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    • 专利摘要:
    METHOD FOR THE MANUFACTURE OF PAPER, PAPER TOWEL, PAPERBOARD OR SOMETHING OF THE GENDER. The present invention relates to a method for making paper, paper towels, cardboard or the like using recycled fiber material as a raw material. The method comprises the following steps: the formation of pulp from recycled paper, cardboard or the like in a pulp former and obtaining a pulp flow comprising (i) an aqueous phase and (ii) at least recycled fibers and starch with a low molecular weight, which are dispersed in the aqueous phase; adding a coagulating agent to the pulp flow or an aqueous process flow comprising low molecular weight starch; placing the coagulant agent to interact with the low molecular weight starch and optionally the formation of aggregates; and adding at least one flocculating agent, after adding the coagulating agent, to any flow, comprising the interacted coagulating agent, and forming a starch-treated flow comprising agglomerate (s); and retaining at least a part of said aggregates and / or said agglomerates in the fibers or in a network, which is formed.
    公开号:BR112014018663B1
    申请号:R112014018663-4
    申请日:2013-02-22
    公开日:2021-03-02
    发明作者:Matti Hietaniemi；Kimmo Strengell；Asko Karppi；Marko Kolari；Jaakko Ekman
    申请人:Kemira Oyj；
    IPC主号:
    专利说明:

    [001] The invention relates to a method for the manufacture of paper, paper towels (tissue), cardboard or the like, from recycled fiber material according to the preamble of the attached independent claim.
    [002] Recycled fiber material, such as old corrugated cardboard (OCC), is normally used as a raw material for paper or cardboard. The recycled fiber material comprises, in addition to fibers, a number of other substances. The particulate foreign material is separated from the pulp in the pulp former or in the sieve. Some substances are naturally retained in the fibers and do not disturb the process. Other substances such as sticking can be separated from the pulp during sieving and removed from the process.
    [003] Typically, the recycled fiber material comprises starch, which has a low molecular weight. This starch comes from the glue on the surface of the paper or cardboard, and is poorly retained in the fibers because it typically has no charge or has a slightly anionic charge. Due to its small size, it is also not effectively separated in sieving. In this way, the low molecular weight starch remains in the water circulation of the pulping and papermaking processes or is removed along with the sieve effluent for the treatment of waste water. In the water circulation, starch increases the risk of microbial growth, as it is a nutrient substance suitable for several microbes. Microbes can affect the functioning of papermaking chemistry and / or the quality of the final product. The high microbial activity can lower the pH and have a marked effect on the final moisture chemistry. The high microbial activity can also create strong odors that can be a nuisance or even a danger to operating personnel, and also destructive to the quality of the product in degrees of packaging. The formation of sludge and bio-films on the surfaces of the tanks and on the machine's chassis leads to defects in the paper, such as spots and holes, or breaks in the net when the protuberances of the sludge are degraded.
    [004] In the treatment of waste water, low molecular weight starch increases the COD load of the water to be treated, that is, it increases the costs of treating waste water.
    [005] The amount of low molecular weight starch in the recycled fiber material can be relatively high, for example, 1 - 3% of the total weight of the recycled fiber. When the starch is lost in the water circulation during the pulp preparation process, the yield of the process is naturally reduced. Therefore, a process that prevents the enrichment of starch in the water circulation and helps its retention to recycled fibers should confer numerous advantages.
    [006] An objective of the present invention is to minimize or even eliminate the disadvantages that exist in the prior art.
    [007] An object of the invention is also to provide a method with which the amount of low molecular weight starch in the water circulation can be reduced when the pulp of the recycled fiber material is formed.
    [008] Another objective of the invention is to provide a method with which the retention of starch, especially low molecular weight starch, is improved.
    [009] These objectives are achieved with the invention that has the characteristics presented below in the characterizing part of the independent claim.
    [0010] The typical method according to the present invention for the manufacture of paper, paper towels, cardboard or the like, when using recycled fiber material as raw material is the method that comprises the following steps: - forming pulp from recycled paper, cardboard or the like in a pulp former and obtain a pulp flow that comprises (i) an aqueous phase and (ii) at least recycled fibers and starch that has a low molecular weight, which are dispersed in the phase aqueous; - adding a coagulating agent to the pulp flow or to an aqueous process flow comprising the low molecular weight starch; - allowing the coagulating agent to interact with the low molecular weight starch and optionally forming aggregates; and - adding at least one flocculating agent, after adding the coagulating agent, to any flow, which comprises the interacted coagulating agent, and forming a starch-treated flow comprising agglomerate (s); - retaining at least a part of said aggregates and / or said agglomerates in the fibers or in a network, which is formed.
    [0011] It has now been surprisingly found that low molecular weight starch in the recycled pulp can be agglomerated by the addition of a coagulating agent, followed by the addition of a flocculating agent. In this way, the low molecular weight starch interacts first with the coagulating agent and then with the flocculating agent and forms agglomerates, or is joined to the agglomerates, which are large enough to be retained in the fibers or in the formed network. In addition, through the sieving of suitable coagulating agents and flocculating agents, the agglomerates can even have surface charges that help in their retention in the fibers. It has been observed that the amount of low molecular weight starch in the water of the circulating process is clearly reduced, when chemical additions according to the present invention are carried out. In addition, the total process performance is improved when more of the starch in the recycled fiber material can be retained in the fibers and, consequently, in the formed cardboard or in the paper web. In addition, it may be possible to reduce the amount of surface glue later in the production process, since trapped starch can improve the strength properties of cardboard or formed paper.
    [0012] According to a preferred embodiment of the invention, the COD value of the treated stream is reduced by at least 10%, preferably at least 20%, more preferably at least 40%, of the COD value of the aqueous phase of the pulp flow or the COD value of the aqueous process flow prior to the addition of the coagulant.
    [0013] In this patent application, recycled fiber material refers to recycled paper, recycled cardboard and / or old corrugated container cardboard (OCC), which comprises fibers and starch, and optionally also other constituents. It should be understood that the pulp and the pulp flow comprise an aqueous phase and a solid material phase, which includes fibers and other possible solids. The method according to the present invention can be used to form the pulp of recycled paper, cardboard and / or the old corrugated container cardboard (OCC), and comprises starch, whereby the COD value typical of the aqueous phase of the untreated pulp flow is> 20 kg / ton, more typically> 35 kg / ton, and sometimes even> 50 kg / ton, before adding the coagulant and flocculating agent. The COD value is determined by disintegrating the recycled fiber material in the water, by centrifuging the pulp obtained in this way and by determining the COD value of the separated aqueous phase using the Hach Lange method, according to the description in the experimental part of this patent application. Preferably, the recycled fiber material is recycled cardboard and / or old corrugated container cardboard, and preferably comprises at least 20 kg / ton of starch, more preferably at least 30 kg / ton of starch, where the starch is determined using the iodine method that is described in the Tappi T419 om-11 standard (Starch on paper), and when using surface glue starch as a reference.
    [0014] A possible advantage, which is provided by the present invention, is that the ash content of the produced paper increases, while the tear resistance of the paper also increases or remains at least at the same level. Typically, in the prior art, an increase in ash content decreases the paper's resistance to breakage. Since the trend is typically the opposite, when the present invention is employed, it can be concluded that the present invention provides possibilities for increasing the ash content and, at least relatively, also the breaking strength. The typical increase in breaking strength is 3 - 15%, more typically 5 - 10%, calculated with respect to the breaking strength of corresponding paper manufactured without the sequential addition of coagulant and flocculating agent. The increase in ash content can be 5 - 25%, more preferably 10 - 20%, typically 15 - 20%, calculated with respect to the ash content of the corresponding paper manufactured without the sequential addition of coagulating agent and flocculation.
