method for making a lignin component, a lignin component and its uses and a product

专利摘要:
METHOD FOR MAKING A LIGNIN COMPONENT, A LIGNIN COMPONENT AND ITS USES AND A PRODUCT. The invention relates to a method for producing a lignin component from lignin material, by an acid treatment, the method comprising: forming a lignin component of lignin material, by treating the lignin material in at least an acid treatment stage; and optimize the process conditions, through a combination of process parameters comprising the retention time, temperature and pH level in the acid treatment stage so that the retention time is 6 hours for at least one stage acid treatment. In addition, the invention relates to the corresponding lignin components, to a use of the lignin component and to a product.
公开号:BR112014013964B1
申请号:R112014013964-4
申请日:2012-12-05
公开日:2021-01-19
发明作者:Mauno Miettinen
申请人:Upm-Kymmene Corporation；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The invention relates to a method for the manufacture of a lignin component. In addition, the invention relates to a lignin component and to a use of the lignin component. In addition, the invention relates to a product. BACKGROUND OF THE INVENTION
[002] A method for separating lignin from black liquor is known from WO 2006/031175. OBJECTIVE OF THE INVENTION
[003] The purpose of the invention is to disclose a new method for the manufacture of a lignin component. Another objective of the invention is to produce a lignin component with improved properties and a product comprising the lignin component. SUMMARY OF THE INVENTION
[004] The method for producing a lignin component from a lignin material according to the present invention is shown in the claims.
[005] The lignin component according to the present invention is shown in the claims.
[006] The use of the lignin component according to the present invention is presented in the claims.
[007] The product according to the present invention is presented in the claims. BRIEF DESCRIPTION OF THE FIGURES
[008] The attached figures, which are included to provide a better understanding of the invention and which form a part of this specification, illustrate some modalities of the invention and, together with the description, help to explain the principles of the invention. In the figures:
[009] Fig. 1 is a flow diagram illustration of a method according to one embodiment of the present invention, Fig. 2 is a flow diagram illustration of a method according to another embodiment of the present invention, Fig. 3 is a flow diagram illustration of a method according to another embodiment of the present invention, Fig. 4 is a flow diagram illustration of a method according to another embodiment of the present invention, Figs . 5a and 5d show lignin structures in cakes of comparative lignin components, Figs. 5b and 5c show the lignin structures in cakes of lignin components according to the present invention, Fig. 6 is a flow diagram illustration of a method according to an embodiment of the present invention, Fig. 7 is a flow diagram illustration of a method according to another embodiment of the present invention, Fig. 8 shows a SEM image of the bolus lignin structure of a lignin component according to the present invention, Fig. 9 shows a flow diagram illustration of a method according to one embodiment of the present invention, Fig. 10 shows a flow diagram illustration of a method according to another embodiment of the present invention, and Fig. 11 shows a device according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION
[010] In the method of the present invention, a lignin component is produced from lignin material by an acid treatment, the method comprising: forming a lignin component of lignin material, by treating the lignin material in at least an acid treatment stage; and optimize the process conditions, through a combination of process parameters comprising the retention time, temperature and pH level in the acid treatment stage so that the retention time is 6 hours, for at least one stage of acid treatment.
[011] One embodiment of the method of the present invention is shown in figure 1. Another embodiment of the method of the present invention is shown in figure 2. Another embodiment of the method of the present invention is shown in figure 3. Another embodiment of the method of the present invention is shown in figure 4. In addition, the lignin structures in cakes of lignin components are shown in Figures 5a - 5d.
[012] In the method of the present invention, a lignin component is produced from a lignin material (1) by treatment with weak acid. According to the invention, a lignin component (3) is formed of lignin material so that the lignin material (1) is treated in at least one acid treatment stage (2a, 2b) and at least one stage acid treatment is optimized by means of a combination of process parameters comprising the retention time, for example, long retention time, the temperature, for example, high temperature and the pH level, for example, low enough, to decrease the ashes and / or carbohydrates in the lignin component, and preferably to remove the undesirable substance from the lignin component and to purify the lignin component.
[013] The invention is especially based on improving the properties of the lignin component. When the lignin material is treated with acid in one or more acid treatment stages, optimizing the retention time, temperature and pH level, then properties, such as purity, dry solids content, filterability, amounts of carbohydrates and ash from the lignin component can be improved. In addition, the odor in the lignin component can be reduced. Then, a lignin component is provided that is suitable for use in typical and special applications.
[014] In this context, a lignin material refers to any material or composition that contains lignin. The lignin material can contain one or more material components. In one embodiment, suitable and desired additives can be added to the lignin material to form a desired lignin component.
