cationic monomer units derived from N, N, N-trialkylammonioalkyl (meth) acrylate, N, N, N-trialkylammonioalkyl (meth) acrylamide or diallylalkyl ammonium halide; and the auxiliary ionic polymer being a cationic polymer comprising monomer units derived from N, N, N-trialkyl-monioalkyl (meth) acrylamide or diallyldialkyl ammonium halide.
[0002]
2. Method according to claim 1, characterized by the fact that the auxiliary ionic polymer has a higher ionicity than that of the ionic polymer; and the relative difference between the ionicity of the auxiliary ionic polymer and that of the ionic polymer is at least 30 mol%.
[0003]
3. Method, according to claim 2, characterized by the fact that: (i) the ionic polymer has an ionicity within the range of 20 to 45 mol%; and (ii) the auxiliary ionic polymer has an ionicity of at least 90 mol%.
[0004]
4. Method according to any one of claims 1 to 3, characterized by the fact that the ionic polymer and / or the auxiliary ionic polymer are added to the cellulosic material in the thick stock area, where the cellulosic material has a consistency of the stock at least 2.0% by weight.
[0005]
5. Method according to any one of claims 1 to 4, characterized by the fact that the ionic polymer and / or the auxiliary ionic polymer are added to the cellulosic material in the thin stock area, where the cellulosic material has a stock consistency less than 2.0% by weight.
[0006]
Method according to any one of claims 1 to 5, characterized by the fact that step (b) prevents microbial degradation of at least a portion of the starch.
[0007]
Method according to any one of claims 1 to 6, characterized by the fact that the starch is a nonionic, anionic, cationic and / or native starch.
[0008]
Method according to any one of claims 1 to 9, characterized by the fact that the one or more biocides are continuously or discontinuously added to the cellulosic material in such a way that: - after 1 month of treatment, the pH value the aqueous phase of the cellulosic material was increased by at least 0.2 pH units, compared to the pH value that was measured immediately before the biocide was added for the first time; and / or - after 1 month of treatment, the electrical conductivity of the aqueous phase of the cellulosic material was decreased by at least 5%, compared to the electrical conductivity that was measured immediately before the biocide was added for the first time; and / or - after 48 hours, the extinction of the starch contained in the aqueous phase of the cellulosic material was increased by at least 5%, compared to the extinction that was measured immediately before the biocide was added for the first time.
[0009]
Method according to any one of claims 1 to 8, characterized by the fact that the one or more biocides are dosed in an amount of at least 5.0 g / metric ton, based on the total amount of the composition containing the cellulosic material and starch.
[0010]
Method according to any one of claims 1 to 9, characterized by the fact that one or more biocides are added to the cellulosic material in the thick stock area, the cellulosic material having a stock consistency of at least 2 , 0%.
[0011]
11. Method according to any one of claims 1 to 10, characterized by the fact that the one or more biocides are added in section (I) and / or (II); and, optionally, also in section (III) and / or (IV) of a papermaking installation comprising a papermaking machine, in which section (I) includes measurements that occur before pulping; section (II) includes measures associated with pulping; section (III) includes measures that occur after pulping, but still outside the papermaking machine; and section (IV) includes measurements that occur within the papermaking machine.
[0012]
12. Method according to any one of claims 1 to 11, characterized in that the one or more biocides comprises an inorganic ammonium salt in combination with a halogen source.
[0013]
13. Method according to any one of claims 1 to 12, characterized in that the one or more biocides are oxidative and / or comprise two components.
[0014]
14. Method according to any one of claims 1 to 13, characterized in that in addition to the one or more biocides added in step (b), an additional biocide is added to the cellulosic material which differs from the one or more biocides added in the step (b).
[0015]
15. Method according to claim 14, characterized by the fact that the additional biocide is added in section (I) and / or (II); and, optionally, also in section (III) and / or (IV) of a papermaking installation comprising a papermaking machine, in which section (I) includes measurements that occur before pulping; section (II) includes measures associated with pulping; section (III) includes measures that occur after pulping, but still outside the papermaking machine; and section (IV) includes measurements that occur within the papermaking machine.
[0016]
16. Method according to claim 14 or 15, characterized by the fact that the additional biocide is non-oxidizing.
[0017]
17. Method according to any one of claims 14 to 16, characterized by the fact that the additional biocide is an organic biocide selected from the group consisting of quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (ADBAC) , poly-- hexamethylenebiguanide (biguanide), 1,2-benzisothiazole-3 (2H) -one (BIT), bronopol (BNPD), bis (trichloromethyl) sulfone, diiodomethyl-p-tolylsulfone, bronopol / quaternary ammonium compounds, benzyl -C12-16-alkyldimethyl chlorides (BNPD / ADBAC), bronopol / didecyldimethylammonium chloride (BNPD / DDAC), bronopol / 5-chloro-2-methyl-2H-isothiazole-3-one / 2-methyl-2H-isothiazole- 3-one (BNPD / Iso), NABAM / sodium dimethyldithiocarbamate, sodium N-dimethyldithiocarbamate, N-dithiocarbamate (NABAM), sodium methyldithiocarbamate, sodium dimethyldithiocarbamate, 5-chloro-2-methyl-4-isothiazolin-3- one (CMIT), 2,2-dibromo-2-cyanoacetamide (DBNPA), DBNPA / bronopol / iso (DBNPA / BNPD / Iso), 4,5-dichloro-2-n-octyl-3-isothiazolin-3-one (DCOIT), didecyldimethylammon chloride (DDAC), didecyldimethylammonium chloride, dimethyl-benzylammonium chloride (DDAC / ADBAC), dodecylguilidine monohydrochloride / quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (DGH / ADBAC), monohydrochloride monohydrochloride / methylene dithocyanate (DGH / MBT), gluteraldehyde (Glut), gluteraldehyde / quaternary ammonium compounds / benzylcoconut alkyldimethyl chlorides (Glut / coconut), gluteraldehyde / didecyldimethylammonium chloride (Glut / DDAC), gluteraldehyde / 5-chloro-2 -methyl-2H-isothiazole-3-one / 2-methyl-2H-isothiazole-3-one (Glut / Iso), gluteraldehyde / methylene dithocyanate (Glut / MBT), 5-chloro-2-methyl-2H-isothiazole- 3-one / 2-methyl-2H-isothiazole-3-one (Iso), methylene dithocyanate (MBT), 2-methyl-4-isothiazolin-3-one (MIT), methanine oxirane (methanes oxirane), sodium bromide (NaBr), nitromethylidinatrimethanol, 2-n-octyl-3-isothiazolin-3-one (OIT), bis (trichloromethyl) sulfone / quaternary ammonium compounds, benzyl-C12-16-alkyldimethyl chlorides (sulfone / ADBAC), simcloseno, te rbutilazine, dazomet (thiona), tetracis (hydroxymethyl) phosphonium sulfate (2: 1) (THPS) and p- [(diiodomethyl) sulfonyl] toluene (tolyl sulfone), and mixtures thereof.
[0018]
18. Method according to any one of claims 1 to 17, characterized by the fact that the ionic polymer and / or the auxiliary ionic polymer is added to the machine housing, mixing box and / or regulation box.
[0019]
19. Method according to any one of claims 1 to 18, characterized in that the ionic polymer and / or the auxiliary ionic polymer has an average molecular weight Mw of at least 100,000 g / mol.
[0020]
20. Method according to any one of claims 1 to 19, characterized in that the ionic polymer and / or the auxiliary ionic polymer comprises non-ionic monomer units derived from acrylamide or methacrylamide.
[0021]
21. Method according to any one of claims 1 to 20, characterized by the fact that the ionic polymer and / or the auxiliary ionic polymer contains at least 5.0 mol% of cationic monomer units.
[0022]
22. Method according to any one of claims 1 to 21, characterized by the fact that: (i) the ionic polymer is added in section (II) and / or (III) and / or (IV); and (ii) the auxiliary ionic polymer is added in section (II) and / or (III) and / or (IV); a papermaking facility comprising a papermaking machine, in which section (II) includes measures associated with pulping; section (III) includes measures that occur after pulping, but still outside the papermaking machine; and section (IV) includes measurements that occur within the papermaking machine.
[0023]
23. Method according to any one of claims 1 to 22, characterized by the fact that it is: -for (re-) fixing starch to cellulosic material; and / or - to increase the strength of paper, cardboard or cardboard; and / or - to increase the drainage and / or production rate of the papermaking machine; and / or - to reduce the effluent COD in the papermaking process; and / or - to reduce the amount of nutrients for microorganisms in the cellulosic material; and / or - to reduce the consumption of fresh starch by recycling the starch that is already contained in the starting material and / or in the water circuit of the papermaking facility.
[0024]
24. Use of an ionic polymer, auxiliary ionic polymer, or a combination of these, characterized by the fact that it is in the method, as defined in any of claims 1 to 23.
[0025]
25. Use of a biocide, characterized by the fact that it is in the method, as defined in any of claims 1 to 23.