    [0015] In this patent application the terms "low molecular starch", "low molecular weight starch" and "low molecular weight starch" are interchangeable and are used interchangeably with each other. The low molecular weight starch in the recycled pulp normally originates from the surface glue, and is typically oxidized starch, degraded starch or enzyme degraded starch. Low molecular weight starch can be, for example, oxidized surface starch that has an average weight in the range of 100,000 - 5,000,000 g / mol, more typically 200,000 - 4,000,000 g / mol. Alternatively, low molecular weight starch can be an acid-degraded or enzyme-degraded surface starch that has an average weight in the range of 30,000 - 3,000,000 g / mol, more typically 40,000 - 2,000,000 g / mol . Typically, the pulp, which is obtained by transforming the recycled fiber material into pulp, comprises low molecular weight starch from different sources. This means that the low molecular weight starch in the currently described process can comprise oxidized surface starch as well as acid-degraded and / or enzyme-degraded surface starch.
    [0016] Surface glue starches can be specified based on the viscosity of the cooked starch, and typical viscosity levels are between 15 and 400 mPas, more typically between 20 and 300 mPas at 70 ° C at 10% concentration . The densities of the load of starches degraded by enzymes are very low, and are very close to zero at pH 7, for example, between -0.05 and 0 meq / g of absolute starch. Oxidized starches are typically more anionic compared to enzyme-degraded starches, about -0.3 to -0.01 meq / g, more typically about -0.2 to -0.02 meq / g calculated from absolute starch.
    [0017] Advantageously the method according to the present invention can be used for the production of paper, paper towels or cardboard, where the consumption of fresh water from the process is <10 m3 / ton of paper or cardboard produced, preferably <5 m3 / ton of paper or cardboard produced and / or the AM water conductivity of the process is> 2,500 μS / cm, preferably> 3000 μS / cm, sometimes even> 4000 μS / cm in the inbox. In other words, the present method is especially suitable for pulping the recycled fiber material in a process that has a low consumption of fresh water. In addition, the present invention is especially intended to retain low free molecular weight starch in the aqueous phase of the pulp in the fibers, which originate from recycled paper, paper towels and / or cardboard.
    [0018] The method according to the present invention is therefore suitable for the production of paper, paper towels, cardboard or the like from recycled fiber material.
    [0019] A method according to one embodiment of the present invention to improve the process of making paper, cardboard or the like, in which the process uses recycled fiber material as a raw material, comprising - forming paper pulp, cardboard or the like recycled in a pulp former and obtaining a pulp that comprises at least recycled fibers and starch that has a low molecular weight dispersed in an aqueous phase, - sieving the pulp and separating the unwanted material from the pulp, - adding a coagulant to the pulp and allow the coagulant to interact with the low molecular weight starch, - add a flocculating agent after adding the coagulant to a process flow and form a starch that comprises agglomerate, whereby the COD value of the aqueous pulp phase is reduced by less than 10% of the COD value of the aqueous phase before the addition of the coagulating agent and the flocculating agent.
    [0020] The coagulating agent interacts, chemically or physically, with the low molecular weight starch, whereby a coagulation, a clot or a loose agglomerate is formed. According to an embodiment of the invention the pulp flow is sieved and the unwanted material from the pulp flow is separated. The sieved pulp flow is densified to a higher concentration, for example, the storage concentration, by separating a part of the aqueous phase from the pulp flow as a discharge flow, and the coagulant is added to the pulp flow before the sieving pulp thickening step or the discharge water flow of the thickening step. In the event that the coagulating agent is added to the pulp flow prior to the thickening of the pulp flow, it is possible to add the coagulant agent immediately after the pulping step, before the sieving step or after the sieving step. The addition of the coagulant to the pulp prior to the thickening step is advantageous because the enrichment of starch in the water circulation is effectively prevented in most processes, and a large amount of starch is effectively retained in the fibers.
    [0021] According to one modality, especially when the process has effective screening and thickening steps, the coagulating agent can be added after the thickening step, for example, after the storage towers. The coagulating agent can be added to the short circulating pulp between the provision of starting material and the inlet box. Even in this embodiment, the flocculating agent is added to the process after the coagulating agent, in a flow, which comprises the interacted coagulating agent.
    [0022] According to an embodiment of the invention the coagulating agent is an inorganic coagulating agent. The coagulating agent can be selected from aluminum compounds, iron compounds, bentonite or colloidal silica. In particular, the coagulant agent is selected from the group comprising aluminum sulfate, aluminum chloride, polyaluminium chloride (PAC), polyaluminium sulfate (PAS), silica and polyaluminium sulfate, sodium aluminate, alum, ferric sulphate (Fe2 (SO4) 3), ferrous sulphate (FeSO4), ferric ferrous sulphate, ferric chloride, ferrous chloride, ferric ferrous chloride, ferric chloride sulphate, ferric nitrate, nitrate ferric sulfate, ferric chloride nitrate, ferric hydroxide, bentonite, silicic material, such as colloidal silica, and any of their mixtures. According to one embodiment, the coagulating agent is selected from the group consisting of bentonite, colloidal silica, aluminum compounds or iron compounds comprising Fe (III). Bentonite must be comprised here of the montmorolonite clay mineral. Aluminum compounds and iron compounds comprising Fe (III) are preferred as coagulating agents.
    [0023] The coagulating agent can be added in an amount of - 0.5 - 10 kg of active aluminum / ton of dry pulp, preferably 0.75 - 8 kg of active aluminum / ton of dry pulp, and more preferably 1 - 5 kg of active aluminum / ton of dry pulp or - 5 - 50 kg of active Fe / ton of dry pulp, preferably 6 - 40 kg of active Fe / ton of dry pulp, and more preferably 8 - 20 kg of active Fe / ton of dry pulp or - 0.5 - 10 kg of dry bentonite / ton of dry pulp, preferably 1 - 8 kg of dry bentonite / ton of dry pulp, and more preferably 2 - 5 kg of bentonite dry / ton of dry pulp, or - 0.1 - 1 kg of dry silica / ton of dry pulp, preferably 0.2 - 0.8 kg of dry silica / ton of dry pulp, preferably 0.25 - 0 , 5 kg of dry silica / ton of dry pulp, depending on the active substance in the coagulant.
    [0024] Bentonite is typically used as a paste of 1 - 5% by weight, and can have a particle size in the range of 200 - 800 nm. Colloidal silica is typically used as a paste of 0.5 - 25% by weight, and can have a particle size in the range of 1 - 50 nm. Bentonite and colloidal silica pastes can also be diluted before use, if necessary.
    [0025] According to one embodiment, the coagulating agent is polyaluminium chloride. Polyaluminium chloride is an inorganic polymer and is typically present in a solution as a highly charged aluminum complex Al13O4 (OH) 24 (H2O) 127+ or AlO2Al12 (OH) 24 (H2O) 247+ complex. In this patent application, polyaluminium chloride is understood as a polymerized aluminum substance, which can also be presented by the general formula Al2 (OH) xCl6-x, where 0 <x <6. The degree of neutralization, that is, the substitution of Cl ions by OH ions, can be expressed when using unitary basicity. The basicity of the polyaluminium compound can generally be expressed by the following formula% basicity = 100 x [OH] / 3 [Al]
    [0026] The higher the basicity, the higher the degree of neutralization. Depending on the basicity of the polyaluminium chloride, fewer ions have a 3+ charge, and more ions are highly charged, on average 5+ to 7+.