[015] In one embodiment, the lignin material includes the material that is selected from a group consisting of lignin from the alkaline pulping process, Kraft lignin, lignin from the sodium process, lignin from a process in that lignin is separated from the raw material by a solution that includes suitable chemicals and their combinations.
[016] In one embodiment, the lignin material includes flash-precipitated lignin. In one embodiment, the flash-precipitated lignin is obtained after precipitation with CO2-. Preferably, flash-precipitated lignin is formed as described in patent application PCT / FI2011 / 050896.
[017] In one embodiment, lignin is precipitated from the black liquor by a continuous process, with CO2 at 3-8 bar overpressure. In one embodiment, lignin is separated by a flash precipitation lignin separation method, as disclosed in patent application PCT / FI2011 / 050896. In one embodiment of the present invention, lignin is flash-precipitated lignin. The term "flash precipitated lignin" should be understood in this specification as the lignin that was precipitated from black liquor in a continuous process by lowering the pH of a black liquor flow, under the influence of an overpressure of 200 - 1000 kPa, up to the level of precipitation of lignin using an acidifying agent based on carbon dioxide, preferably carbon dioxide, and subtly releasing the pressure to precipitate the lignin. The residence time in the above method is less than 300 s. Flash-precipitated lignin particles, having a particle diameter of less than 2 μm, form agglomerates that can be separated from the black liquor using, for example, filtration. Flash-precipitated lignin can be purified and / or activated, if necessary for further processing. Flash precipitated lignin has many advantages, for example, activity, dispersibility, solubility, drainability and preservability. In one embodiment of the present invention, the lignin component is a flash precipitated kraft lignin. Preferably, the flash precipitated kraft lignin is undrained. Therefore, lignin has greater activity, and lignin can be redissolved. Lignin needs only a very simple redispersion stage when it is added, for example, in an adhesive mixture. In addition, controlling the amount of water in the lignin-based composition is easier when redispersion is easier. In addition, lignin is easier to handle in the process because lignin is not dusty. Preferably, flash-precipitated kraft lignin has a dry matter content of 50 - 80%.
[018] In one embodiment, the lignin material is treated chemically and / or mechanically before at least one acid treatment stage of the present invention. In one embodiment, the lignin material is precipitated before at least one acid treatment stage. In one embodiment, the lignin material is resuspended before at least one acid treatment.
[019] In this context, a lignin component means the product formed from lignin material in one or more stages. The term "lignin component" is used after the first stage of treatment.
[020] In this context, a carbohydrate refers to any carbohydrates, especially hemicellulose.
[021] In one embodiment, the at least one acid treatment stage is the acid wash (2a). In acid washing, an amount of ash can be reduced in the lignin component. In addition, in acid washing, the filterability of the lignin component can be improved. In addition, the acid wash of the dry solids content of the lignin component can be improved. The improved dry solids content of the filter cake leads to less energy consumption in drying and less water consumption in washing to achieve the same purity. In addition, the dryer can be smaller, which leads to savings in investment. Savings in water consumption are important, as the wash water is likely to circulate back to the evaporation plant. In addition, a certain dry solids content is necessary to maintain the processability of lignin cakes. For applications that do not require any drying, for example, firing, the low water content in the filter cake is a benefit.
[022] In one embodiment, the at least one acid treatment stage is acid hydrolysis (2b). In acid hydrolysis, an amount of carbohydrates can be decreased in the lignin component. In addition, in acid hydrolysis, an amount of ash can be further reduced in the lignin component. It is important that the lignin is soft before or during acid hydrolysis; then the carbohydrates can be removed from the lignin component and the lignin component can be purified. Softening is preferably carried out slowly at the correct temperature to prevent condensation of lignin and the formation of charcoal. Softening can be carried out over a wide pH range.
[023] In one embodiment, the lignin material (1) is treated in two acid treatment stages in which the first stage is the acid wash (2a) and the second stage is the acid hydrolysis (2b). The first stage can be a typical acid wash. Preferably, the second stage is a purification stage.
[024] In this context, acid washing refers to any acid washing method. In one embodiment, the acid wash is carried out with H2SO4, another acid or another suitable acidifying chemical. The optimization of the invention positively affects the consumption of H2SO4 or another acid or other acidifying chemical.
[025] In this context, acid hydrolysis refers to any method of acid hydrolysis. In one embodiment, acid hydrolysis is carried out using H2SO4, or another suitable acidifying chemical, typically in the presence of water.