类似技术:

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同族专利:

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公开号 | 公开日

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AU2011295397A1|2013-02-28|

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US20130186584A1|2013-07-25|

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TW201219622A|2012-05-16|

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AU2011295397B2|2015-07-02|

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CN103180510B|2015-08-26|

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EP2609250A1|2013-07-03|

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EP2609250B1|2016-08-17|

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CN103180510A|2013-06-26|

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CA2807677A1|2012-03-01|

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KR101852942B1|2018-04-30|

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KR20130096728A|2013-08-30|

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JP2013538299A|2013-10-10|

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TWI522513B|2016-02-21|

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US8758562B2|2014-06-24|

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JP5933550B2|2016-06-08|

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PL2609250T3|2017-04-28|

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MX2013001782A|2013-04-03|

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CA2807677C|2017-09-26|

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PT2609250T|2016-10-26|

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BR112013004430A2|2016-05-31|

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ES2594978T3|2016-12-27|

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WO2012025228A1|2012-03-01|

引用文献:

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法律状态:
2018-02-06| B25A| Requested transfer of rights approved|Owner name: SOLENIS TECHNOLOGIES CAYMAN, L.P. (CH) |

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2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-05-14| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-07-07| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2020-10-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-12-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-02| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/08/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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EP10008834|2010-08-25|

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EP10008834.3|2010-08-25|

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EP11000063|2011-01-06|

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EP11000063.5|2011-01-06|

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PCT/EP2011/004253|WO2012025228A1|2010-08-25|2011-08-25|Method for increasing the advantages of starch in pulped cellulosic material in the production of paper and paperboard|

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