    [0027] According to a preferred embodiment of the present invention, the coagulant is polyaluminium chloride which has an aluminum content of 4 - 20%, preferably 7 - 18%, and a basicity of 20 - 80%, preferably 30 - 70%, and more preferably 35 - 55%. Typically, polyaluminium chloride can be used as an aqueous solution at 20 - 40% by weight, and more typically at 30 - 40% by weight. The pH of the polyaluminium chloride solution is typically 0.5 - 4.2.
    [0028] The interaction between low molecular weight starch and the coagulating agent can be chemical and / or physical. For example, polyaluminium chloride, alum and iron sulphates interact chemically with low molecular weight starch and form coagulations, clots or loose clumps. It is assumed that bentonite and colloidal silica physically adsorb or bind starch, whereby loose clumps are formed. In the case where the coagulant is a metal coagulant with high cationicity, such as polyaluminium chloride or polyaluminium sulphate, it can form an inorganic polymer, which attracts and interacts with the low molecular weight starch, the fines and the possible charge particles. The size of the coagulation, clot or loose clump formed is then further increased when it comes into contact with the flocculating agent.
    [0029] The flocculating agent is added after the addition of the coagulating agent so that the flocculating agent comes into contact with the coagulating agent or coagulant, the clot or the loose agglomerate that is formed, when the low molecular weight starch it is bound to or attached to the coagulant or absorbed into the coagulant. In other words, the flocculating agent is added to a flow, which comprises the interacting coagulating agent, for example, the pulp flow, preferably after the pulp storage towers or silos and before the inlet machine box. paper, paper towel or cardboard. In this way, the flocculating agent is preferably added to the short circulation of a paper, paper towel or cardboard machine, however, after adding the coagulating agent to a flow comprising the interacted coagulating agent. The flocculating agent can be added at one feed site or at several separate feed sites. The flocculating agent can be added directly to the pulp flow, or it can be added first to an aqueous process flow, which is later combined with the pulp flow. It is possible to add the flocculating agent to the pulp flow and to one or more aqueous process flows. The flocculating agent (s) is (are) typically added as an aqueous dispersion in an amount of 20 - 2000 g / ton of paper or cardboard, typically 50 - 1000 g / ton of paper or cardboard , preferably 100 - 500 g / ton of paper or cardboard, and values are provided as an amount of active flocculating agent (s).
    [0030] According to a preferred embodiment, several different flocculating agents can be added, such as two, three or four different flocculating agents, preferably at several separate feeding sites. If several flocculating agents are added, advantageously at least one of them is anionic. For example, anionic polyacrylamide can be added after adding cationic polyacrylamide. In any case, the first flocculating agent is preferably added to a flow comprising the interacting coagulant.
    [0031] The flocculating agent is typically added after the coagulant to a flow comprising the interacting coagulant, the reaction time for the interaction between the coagulant and the low molecular weight starch is> 1 minute, preferably at range of 2 - 30 minutes, and more preferably in the range of 5 - 15 minutes. This means that the flocculating agent is added after the required reaction time has elapsed. For example, when polyaluminium chloride is used as a coagulating agent, it is added to the pulp flow or to a water flow comprising low molecular weight starch, and a typical reaction time for the interaction between polyaluminium chloride and low molecular weight starch, preceding the addition of the flocculating agent, is in the range of 7 - 12 minutes, more typically about 10 minutes.
    [0032] According to an embodiment of the invention, the flocculating agent is selected from the group comprising cationic polyacrylamide (C-PAM), anionic polyacrylamide (A-PAM), polyvinyl amine (PVAm), polyethylene oxide (PEO), imine polyethylene (PEI) and mixtures thereof. According to an embodiment of the invention the flocculating agent is cationic polyacrylamide (C-PAM) and / or anionic polyacrylamide (A-PAM) and has an average molecular weight (MW) in the range of 4,000,000 - 22,000,000 g / mol, more preferably 6,000,000 - 20,000,000 g / mol, and even more preferably 7,000,000 - 18,000,000 g / mol. According to an advantageous embodiment, the flocculating agent is a polymer that has an average molecular weight (MW)> 8,000,000 g / mol, and preferably 9,000,000 - 18,000,000 g / mol. In this patent application, the "average molecular weight" value is used to describe the magnitude of the polymer chain length. Average molecular weight values are calculated from the results of intrinsic viscosity measured in a known manner in 1N NaCl at 25 ° C using a Ubbelohde capillary viscometer. The selected capillary is appropriate, and in the measurements of this patent application, a Ubbelohde capillary viscometer with the constant K = 0.005228 was used. The average molecular weight is then calculated from the result of the intrinsic viscosity in a known way when using the Mark-Houwink equation fo] = K ^ Ma, where ft] is the intrinsic viscosity, M is the molecular weight (g / mol ), and K and a are parameters provided in the Polymer Handbook, fourth edition, volume 2, editors: J. Brandrup, EH Immergut and EA Grulke, John Wiley & Sons, Inc., USA, 1999, p. VII / 11 for poly (acrylamide chloride acrylate-co-N-N, N-trimethyl aminoethyl), 70% acrylamide. Therefore, the value of parameter K is 0.0105 ml / g and the value of parameter a is 0.3. The average molecular weight range provided for the parameters under conditions of use is 450,000 - 2,700,000 g / mol, but the same parameters are also used to describe the magnitude of the molecular weight outside this range. For polymers that have a low average molecular weight, typically about 1,000,000 g / l or less, the average molecular weight can be measured when using HPLC size exclusion chromatography, when using PEO for calibration. HPLC size exclusion chromatography is used especially if no significant results can be obtained when using intrinsic viscosity measurement.
    [0033] Preferably, after adding the coagulating agent and the flocculating agent, in that order, and obtaining a starch that comprises the agglomerate, the agglomerate is retained in the recycled fibers in the pulp or in the network that is formed.
    [0034] It is also possible to add a biocide and / or an amylase enzyme inhibitor to control microbes in the process. The biocide and / or the amylase enzyme inhibitor can be added to the pulp former and / or to a process flow, such as pulp flow or aqueous process flow. The biocide and / or amylase enzyme inhibitor is preferably added to the process flow and / or to the pulp flow before the pulp storage towers or silos located after the pulp thickening step. The biocide / enzyme inhibitor can be added to the pulp in the pulp former or prior to the thickening of the sieved pulp. According to a preferred embodiment of the present invention the biocide and / or the amylase enzyme inhibitor is added to the pulp flow within 2 hours from the moment the pulp flow leaves the pulp former. In addition, the biocide or amylase enzyme inhibitor can be added to the pulp between the pulp former entrance and the sieve pulp thickening step. The initial addition of the biocide or amylase enzyme inhibitor is preferred, as it minimizes further degradation of low molecular weight starch, and can improve the coagulation and flocculation of low molecular weight starch, and thus the retention of starch in recycled fibers. It is possible to add the biocide and / or the amylase enzyme inhibitor to only one biocide feeding site. Alternatively, the biocide and / or the amylase enzyme inhibitor can be added at various feed sites of the separate biocide, spaced apart, whereby the addition of the biocide / enzyme can be targeted at known problem points in the process. It is also possible to add the biocide to the feed site (s) of the first biocide and the amylase enzyme inhibitor to the different and separate biocide feed site (s).