[026] In one embodiment, the lignin material is treated in at least one acid treatment stage with H2SO4.
[027] In one embodiment, the method comprises two stages of the acid treatment method. In one embodiment, the first step is the removal of ash and the second step is the removal of carbohydrates. In one embodiment, the first step is an increase in the dry solids content in the lignin component and the second step is the removal of carbohydrates from the lignin component. In one embodiment, the first step involves removing ash and increasing the dry solids content in the lignin component, and the second step is removing the carbohydrates from the lignin component.
[028] In one embodiment, the method comprises a pre-treatment step before at least one acid treatment step. In one embodiment, the lignin material is resuspended in the pre-treatment step. In a preferred embodiment, the pretreatment step is a lignin softening step, in which the lignin is softened and the lignin structure is modified. An acid is able to hydrolyze carbohydrates to lignin after the softening step.
[029] Preferably, at each acid treatment stage of the invention, an appropriate combination of temperature, retention time and pH level is selected. The selected combination varies based on acid wash or acid hydrolysis. The process conditions are selected so that the lignin does not alternate with carbon or carbon during treatment with acid.
[030] Preferably, the long retention time is used in the acid treatment according to the invention. In one embodiment, the retention time is more than 1 hour. In one embodiment, the retention time is greater than 4 hours, preferably greater than 6 hours, more preferably, greater than 8 hours. In one embodiment, the retention time is more than 16 hours.
[031] In this context, the retention time means the time of the treatment stage. The retention time does not include a filtration time.
[032] In one embodiment, the temperature is above 60 ° C during the treatment stage. In one embodiment, the temperature is greater than 70 ° C, preferably greater than 72 ° C, more preferably greater than 73 ° C, and more preferably greater than 75 ° C.
[033] In one embodiment, the preferred pH level is low enough during the treatment stage. In one embodiment, the pH level is 3.5, preferably between 2 - 3. In one embodiment, the pH level is less than 2.0, preferably between 0.5 - 1.5. In one embodiment, the pH level, which is between 2-4, can be used.
[034] In one embodiment, the pH level is between 0.5 - 4.0, preferably 0.8 - 1.5, the temperature is between 80 - 130 ° C, preferably 80 - 105 ° C , and the retention time is between 2 - 60 hours, preferably 6 - 30 hours, in at least one acid treatment stage, for example, in the acid hydrolysis stage. The temperature is below the glass transition point of lignin.
[035] In one embodiment, the pH is between 2.5 - 3.5, the temperature is between 65 - 80 ° C, preferably between 70 - 80 ° C and more preferably about 70 ° C, and the retention time is more than 1 hour in the acid wash stage. Increasing the temperature and / or retention time and / or reducing the pH level of the dry solid content and filterability can be improved.
[036] In one embodiment, the lignin material is treated in at least one acid treatment stage and the at least one acid treatment stage is optimized using process parameters selected from the retention time, temperature, pH level, mixture, oxidation and their combinations. In one embodiment, the combination of the selected process parameters is optimized in at least one acid treatment stage. In one embodiment, the combination of selected process parameters is optimized at each stage of treatment with acid.
[037] In one embodiment, the acid treatment stage is adjusted using process parameters to increase lignin fragments of low molecular weight. If severe reaction conditions, for example, temperature above 70 ° C, retention time greater than 8 hours and pH level between 1 - 1.5, are applied in acid hydrolysis, then low molecular weight lignin can be achieved by improving productivity.
[038] In one embodiment, when pretreatment is done before acid treatment so that the pretreatment retention time is less than 2 hours, the temperature is between 55 - 70 ° C and the pH is between 9 - 10.5. In one embodiment, when pretreatment is done before acid treatment so that the pretreatment retention time is less than 2 hours, the temperature is between 55 - 75 ° C and the pH is 9 - 10 , and in acid treatment, the retention time is more than 8 hours, the temperature is between 70 - 80 ° C and the pH is less than 3.5. Alternatively, when the pretreatment is done before the acid treatment so that the pretreatment retention time is more than 8 hours, the temperature is between 60 - 75 ° C and the pH is 9 - 10, and in the treatment with acid the retention time is less than 2 hours, the temperature is between 65 - 80 ° C and the pH is less than 3.5.
[039] It is important for the invention that the retention time is used in at least one stage. Alternatively, the retention time can be used in more than one stage. The long retention time can be used in the acid treatment stage, for example, in the acid wash and / or acid hydrolysis, and / or in the pre-treatment step.
[040] In one embodiment, the formed lignin component (3) is filtered in the filtration stage (4a, 4b) after at least the last acid treatment stage (2a, 2b). In one embodiment, the formed lignin component is filtered after each of the at least one acid treatment stage.
[041] In this context, filtration refers to any filtration method that can be used to filter lignin. Preferably, in filtration, the lignin component is washed with water and pressed and, optionally, air-dried. Filtration can be carried out by any suitable filtration device. In one embodiment, the formed lignin component is filtered by filtration under pressure or filtration under vacuum. In one embodiment, the pressure is between 10 - 20 bar (1000 - 2000 kPa), preferably 13 - 17 bar (1300 - 1700 kPa) and more preferably, about 15 bar in pressure filtration.
[042] Preferably, improved filterability, especially a better filtration rate, achieved through optimization leads to less pressure on filtration and shorter filtration times. Then, cheaper filters, for example, based on the size and type of device, can be used.
[043] In one embodiment, the pH level is adjusted shortly before filtration, especially if the shorter retention time is used in the acid treatment stage.
[044] In one embodiment, the temperature is above 50 ° C and the pH is between 2 and 4 during filtration.
[045] In one embodiment the lignin material is treated in at least one acid treatment stage such that the dry solids content of the lignin component can be increased by more than 5%, preferably 5 - 15% more preferably about 10 - 15%, compared to the standard lignin component formed by a known acid washing method. In one embodiment, the dry solids content of the lignin component is greater than 60%, preferably greater than 70%, more preferably between 70 - 90% and even more preferably between 70 - 80%.
[046] In one embodiment, the lignin material is treated in at least one acid treatment stage such that the carbohydrate content of the lignin component is less than 1.0%, preferably less than 0.5 %, more preferably, less than 0.2% and even more preferably, less than 0.1%.
[047] In one embodiment, the lignin material is treated in at least one acid treatment stage such that the ash content of the lignin component is less than 1.0%, preferably less than 0.5%, more preferably less than 0.2% and even more preferably less than 0.1%.
[048] In a dissolved during at least one acid treatment stage it is adjusted by means of process parameters selected from retention time, temperature, pH level, mixing efficiency, type of mixer, oxidation and its combinations. Then, the low molecular weight lignin component can be achieved. In one embodiment, the proportion of dissolved lignin is adjusted during the acid hydrolysis phase.
[049] In one embodiment, additional oxidation is carried out after filtration in which an acid filtrate is further oxidized.
[050] In one embodiment, the lignin component is further oxidized during the acid treatment stage, for example, in the acid hydrolysis stage. Additional oxidation can be carried out by means of air, oxygen, another oxidizing agent or their combinations, to stabilize the structure of the lignin component, to increase the purity of lignin and to remove odor.
[051] The lignin component (3) that can be obtained by the method of the present invention can be used as a component in the manufacture of a final product selected from activated carbon, carbon fiber, lignin composite, for example, composite of lignin-plastic or lignin fiber composite, binder material, phenolic component, dispersing agent and their combinations.
[052] The final product or product comprises the lignin component of the present invention. Preferably, the pure lignin component is required according to the present invention in the manufacture of carbon fibers and activated carbon.
[053] The method according to the present invention provides the lignin component with good quality. By improving the purification and increasing the dry solids content of the lignin component then better properties of the lignin component and the final product can also be provided.
[054] The present invention provides an industrially applicable, simple and inexpensive way to produce the lignin component from the lignin material. The method according to the present invention is simple and easy to carry out as a production process. The method according to the present invention is suitable for use in the manufacture of different lignin components from different lignin materials.
[055] The invention is described in more detail by the following examples 1 - 6 with reference to the attached figures 1 - 4 and 5a-d. Example 1
[056] In this example and in Figure 1, a lignin component (3) is formed by an acid treatment.
[057] A lignin starting material (1), which is flash-precipitated lignin, is treated by two stages of acid treatment (2a, 2b). The first stage (2a) is an acid wash stage and the second stage (2b) is an acid hydrolysis stage. The process conditions are as follows in the first stage: temperature above 70 ° C, retention time greater than 1 hour and the pH level of about 3. The acid wash is carried out with H2SO4. The process conditions are as follows in the second stage: temperature above 70 ° C, retention time over 8 hours and pH level between 1 - 1.5. The acid treatment in the hydrolysis is carried out with H2SO4.
[058] The lignin component (3) is filtered after each acid treatment step (2a, 2b), by pressure filtration (4a, 4b). Temperature is above 50 ° C and the pH is about 2 to 4, during filtration.
[059] The lignin component can be further oxidized during the acid treatment stage.