    [0035] Preferably, the biocide and / or the amylase enzyme are added as soon as possible in order to minimize further degradation of the low molecular weight starch. The biocide and / or the amylase enzyme can be added, for example, to the aqueous dilution stream, which is conducted to the pulp former. For example, the biocide and / or the amylase enzyme can be added to the pulp former dilution water storage tank.
    [0036] The biocide can be any appropriate biocide, which should reduce the number of viable bacteria and / or microbes in the process by at least 80%. Similarly, the amylase enzyme inhibitor can be any substance that inhibits the formation of or deactivates the amylase enzyme, such as a zinc inhibitor. Preferably, the amylase enzyme inhibitor can be any appropriate inhibitor that reduces the activity of the amylase enzyme under process conditions by at least 20%.
    [0037] According to an embodiment of the invention, the biocide can be selected from a group comprising oxidation biocides, such as sodium hypochlorite, hypobromous acid, chlorine dioxide; halogenated hydantoins, such as bromochloro-dimethyl hydantoin; partially halogenated hydantoins, such as monochloro-dimethyl hydantoin; haloamines, such as chloramines or bromamines; and their mixtures. A haloamine, which is suitable for use in an embodiment of the present invention, can be formed by combining an ammonium source, such as ammonium sulfate, ammonium chloride, ammonium bromide, ammonium phosphate, nitrate of ammonium or any other ammonium salt, including urea, with an oxidant such as sodium hypochlorite. The biocide can be added continuously to provide a total active chlorine concentration of about 0.1 - 5 ppm across all treated parts of the process. Most preferably, the active chlorine concentration in these parts of the process is about 0.75 - 2 ppm. It is also possible to add the biocide by using a generatrix dosage, which refers to the periodic, or batch, dosage of the biocide in the process, in contrast to a continuous dosage. Typically, a generatrix dose is 1 - 10 ppm, and preferably 3 - 7 ppm. Generatrices should preferably be fed for about 3 - 30 minutes every about 6 - 24 times a day, and are most preferably fed for about 5 - 15 minutes every about 12 - 24 times a day.
    [0038] Reinforcing agents and / or flocculating additives can be added to the pulp flow. According to an embodiment of the invention the reinforcing agent is selected from the group comprising starch, cationic polyacrylamide (C-PAM), anionic polyacrylamide (A-PAM), glyoxalated polyacrylamide (G-PAM), amphoteric polyacrylamide, polydialyl dimethyl chloride ammonium (poly-DADMAC), polyacrylic amide (PAAE), polyvinyl amine (PVAm), polyethylene oxide (PEO), polyethylene imine (PEI), chitosan, guar gum, methyl cellulose carboxy (CMC) and mixtures thereof. Starch can be cationic, anionic or amphoteric. The starch can be either non-degraded or highly cationic degraded starch having DS> 0.05, with non-degraded starch being preferred. When the reinforcing agent is a synthetic polymer it can have an average molecular weight in the range of 100,000 - 20,000,000 g / mol, typically 300,000 - 8,000,000 g / mol, and more typically 300,000 - 1,500,000 g / mol mol, as long as the molecular weight of the reinforcing agent is lower than the molecular weight of the corresponding flocculating agent. Average molecular weights are measured when using a Ubbelohde capillary viscometer, as described above in this patent application.
    [0039] The reinforcing agent is typically added as an aqueous dispersion in an amount of 0.1 - 20 kg / ton of paper or cardboard, typically 0.3 - 5 kg / ton of paper or cardboard, preferably 0 , 5 - 3 kg / ton of paper or cardboard, supplied as an amount of active substance. The addition of a reinforcing agent can preferably be done prior to the addition of the flocculating agent, and the addition of the reinforcing agent is preferably done to the pulp flow, preferably to the flow of coarse starting material, and the consistency of the thick starting material is 2 - 6% by weight.
    [0040] It is also possible to use a flocculant additive that is selected from the group comprising bentonite, colloidal silica and conventional papermaking fixatives, such as polydialyl dimethyl ammonium chloride (poly-DADMAC) or polyamines. The flocculant additive is typically added to the process before or after the addition of the flocculating agent, but after the addition of the coagulating agent. The flocculant additive, especially the fixative, which can be used as a flocculant additive, is added to the pulp flow, typically in an amount of 50 - 4,000 g / ton of paper or cardboard, typically 100 - 2,000 g / ton of paper or cardboard, and preferably 200 - 800 g / ton of paper or cardboard, supplied as an amount of active substance.
    [0041] According to an embodiment of the invention, the coagulant is added to the flow of discharge water from the thickening step, that is, to the flow of discharge water from a thickener, in a feeding place or in more feeding places . In this embodiment, the flow of discharge water from the thickening step can be carried forward in the process and used as dilution water between the machine housing and the inlet housing. The coagulating agent is introduced into the flow of the discharge water which comprises the starch which has a low molecular weight after the thickening step, but before the machine box. The coagulant agent can be fed at one feeding site or simultaneously at two, three or more feeding sites. Starch interacts with the coagulating agent and forms loose coagulants, clots or clumps. The flocculating agent is added to the pulp flow and / or to the discharge water flow at flocculation feeding sites after the addition of the coagulating agent. For example, it is also possible to add the flocculating agent to the discharge flow of the thickening step. However, the flocculating agent is added after adding the coagulating agent to at least one of the coagulant feeding sites, but before the machine box to ensure the retention of the recycled starch in the fibers and / or the (s) network (s) to be formed.
    [0042] The invention is described in more detail below with reference to the attached schematic drawings, in which
    [0043] Figure 1 shows a first embodiment of the present invention for the manufacture of recycled cardboard,
    [0044] Figure 2 shows a second embodiment of the present invention for the manufacture of paper, paper towels or recycled cardboard, and
    [0045] Figure 3 shows yet another embodiment of the invention for the manufacture of recycled cardboard.
    [0046] In Figure 1, a first embodiment of the present invention for the manufacture of recycled cardboard is shown. The bales of paper and / or recycled cardboard 20 are introduced into a pulp former 1 through an inlet. In the pulp former 1, the bales of paper and / or cardboard are disintegrated and a pulp stream comprising recycled fibers and starch that has a low molecular weight is led out of the pulp former 1 to a dump box 2 of the former of pulp. From the pulp former dump box, the pulp is sent to fractionation sieving 3 and fine sieving 4 or short fiber thickener 5. From fine sieving 4, the fibers are fed to the long fiber thickener 6 and the rejected material from the sieving stage is led to the thickening of rejected material 7. In the thickening of rejected material, the particulate material 7 is separated and still others are separated from the water, and led out of the process as sludge rejected material 19. The water is removed as effluent 18 for an effluent treatment (not shown). In conventional processes, low molecular weight starch leaves the process through these material flows, and the charged effluent 18 or the sludge discarded material 19.
    [0047] The coagulant can be introduced into the pulp which comprises recycled fibers and starch that has a low molecular weight in the plurality of alternative coagulant feeding sites 26. It is possible to feed the coagulating agent to a feeding site 26 or simultaneously feed the coagulant at two or more feeding sites 26. The coagulant feeding sites 26 are located, finally, before the short fiber thickener 5 and / or the long fiber thickener 6. From these thickeners 5, 6, the separated water is led to the white water tank 17 and also back to the pulp former 1 as the water 24 of the pulp former. The coagulant feeding sites 26 are located so that the coagulant agent interacts with the starch before the thickeners 5, 6. In this way, the starch is progressing at least mainly forward with the fiber phase in the process and is not recirculated back to the white water tank 17 or pulp former 1 with the water phase.