[060] In these tests, it was discovered that the lignin component can be produced with excellent properties. The formed lignin component has a low ash and carbohydrate content. It was found that the ash content can be reduced during the first stage. In addition, the ash content can be further reduced during the second stage. It has been found that the carbohydrate content can be reduced, especially during the second stage, but a portion of carbohydrates can be reduced, during the first stage. By means of high temperature, long retention time and low pH, lignin is softened. After softening, the acid is able to hydrolyze carbohydrates and oxidize accessible part of lignin into soluble compounds. Carbohydrates can be removed during treatment with acid.
[061] In addition, it has been found that the dry solids content of the final lignin component cake can be increased and filterability can be increased already in the first stage. Dry solids content of the lignin component can be increased for more than 5% compared to the standard lignin component. The lignin component has an ash content of less than 0.1% and a carbohydrate content of less than 0.2%. In addition, at least part of the inorganic sulfur was removed in the acid hydrolysis stage. In addition, by means of acid hydrolysis, the glass transition temperature of lignin and / or the temperature of lignin decomposition can be increased.
[062] In addition, the lignin structure in the lignin component cake was found to be in the form of single large particles. This explains the good filterability and the high dry solids content.
[063] Furthermore, in these tests, it was found that the good special optimization results were achieved by the two-stage process. Example 2
[064] In this example and in Figure 2, a lignin component (3) is formed by an acid treatment.
[065] A lignin starting material (1) is treated by an acid treatment stage, which is an acid wash stage (2a). The process conditions are as follows: temperature is about 70 ° C, retention time is over 1 hour and the pH level is about 3. The acid wash is carried out with H2SO4.
[066] The lignin component (3) is filtered after acid washing by pressure filtration (4a). The temperature is above 50 ° C and the pH is about 2 to 4, during filtration.
[067] In these tests, it was found that the formed lignin component has a low ash content, but the carbohydrate content has not decreased, as in example 1. It has been found that the ash content can be reduced during acid washing . Example 3
[068] In this example and in Figure 3, a lignin component (3) is formed by an acid treatment.
[069] A lignin starting material (1) is treated by an acid treatment stage, which is an acid hydrolysis (2b). The process conditions are as follows: temperature above 70 ° C, retention time over 8 hours and the pH level between 1 - 1.5.
[070] The lignin component (3) is filtered after acid hydrolysis by means of pressure filtration (4b). The temperature is above 50 ° C during filtration.
[071] In these tests, it was discovered that the lignin component can be produced with good properties. The formed lignin component has low levels of ash and carbohydrates. It has been found that ash content and carbohydrate content can be reduced during acid hydrolysis. Example 4
[072] In this example, and in figure 4, a lignin component (3) is formed by an acid treatment.
[073] A lignin starting material (1) is treated, firstly, in a pre-treatment stage (5), in which a resuspension stage is performed, and secondly, in an acidic washing stage (2a), to produce a lignin component. After the acid wash, the lignin component is filtered (4a).
[074] In tests 1 - 4, pretreatment is performed so that short retention times and high pH are used. Then, in acid wash, long retention times and low pH are used.
[075] In tests 5 and 6, pretreatment is performed so that long retention times and high pH are used. In acid washing, shorter retention times and a low pH of about 2.5 are used. It was found that, during the pretreatment of tests 5 and 6, the softening and growth of lignin particles occurs thanks to the long retention time. Therefore, the shorter retention time is sufficient for acid washing.
[076] The process conditions are described in table 1. Table 1
where T5 is the pre-treatment temperature t5 is the pre-treatment retention time T2a is the acid wash temperature t2a is the acid wash retention time Tfilt is the filtration temperature
[077] In these tests, it was discovered that the lignin component with good dry matter of the cake can be produced. In tests 1-4, it was found that the dry matter of the cake can be increased when the acid wash temperature is above 70 ° C, the acid wash retention time is long and the pH is low, around 2, 5.
[078] Furthermore, in tests 5 - 6, it was found that the dry matter of the cake can be increased when the pretreatment temperature is above 70 ° C and the pretreatment retention time is long.
[079] It has been found that it is important for the invention that the long retention time and temperature of 70 ° C are used in at least one acid treatment stage.
[080] Two lignin components of the present invention were shown in figures 5b (Test 2) and 5c (Test 5) (SEM images). As a comparison, figures 5a (Test 1) and 5d (Test 6) (SEM images) show structures of comparative lignin components. The improvements in filterability and dry matter of the cake between Test 1 and Test 6 are mainly due to the increase in agglomeration. The improvement in cake dry matter between Test 6 and Tests 2 - 5 is due to softening of the lignin and restructuring into larger individual particles. Example 5
[081] In this example and in figure 2, a lignin component (3) is formed by an acid treatment.
[082] A lignin starting material (1) is resuspended, and then the lignin is then treated in an acid treatment stage (2a) to produce a lignin component. After treatment with acid, the lignin component is filtered (4a).
[083] The delay between resuspension and acid treatment is about 1 hour and the temperature is about 60 - 65 ° C.
[084] The conditions of the acid treatment process are described in table 2 In tests 3 - 4 the treatment with acid is carried out so that long retention times and low pH are used. Tests 1 and 2 are comparative tests. In test 1 a low temperature and a short retention time are used. In test 2, a low temperature and a long retention time are used. Table 2
where T2a is the temperature of the treatment with acid t2a is the retention time of the treatment with acid Tfilt is the temperature of the filtration
[085] In these tests, it was discovered that the lignin component with good cake dry matter can be produced. In tests 1 - 4, it was found that the dry matter of the cake can be increased when the temperature of the acid treatment is above 70 ° C, the retention time of the acid treatment is long and the pH is low, of about 2.5. Example 6
[086] In this example and in Figure 1, a lignin component (3) is formed by two stages of treatment with acid.
[087] A lignin starting material (1) is resuspended, and after that the lignin is treated with a two-stage acid treatment (2a, 2b) to produce a lignin component. The first stage of acid treatment, in this example, is test 5 in Table 1. The first stage is an acid wash and the second stage is an acid hydrolysis. After each stage of the acid treatment, the lignin component is filtered (4a, 4b).
[088] Lignin cake from the acid wash stage was resuspended for 1 hour at 60 ° C - 70 ° C. The pH of the lignin suspension was adjusted just before the acid hydrolysis stage.
[089] The conditions of the acid hydrolysis process are described in Table 3. Table 3
Where T2b is the acid hydrolysis temperature t2b is the acid hydrolysis retention time Tfilt is the filtration temperature
[090] Test 9 with T2b of 140 ° C, t2b of 1 hour and pH of 3.5, resulted in the formation of coal, which adhered to the reactor walls.
[091] In these tests of examples 1 - 6 it was discovered that the lignin component with good ash content and carbohydrate content can be produced. Starting from the lignin material for the hydrolysis tests, then Test 5 in Table 1 had a carbohydrate content of 0.73%. In tests, it was found that the ash and carbohydrate content can be decreased when the acid hydrolysis temperature was high, above 75 ° C, the acid hydrolysis retention time was long and the pH was low. The long retention time in the acid wash stage decreases the time required in the acid hydrolysis stage. The molecular weight of lignin after acid hydrolysis reveals that extensive condensation has not been found. The consumption of acidic sulfuric acid increases rapidly when the pH is below 1.
[092] One embodiment of the method of the present invention is shown in figure 6. Another embodiment of the method of the present invention is shown in figure 7. A structure of a lignin component is shown in figure 8.
[093] The invention relates to the optimization of acid treatment in the lignin separation process. In the method of the present invention, a lignin component is formed from a lignin material, by an acid treatment, the method comprising: forming a lignin component (3) of lignin material (1) by treatment of the lignin material. lignin in an acid treatment stage (2) by means of an acidic composition; and optimize the process conditions in the acid treatment stage (2), so that the high temperature above 70 ° C, long retention time, such as the delay time, above 6 hours and the pH level between 4,5 - 7 are used during acid treatment to remove the undesirable substance from the lignin component and to purify the lignin component and to reduce acid consumption in the treatment of acid lignin.
[094] In a preferred embodiment, the lignin material (1) is treated by an acidic wash (2), to form a lignin component (3). The lignin material (1) is treated in an acid wash stage (2). The long retention time over 6 hours, the high temperature above 70 ° C, and the pH level between 4.5 and 7 are used in acid washing.
[095] The invention is based especially on improving the properties of the lignin component. When the lignin material is treated with acid, by optimizing the process conditions and parameters, for example, retention time and temperature, then the highest pH level, for example, 4.5 - 7, instead of about 2.5, can be used, and then properties, such as purity, dry solids content and filterability of the lignin component, are good. In addition, consumption of acid such as virgin acid can be decreased. Preferably, the destabilization of the lignin occurs before filtration thanks to the high temperature and the long retention time in the acid treatment. In addition, the odor in the lignin component can be reduced. Next, the lignin component is provided which is suitable for use in typical and special applications.