    [0048] From the short fiber thickener 5 the short fiber pulp is fed to the short fiber storage tower and, correspondingly, the long fiber pulp is fed from the long fiber thickener 6 to the long fiber storage tower 9. From the fiber storage towers 8, 9, the pulps are conveyed to the upper layer 10 machine box or the rear layer machine box and also to the upper layer 12 inlet box or the entrance of the back layer 13. The paper or cardboard nets for the top layer or the back layer are formed on the top layer 14 thread or on the back layer thread 15 and gathered after their initial formation. The water that is removed from the net is either circulated directly back to the process or collected in a white water box 16. Finally, the formed paper or cardboard net 21 is transferred further to pressing and drying. Fresh water 22 is added to the process through shower pipes 23.
    [0049] The flocculating agent is added to the pulp at the flocculation feeding sites 28. The flocculating agent can be added only to the short fiber pulp of the short fiber storage tower 8 or only to the long fiber pulp of the storage tower. long fiber storage 9, or preferably to the short fiber pulp of the short fiber storage tower 8 and to the long fiber pulp of the long fiber storage tower 9. The flocculating agent is added after the addition of the coagulation agent at one of the coagulant feeding sites 26, but before the inbox 12, 13 in order to guarantee the retention of the recycled starch to the fibers and / or to the network (s) to be formed.
    [0050] The biocide or the amylase enzyme inhibitor is preferably added to the process at one or several biocide feed sites 25 for the control of microbes. It is possible to add the biocide to only one biocide feed site or to add separate dosages of biocide / enzyme inhibitor to multiple feed sites. It is also possible to add the biocide at one feed site and the enzyme inhibitor at a different feed site.
    [0051] In one embodiment, it is also possible to add the reinforcing agent and / or the flocculation additive to the process at the additive 27 feeding sites. Typically, the reinforcing agent and / or the flocculation additive are added after the towers of storage 8, 9, but finally immediately before the inbox 12, 13. Preferably, the reinforcing agents and / or flocculation additives are added after the addition of the coagulation agent, but before the addition of the coagulation agent. flocculation.
    [0052] A second embodiment of the present invention is shown in Figure 2 for the manufacture of recycled paper, paper towels or cardboard. The bales of paper and / or recycled cardboard 20 are introduced into a pulp former 1 through a pulp former entrance. In the pulp former 1 the bales of paper and / or cardboard are disintegrated and a pulp stream comprising recycled fibers and starch that has a low molecular weight is led out of the pulp former 1 to a dump box 2 of the former pulp. From the pulp former dump box 2, the pulp is fed to a flotation unit (optional) and also to the primary fine sieving stage 41. From the primary fine sieving stage 41, the fibers are conducted to a thickener 61 or a fine sieving rejection stage 51. From the fine sieving rejection stage 51, the fibers are carried to the thickener 61 and the rejected material is led to the thickening of the rejected material 7. In the thickening of the rejected material the particulate material 7 is separated, and others still, from water, and carried out of the process as sludge discarded material 19. The water is removed as effluent 18 for an effluent treatment (not shown). In conventional processes, starch that has a low molecular weight leaves the process through these material flows, and the charged effluent 18 or the sludge discarded material 19.
    [0053] The coagulant can be introduced into the pulp which comprises recycled fibers and starch which has a low molecular weight in the plurality of alternative coagulant feeding sites 26. It is possible to feed the coagulating agent to a feeding site 26 or simultaneously feed the coagulant at two or more feeding sites 26. The coagulant feeding sites 26 are located, finally, before the thickener 61, from which the separated water is conveyed to the white water tank 17 and also back to the pulp former 1 as water 24 from the pulp former. The coagulant feeding sites 26 are located so that the coagulant agent interacts with the starch prior to the thickener 61. In this way the starch is progressing at least mainly forward with the fiber phase in the process and is not recirculated back to the deposit of white water 17 or to the pulp former 1 with the water phase.
    [0054] From the thickener 61, the pulp is taken to a fiber storage tower 81. From the fiber storage tower 81, the pulp is taken to a machine box 101 and also to an inbox 121. The paper net, paper towel or cardboard is formed like a thread 141. The water that is removed from the formed net is either circulated directly back to the process or collected in a white water box 16. Finally, the paper, paper towel or formed cardboard net 21 is transferred to pressing and drying. Fresh water 22 is added to the process through shower pipes 23.
    [0055] The flocculating agent is added to the pulp at the flocculating feed site 28. The flocculating agent is added after adding the clotting agent to one of the coagulant feed sites 26, but finally immediately before the inlet 121 in order to ensure the retention of the recycled starch in the fibers and / or in the network to be formed.
    [0056] The biocide or amylase enzyme inhibitor is preferably added to the process at one or several biocide feed sites 25. It is possible to add the biocide only at one biocide feed site or to add separate dosages of the biocide / feed inhibitor enzyme in various feeding sites. It is also possible to add the biocide at one feed site and the enzyme amylase inhibitor at a different feed site.
    [0057] In one embodiment, it is also possible to add the reinforcing agent and / or the flocculating additive to the process at the additive 27 feeding sites. Typically, the reinforcing agent and / or the flocculating additive is added after the tower of fiber storage 81, but before the inbox 121. Preferably, the reinforcing agents and / or the flocculating additives are added after the addition of the coagulation agent, but before the addition of the flocculating agent.
    [0058] Figure 3 shows yet another embodiment of the invention for the manufacture of recycled cardboard. The bales of paper and / or recycled cardboard 20 are introduced into a pulp former 1 through a pulp former entrance. In pulp former 1 the bales of paper and / or cardboard are disintegrated and a pulp stream comprising recycled fibers and starch that has a low molecular weight is led out of the pulp former 1 to a dump box 2 of the former pulp. From the pulp former dump box 2, the pulp is passed to fractionation sieving 3 and also to fine sieving 4 or short fiber thickener 5. From fine sieving 4 the fibers are led to the long fiber thickener 6 and the material rejected from the sieving stage is carried out to the thickening of rejected material 7. In the thickening of rejected material the particulate material 7 is separated, and still others, from the water, and carried out of the process as rejected material of mud 19. The water is removed as effluent 18 for an effluent treatment (not shown).
    [0059] The discharge water of thickeners 5, 6 is carried forward in the process and used as dilution water between machine box 10, 11 and inlet box 12, 13. The coagulant is introduced into the discharge stream of short fiber thickener or in the discharge stream of long fiber thickener at the coagulant feed sites 26. The discharge stream comprises starch that has a low molecular weight and that starch interacts with the coagulant and forms loose or agglomerated coagulants. It is possible to feed the coagulant agent at a feed site 26 or simultaneously feed the coagulant at two or more feed sites 26. The coagulant feed sites 26 are located after the short fiber thickener 5 and / or the long fiber thickener 6, but before the inbox 12, 13.
    [0060] From the short fiber thickener 5 the short fiber pulp is fed to the short fiber storage tower 8 and, correspondingly, the long fiber pulp is fed from the long fiber thickener 6 to the long fiber storage tower 9. From the fiber storage towers 8, 9 the pulps are conveyed to the upper layer 10 machine box or the rear layer 11 machine box and also to the upper layer 12 input box or the input box of the back layer 13. The paper or cardboard nets for the top layer or the back layer are formed on the thread of the top layer 14 or on the thread of the back layer 15 and gathered after their initial formation. The water that is removed from the network is either circulated directly back to the process or collected in a white water box 16. Finally, the formed paper, paper towel or cardboard network 21 is further transferred to pressing and drying. Fresh water 22 is added to the process through shower pipes 23.