[096] In this context, a lignin material refers to any material or composition that contains lignin. The lignin material can contain one or more material components. In one embodiment, suitable and desired additives can be added to the lignin material to form a desired lignin component.
[097] In one embodiment, the lignin material includes material that is selected from a group consisting of lignin from the alkaline pulping process, Kraft lignin, lignin from the sodium process, lignin from a process in which the lignin it is separated from the raw material by a solution that includes suitable chemicals and their combinations.
[098] In one embodiment, the lignin material includes flash-precipitated lignin. In one embodiment, lignin precipitated in flash is obtained after precipitation with CO2. Preferably, the flash-precipitated lignin is formed as described in patent application PCT / FI2011 / 050896.
[099] In one embodiment, the lignin is precipitated from the black liquor by a continuous process, with CO2 at 6 - 10 bar (600 - 1000 kPa) of overpressure. In one embodiment, lignin is separated by a flash precipitation lignin separation method, as disclosed in patent application PCT / FI2011 / 050896. In one embodiment of the present invention, lignin is flash-precipitated lignin. The term "Flash precipitated lignin" should be understood in this specification as the lignin that was precipitated from black liquor in a continuous process by reducing the pH of the black liquor flow, under the influence of an overpressure of 200 - 1000 kPa , to the level of precipitation of lignin using an acidifying agent based on carbon dioxide, preferably carbon dioxide, and suddenly releasing the pressure to precipitate the lignin. The residence time in the above method is less than 300 s. The flash-precipitated lignin particles, having a particle diameter of less than 2 μm, form agglomerates that can be separated from the black liquor, for example, using filtration. Flash-precipitated lignin can be purified and / or activated, if necessary, for further processing. Flash precipitated lignin has many advantages, for example, activity, dispersibility, solubility, drainability and preservability. In one embodiment of the present invention, the lignin component is a flash precipitated kraft lignin. Preferably, the flash precipitated kraft lignin is undrained. Therefore, lignin has greater activity, and lignin can be redissolved. Lignin needs only a very simple redispersion stage when it is added, for example, in an adhesive mixture. In addition, controlling the amount of water in the lignin-based composition is easier when redispersion is easier. In addition, lignin is easier to handle in the process because lignin is not dusty. Preferably, flash-precipitated kraft lignin has a dry matter content of 50 - 80%. [100] In one embodiment, the lignin material is treated chemically and / or mechanically before the acid treatment stage of the present invention. In one embodiment, the lignin material is precipitated before the acid treatment stage. In one embodiment, the lignin material is resuspended before treatment with acid. [101] In this context, a lignin component means the product formed from lignin material in one or more stages. The term "lignin component" is used after the first stage of treatment. [102] In this context, acid washing refers to any acid washing method. In one embodiment, the acid wash is carried out with an acidic composition containing sulfuric acid (H2SO4), another acid or other suitable acidifying chemical or combination thereof. The optimization of the process positively affects the consumption of H2SO4 or another acid or other acidifying chemical. [103] In one embodiment, the acidic composition contains sulfuric acid, which can be either virgin acid or recycled acid. Without any improvement in the processes according to the invention, the consumption of sulfuric acid is quite high. Sulfuric acid is inexpensive, but a large amount of sodium hydroxide is needed to meet the Na / S balance of the pulp mill. In addition, any extra sulfur added to the process must be discharged from the recovery boiler, which means extra cost. [104] In a preferred embodiment, the acidic composition contains another acid or another salt containing an acidifying chemical. The salt can be selected from the salt group of K, Na, Mg, Al, Ca or any other suitable salt. In one embodiment, the acidic composition contains sulfate compound with salt. In one embodiment, the acidic composition contains sodium sesquisulfate. Sodium sesquisulfate (SSS) is a fraction of waste from the chlorine dioxide facility at the pulp mill. In one embodiment, the residual acid is used as another acid or another acidifying chemical. [105] Preferably, the composition contains sulfuric acid and other acids or other acidifying chemical with salt. In one embodiment, the acidic composition contains sulfuric acid and sodium sesquisulfate. In one embodiment, the acidic composition contains sulfuric acid in about 10 - 90% by weight, in one embodiment, 60 - 70% by weight, and sodium sesquisulfate in about 10 - 90% by weight, in an embodiment of 30 - 40% by weight. The high pH saves acid or another acidifying chemical containing salt that is good for the pulp mill and takes less salt to process and less water is needed for washing. [106] Preferably, in the acid treatment stage of the invention, a suitable combination of temperature, retention time and pH level is selected. The selected combination varies based on the acid wash method, lignin material, acid composition and the desired