    [0061] The flocculating agent is added to the pulp and / or the discharge flows at the flocculation feeding sites 28. The flocculating agent can be added only to the short fiber pulp of the short fiber storage tower 8 or only to the long fiber pulp from the long fiber storage tower 9, or preferably to the short fiber pulp from the short fiber storage tower 8 and the long fiber pulp from the long fiber storage tower 9. It is also possible to add the agent of flocculation to the discharge flow of the short fiber thickener 5 and / or to the discharge flow of the long fiber thickener 6. The flocculating agent is added after the addition of the clotting agent to one of the coagulant feeding sites 26, but before the inbox 12, 13 in order to guarantee the retention of the recycled starch to the fibers and / or network (s) to be formed.
    [0062] The biocide or amylase enzyme inhibitor is preferably added to the process at one or more biocide feed sites 25 for the control of microbes. It is possible to add the biocide to only one biocide feed site or to add separate dosages of the biocide / enzyme inhibitor to multiple feed sites. It is also possible to add the biocide at one feed site and the amylase enzyme inhibitor at a different feed site.
    [0063] In one embodiment, it is also possible to add the reinforcing agent and / or the flocculation additive to the pulp at the additive 27 feeding sites. Typically, the reinforcing agent and / or the flocculation additive is added to the pulp afterwards of the storage towers 8, 9 but finally immediately before the machine box 12, 13. Reinforcing agents and / or flocculating additives can be added to the pulp prior to the addition of the coagulating agent and the flocculating agent. EXPERIMENTAL PART
    [0064] Some embodiments of the invention are also described in the following non-limiting examples. Example 1.
    [0065] The test paste is prepared using refined bleached pine kraft pulp in a Valley Hollander instrument at a Schopper Riegler value of 25 and degraded starch (Perfectamyl A 4692, Avebe), which is a low oxidized potato starch weakly anionic viscosity. The starch content measured in the test paste is 301 mg / l. The test paste is diluted to a consistency of 5 g / l and adjusted to an ambient temperature of + 23 ° C.
    [0066] The test chemicals used are diluted to the appropriate concentration prior to addition to the test paste. The dilution level is selected in such a way that the dosage of a diluted test chemical is between 1 and 3 ml. They are added to the test paste as shown in Table 1 and a dynamic drainage bottle, DDJ (Paper Research Materials, Inc., Seattle, WA) is used to control the degree of starch retention in the paper and how much starch remains in the paper. filtered material.
    [0067] The test chemicals used are:
    [0068] Prod A: coagulating agent, polyaluminium silicate product, Al content of 7.8% by weight, alkalinity of 4%.
    [0069] Prod B: reinforcing agent, glyoxylated PAM product, acrylamide copolymer and diallyl dimethyl ammonium chloride, which is treated with glyoxal, charge density of 0.5 meq / g dry polymer product, average MW of 200,000 g / mol, dry solids 7.5%.
    [0070] Prod C: flocculating agent, anionic polyacrylamide reinforcing resin product, aqueous solution of acrylamide copolymer and acrylic acid, charge density: -2.9 meq / g dry polymer product, average MW of 400,000 g / mol, 20% dry solids, 6000 mPas viscosity at 25 ° C measured with a Brookfield DVI + instrument, equipped with small sample adapter, and spindle 31.
    [0071] Prod D: flocculating agent, cationic polyacrylamide product, acrylamide copolymer and ethyl trimethyl ammonium acryloyl chloride, charge density of 1.0 meq / g dry polymer product, average MW of 7,000,000 g / mol, 90% dry solids.
    [0072] Prod E: coagulating agent, colloidal silica product, 15% solids content, 5 nm particle size, S-value 60.
    [0073] The volume of the pulp paste in DDJ is 500 ml, the speed of the agitator is 1,000 rpm and the type of wire is M60. The test chemical addition times are indicated as negative time before drainage begins in Table 1. Stirring is started 45 s before drainage and is continued after drainage until the sample volume is filtered. The sample is taken from the first 100 ml filtered material. The filtered material is centrifuged at a speed of 3,000 rpm 4 - 5 hours after the addition of starch.
    [0074] From the centrifuge, the COD of the supernatant is measured using the HK Lange LCK 1041 method according to the manufacturer's instructions. the 2 ml supernatant is carefully pipetted into a sample cell, which is closed and completely cleaned, and inverted. The sample cell is heated in a thermostat for 15 minutes at 175 ° C. The hot sample cell is allowed to cool to 80 ° C in the thermostat, after which it is removed from the thermostat, carefully inverted twice, and allowed to cool to room temperature outside the thermostat. The outside of the sample cell is cleaned and the evaluation is performed. According to the test method, oxidizable substances react with the solution of sulfuric acid - potassium dichromate in the presence of silver sulfate as a catalyst. Chloride is masked by mercury sulfate. The green color of Cr3 + is evaluated, and it is the indicator of the COD value of the sample. The evaluation is done when using a spectrometer.
    [0075] Starch is measured from the filtered material when using Hach Lange's LCK 357 method according to the manufacturer's instructions. The 2.0 ml sample is pipetted into an open cuvette, the cuvette is closed and mixed, evaluated after 10 minutes. The pH of the sample must be in the range of 4 - 7, temperature of 22 ° C. The sample analyzed must be colorless and free from clouding. A slight coloration can be obtained with the help of a specific blank value of the sample, prepared by using 0.4 ml of distilled water and 2 ml of sample. Turbidity can be eliminated by passing the sample through a membrane filter (LCW 904). The evaluation of the sample is made by spectrophotometric measurement at 535 nm, factor 127, when using an RD Lange photometer, LASA 100 v. 1.20. The calibration curve for the measurement is prepared by using the Cargill C * film starch TCF07312, which is cooked at 94 - 98 ° C, about 30 minutes.
    [0076] The results of Example 1 are shown in Table 1. From Table 1 it can be seen that the addition of the coagulating agent and the flocculating agent, in that order, clearly improves the starch retention, that is, the amount of starch in the filtered material is decreased. The COD value of the filtered material is similarly decreased. This indicates that the starch must be retained in the fibers in the thickening step or in the yarn section of the paper machine. Table 1 Retention test for starch with the dynamic drainage bottle (DDJ).
    * product dosage, not calculated as active substance Example 2.
    [0077] The test paste is prepared from lining cardboard containing surface glue starch. The dry cardboard is cut into 2 x 2 cm pieces and a batch of disintegrated pulp is prepared by adding 30 g of cut pieces of cardboard in 1.5 liters of tap water, at a temperature of + 45 ° C. After soaking for 5 minutes, the cardboard pieces were disintegrated in a bottle of Britt (Paper Research Materials, Inc., Seattle, WA) for 50,000 rotations.
    [0078] The pulp obtained is diluted to reach a consistency of 0.5%. The total diluted volume of the pulp is 20 liters. 0.5 liter of OCC - pulp with a high number of bacteria and amylase activity is used as dilution water, and the rest of the dilution water is fresh water. Starch was added in an amount of 3 g / l to the OCC pulp, and in addition to the natural bacterial flora of the process water, two positive amylase bacteria that originate from paper machines, Deinococcus geothermalis Hambi 2411 and Meiothermus silvanus Hambi 2478, were inoculated in the water. The water was incubated at + 45 ° C, with shaking at 120 rpm, for 3 days.
    [0079] Two 1 liter portions are removed as reference samples and the rest of the paste is treated with monochloramine as a biocide so that the measurable residual total chlorine is about 1.5 mg / l. In addition, 100 mg / l of zinc, which originates from zinc chloride, is added to the pulp paste to control microbes. The temperature of the pulp paste is adjusted to room temperature, + 23 ° C.
    [0080] The retention test is performed 2 - 4 hours after adding the biocide. The test chemicals used are added as shown in Table 2 to a dynamic drain bottle, DDJ (Paper Research Materials, Inc., Seattle, WA), to control the degree of starch retention in the paper and how much starch remains in the filtered material. The pulp paste volume in the DDJ is 500 ml, the agitator speed is 1,000 rpm and the wire is of the M60 type.
    [0081] The test chemicals used are:
    [0082] Mca: Biocide, monochloramine.
    [0083] Prod F: coagulating agent, aluminum sulfate, 9% Al content, dry powder.
    [0084] Prod G: coagulating agent, bentonite, activated by alkali, finely crushed, dry solids at 88%, dispersed up to 3% of the paste.
    [0085] Prod H: coagulating agent, polyaluminium chloride, Al content 9.3%, alkalinity: 43%.
    [0086] Prod E: coagulating agent, colloidal silica.
    [0087] Prod D: flocculation agent, cationic polyacrylamide product, acrylamide copolymer and ethyl trimethyl ammonium acryloyl chloride, charge density of 1.0 meq / g dry polymer product, average MW 7,000,000 g / mol , 90% dry solids.
    [0088] Prod J: flocculating agent, anionic polyacrylamide product, acrylamide and acrylic acid copolymer, charge density of -2.7 meq / g of dry polymer product, average MW 15,000,000 g / mol, solids dry: 90%.
    [0089] Prod C: flocculating agent, resistant anionic polyacrylamide resin product, aqueous solution of acrylamide copolymer and acrylic acid, charge density of -2.9 meq / g of dry polymer product, average MW 400,000 g / mol, 20% dry solids, 6,000 mPas viscosity at 25 ° C measured with a Brookfield DVI + instrument, equipped with a small sample adapter, and spindle 31.
    [0090] Prod K: flocculation agent, product of aqueous dispersion of cationic polyacrylamide micropolymer, active polymer content of 22%, charge density of 1.1 meq / g dry polymer active product, average MW of polymer 5,000 .000 g / mol.
    [0091] The addition times of the chemical compounds are shown in Table 2 as a negative time before the drainage begins. The sample is taken from 100 ml of the first filtered material. The filtered material is centrifuged at 3,000 rpm for 4 - 5 hours after adding the biocide. From the centrifuge, the supernatant COD is measured using the Hach Lange LCK 1041 method according to the manufacturer's instructions, as described above. Starch is measured from the filtered material using the HK Lange LCK 357 method according to the manufacturer's instructions, as described above. The results are shown in Table 2.
    [0092] From Table 2 it can be seen that the addition of the coagulating agent and the flocculating agent, in that order, clearly improves the starch retention, that is, the amount of starch in the filtered material is decreased. The COD value of the filtered material is similarly decreased. This indicates that the starch must be retained in the fibers in the thickening step or in the wire section of the paper machine. Table 2. Results of Example 2.
    * product dosage, not calculated as active substance. ** dosage calculated based on the dry active substance. Example 3.
    [0093] The test pulp paste is prepared from old corrugated cardboard (OCC) test liner packaging paper. The test lining paper is cut into 2 × 2 cm pieces. The dilution water comprises 50% of the water in the tray of the test lining machine and 50% of tap water. The conductivity of the tap water is adjusted to the same level as that in the tray water when adding NaCl. The pieces of paper are soaked in the dilution water, which is heated to + 50 ° C, for 10 minutes at 2% of the consistency. Wet disintegration is performed in the Britt flask (Paper Research Materials, Inc., Seattle, WA) 50,000 rotations, 20 hours before sheet preparation.
    [0094] Monochloramine (MCA) and zinc are added to the dilution water of some of the samples. Zn is dosed as a zinc chloride solution, and the dosage is 50 ppm. The dosage of MCA is also 50 ppm, high enough to have residual chloride in the pulp paste the next day. The properties of the test pulp paste are shown in Table 3. Table 3 Properties of the test pulp paste.

    [0095] The pulp of the test pulp is further diluted with tap water adjusted to the conductivity at a concentration of 1% one to two hours before the preparation of the leaf. The conductivity of the tap water is adjusted to the same level as that in the tray water when adding NaCl.
    [0096] The general principle of producing foil for hands with the foil formed for Rapid Kothen hands is as follows:
    [0097] The leaves are formed with the leaves formed by Rappid Kothen hands according to the ISO 5269/2 standard. The pulp suspension is stirred at a constant rate of stirring and a dry strength additive is added to the suspension. Stirring of the test paste is carried out at 1,000 rpm with the paddle mixer. All sheets are dried in vacuum dryers for 5 minutes at a pressure of 1,000 mbar and at a temperature of 92 ° C. After drying, the leaves are preconditioned for 24 h at 23 ° C at a relative humidity of 50%. The base weight of the sheet is 113 g / m2 in the air-conditioned state. The base weight is adjusted by the dosage of the cationic polyacrylamide retention polymer (C-PAM), to maintain constant retention.
    [0098] The properties of the test chemicals are described in Table 4. The following abbreviations are used: G-PAM is glyoxylated polyacrylamide; C-PAM-S is the cationic polyacrylamide reinforcing polymer; PEI is the polymer fixed cross-linked with ethylene imine groups in the polymer main chain; Silica is colloidal silica in the water solution, 15% solids content, particle size 5 nm, S-value 60; Ret C-PAM is the cationic polyacrylamide retention polymer; A-PAM is the anionic polyacrylamide dispersion retention polymer; A-PAM-S is the anionic acrylamide reinforcing polymer in the water solution. Table 4. Properties of the test chemicals used.

    [0099] The chemical sequence of the test is shown in Table 5. The sequence always begins with the addition of the biocide if not otherwise indicated. Table 5. Sequence of test chemical compounds.

    [00100] After the formation of the leaves for the hands, the leaves for the hands obtained are tested for various properties using the methods presented in Table 7. The starch content in the leaves is measured by soaking 4 g of leaves for the hands dried in 200 ml of water, to obtain 2% of concentration, when using an immersion mixer for 1 minute. The sample of the soaked pulp paste is then acidified to a pH <3, typically a pH of 2.5 - 2.9, with HCl, centrifuged for 15 minutes, at 5,000 rpm, in a centrifuge (Megafuge 2.0, Heraeus Instruments) and filtered through a 0.45 μm syringe filter (ACRODISC PSF Syringe Filters GxF / PVDF 0.45 μm, Pall). To a 50 ml flask is added 15 ml of the filtered sample, which is tinted with an iodine solution which has 7.5 g / l KI and 5 g / l I2. The dose of dye is 2.5 ml / sample, and 6.5 ml of 1% HCl is added to the vial and the vial is filled to the 50 ml mark with water. Absorbance is measured at 583 nm with a UV spectrophotometer (Shimadzu UV-1800). Calibration solutions for starch concentration versus absorbance determination are prepared from Cargill C * Film TCF 70325 starch. The linear adjustment line is designed to correlate absorbance to starch content. Table 6. Test program and addition times
    Table 7. Measured sheet properties for hands and standard methods used.

    [00101] The results for measurements of the properties of the leaf for the hands are shown in Table 8. It can be seen that the starch content in the leaf for the hands is increased when the addition sequence according to the invention is used in the comparison with reference samples A and B. The increased starch content in the leaves for the hands also indicates that the COD value in the process water, which is discharged in the thickening step or in the preparation of the leaf, is decreased. Table 8 Results for the measurement of leaf properties for hands.

    [00102] Even though the invention has been described with reference to what at present appear to be the most practical and most preferred modalities, it should be appreciated that the invention will not be limited to the modalities described above, but the invention also lends itself to cover different modifications and equivalent technical solutions within the scope of the appended claims.
    权利要求:
    Claims (15)
    [0001]
    1. Method for making paper, paper towels, cardboard or the like by using recycled fiber material as a raw material, in which the method comprises the following steps: - forming pulp from recycled paper, cardboard or something of the genus in a pulp former and obtain a pulp flow comprising (i) an aqueous phase and (ii) at least recycled fibers and low molecular weight starch, which are dispersed in the aqueous phase; characterized by - adding a coagulating agent to the pulp flow or to an aqueous process flow comprising the low molecular weight starch; - allowing the coagulating agent to interact with the low molecular weight starch and optionally forming aggregates; and - adding at least one flocculating agent, after adding the coagulating agent, to any flow, which comprises the interacted coagulating agent, and forming a starch-treated flow comprising agglomerate (s); - retaining at least a part of said aggregates and / or said agglomerates in the fibers or in a network, which is formed.
    [0002]
    Method according to claim 1, characterized by reducing the COD value of the treated stream by at least 10%, preferably at least 20%, and more preferably at least 40%, by the COD value of the aqueous phase the pulp flow or the COD value of the aqueous process flow to which the coagulant is added.
    [0003]
    Method according to claim 1 or 2, characterized in that - sieving the pulp flow and separating the unwanted material from the pulp flow; - thicken the sieved pulp flow to a higher concentration, that is, storage concentration by separating a part of the aqueous phase from the pulp flow as a discharge flow; and - adding the coagulating agent to the pulp flow prior to the thickening step or to the discharge flow of the thickening step.
    [0004]
    Method according to claim 1 or 2, characterized in that - sieving the pulp flow and separating the unwanted material from the pulp flow; and - adding the coagulant immediately after the pulping step, before the sieving step or after the sieving step.
    [0005]
    Method according to any one of claims 1 to 4, characterized in that the coagulating agent is an inorganic coagulating agent, selected from the group comprising aluminum sulphate, aluminum chloride, polyaluminium chloride (PAC), sulphate polyaluminium (PAS), silica and polyaluminium sulfate, sodium aluminate, alum, ferric sulfate (Fe2 (SO4) 3), ferrous sulfate (FeSO4), ferric ferrous sulfate, ferric chloride, ferrous chloride, ferrous ferric chloride, sulfate ferric chloride, ferric nitrate, ferric sulfate nitrate, ferric chloride nitrate, ferric hydroxide, bentonite, silicic material, such as colloidal silica, and mixtures thereof.
    [0006]
    Method according to claim 5, characterized by selecting the bentonite coagulating agent, colloidal silica, aluminum compounds and iron compounds comprising Fe (III).
    [0007]
    Method according to claim 6, characterized by adding the coagulant in an amount of - 0.5 - 10 kg of active aluminum / ton of dry pulp, preferably 0.75 - 8 kg of active aluminum / ton of dry pulp, more preferably 1 - 5 kg of active aluminum / ton of dry pulp or - 5 - 50 kg of active Fe / ton of dry pulp, preferably 6 - 40 kg of active Fe / ton of dry pulp, with more preferably 8 - 20 kg of active Fe / ton of dry pulp or - 0.5 - 10 kg of dry bentonite / ton of dry pulp, preferably 1 - 8 kg of dry bentonite / ton of dry pulp, more preferably 2 - 5 kg of dry bentonite / ton of dry pulp, or - 0.1 - 1 kg of dry silica / ton of dry pulp, preferably 0.2 - 0.8 kg of dry silica / ton of dry pulp, preferably 0.25 - 0.5 kg of dry silica / ton of dry pulp, depending on the active substance in the coagulant
    [0008]
    Method according to any one of claims 1 to 7, characterized by adding flocculating agent to the flow, which comprises the interacting coagulating agent, after the pulp storage silos and before a paper machine inbox or cardboard.
    [0009]
    Method according to any one of claims 1 to 8, characterized by selecting the flocculating agent from the group comprising cationic polyacrylamide (C-PAM), anionic polyacrylamide (A-PAM), polyvinyl amine (PVAm), oxide of polyethylene (PEO), polyethylene imine (PEI) and mixtures thereof.
    [0010]
    Method according to any one of claims 1 to 9, characterized by adding the flocculating agent (s) in an amount of 20 - 2000 g / ton of paper or cardboard, typically 50 - 1000 g / ton ton of paper or cardboard, preferably 100 - 500 g / ton of paper or cardboard, values are provided as an amount of active flocculating agent (s).
    [0011]
    11. Method according to claim 1, characterized in that the low molecular weight starch comprises an oxidized surface glue starch that has an average weight in the range of 100,000 - 5,000,000 g / mol, more typically of 200,000 - 4000,000 g / mol, or the low molecular weight starch comprises an acid or enzyme degraded surface starch that has an average weight in the range of 30,000 - 3,000,000 g / mol, more typically 40,000 - 2,000. 000 g / mol.
    [0012]
    Method according to claim 1, characterized in that it adds a biocide and / or an amylase enzyme inhibitor to the pulp former and / or to a process flow, such as the pulp flow or the aqueous process flow.
    [0013]
    Method according to claim 12, characterized in that - adding the biocide and / or the amylase enzyme inhibitor to the pulp between the pulp former entrance and the thickening step of the sieved pulp flow, or - adding the biocide and / or the amylase enzyme inhibitor to the pulp flow before the pulp storage towers or silos located after the thickening step.
    [0014]
    14. Method according to claim 1, characterized by adding reinforcing agents and / or flocculating additives to the pulp flow, the reinforcing agent being selected from the group comprising starch, cationic polyacrylamide (C-PAM), anionic polyacrylamide ( A-PAM), glyoxylated polyacrylamide (G-PAM), amphoteric polyacrylamide, polydialldimethylammonium chloride (poly-DADMAC), polyacrylic amide (PAAE), polyvinyl amine (PVAm), polyethylene oxide (PEO), polyethyleneimine (PEI), polyethyleneamine , guar gum, carboxymethyl cellulose (CMC), and mixtures thereof.
    [0015]
    Method according to any one of claims 1 to 14, characterized by the pulp of recycled paper, cardboard and / or old corrugated container (OCC) cardboard, comprising starch, wherein the COD value of the aqueous phase of the flow of the untreated pulp is> 20 kg / ton, more typically> 35 kg / ton, before adding the coagulant and flocculating agent.
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    ES2607797T3|2017-04-04|
    EP2817453A1|2014-12-31|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2020-02-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-12-08| B09A| Decision: intention to grant|
    2021-03-02| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 22/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    FI20125204|2012-02-22|
    FI20125204A|FI124202B|2012-02-22|2012-02-22|Process for improvement of recycled fiber material utilizing the manufacturing process of paper or paperboard|
    PCT/FI2013/050201|WO2013124542A1|2012-02-22|2013-02-22|Method for making of paper, tissue, board or the like|
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