product. [107] Preferably, the long retention time is used in the acid treatment according to the invention. In one embodiment, the retention time is greater than 6 hours, preferably greater than 10 hours, and more preferably, between 10 and 20 hours. [108] In this context, the retention time means the time of the treatment stage. The retention time does not include a filtration time. [109] In one embodiment, the temperature is greater than 80 ° C during the acid treatment stage, preferably greater than 85 ° C, and more preferably, between 80 ° C and 90 ° C. [110] In a preferred embodiment, the pH level is high enough during the acid treatment stage. In one embodiment, the pH level is greater than 4.5, preferably greater than 5. In one embodiment, the pH level is less than 7, preferably less than 6. In a preferred embodiment, the level of pH ranging between 5 and 6 can be used. When the high pH is used according to the invention, then this leads to the production of non-corrosive lignin as a product. Then stainless steel instead of more expensive acid-proof steel can be used in the process devices. [111] In one embodiment, the pH level is between about 4.5 - 7, preferably about 5 - 6, the temperature is between 70 - 100 ° C, preferably 80 - 90 ° C, and the retention time is greater than 1 hour, preferably 6 - 30 hours and more preferably, between 10 and 20 hours, in the acid treatment stage. [112] Increased temperature and / or retention time and / or pH level of dry solid content and filterability can be improved. The improvement in the dry solids content of the filter cake leads to less energy consumption in drying and less water consumption in washing to achieve the same purity. In addition, the dryer can be smaller, which leads to savings in investment. Savings in water consumption are important, as the wash water should probably be circulated back to the plant for evaporation. Also a certain dry solids content is necessary to maintain the processability of the lignin cakes. For applications that do not require any drying, for example, firing, the low water content in the filter cake is a benefit. [113] In the present invention, it has been noted that the use of high temperature and long delay time combined with a high pH, for example, 5 - 7, and the use of sodium sesquisulfate can reduce acid consumption even by about 65%, which means the acid consumption of about 70 kg / t of lignin. In the process of the invention, washing the normal cake with water after treatment with acid is sufficient to increase or maintain the pH of the final lignin between 5 and 7.5, preferably 6 - 7. Therefore, the lignin is not corrosive. The production of neutral lignin is a necessity for most applications. If the lignin has a pH of 2.5, an additional process stage is needed to neutralize the lignin. [114] The method of the invention can be used in connection with any acid treatment process, containing one or more acid treatment stages. In one embodiment, the acid treatment process comprises the acid hydrolysis step, before or after the acid wash stage. [115] The method of the invention can be used in connection with the acid treatment process described in patent application FI20116253. [116] In one embodiment, the method of the present invention comprises a pre-treatment step (5) before the acid treatment stage (2). In one embodiment, the lignin material is resuspended in the pre-treatment step. In a preferred embodiment, the pretreatment step is a lignin softening step, in which the lignin is softened and the structure of the lignin is modified. [117] In one embodiment, when pretreatment (5) is done before acid treatment so that the pretreatment retention time is less than 2 hours, the temperature is between 55 - 70 ° C and the pH is between 9 and 10.5. [118] It is important for the invention that the retention time is used in the treatment with acid. Alternatively, the retention time can also be used at another stage such as the pre-treatment stage. The long retention time can be used in the acid wash and / or in the pre-treatment step. [119] In one embodiment, the formed lignin component (3) is filtered at the filtration stage (4), after the acid treatment stage (2). [120] In this context, filtration refers to any filtration method that can be used to filter lignin. Preferably, in filtration, the lignin component is washed with water and pressed and optionally air-dried. Filtration can be carried out by any suitable filtration device. In one embodiment, the formed lignin component is filtered by filtration under pressure or filtration under vacuum. In one embodiment, the pressure is between 10 - 20 bar (1000 - 2000 kPa), preferably 13 - 17 bar (1300 - 1700 kPa) and more preferably, about 15 bar (1500 kPa) in pressure filtration. [121] Preferably, the improved filterability, especially a better filtration rate, achieved by means of the invention leads to less pressure demand on the filtration and to a shorter filtration time. Then, cheaper filters, for example, based on the size and type of device, can be used. [122] In one embodiment, the temperature is above 50 ° C and the pH is between 5 and 7 during filtration. In one embodiment, the pH level is readjusted just before filtration. [123] In one embodiment, the process comprises at least two stages of filtration. In one embodiment, there is a filtration stage after each acid treatment stage. In one embodiment, there is the first stage of filtration before the acid wash of the invention and the second stage of filtration after the acid wash of the invention. In the first filtration stage, the washed lignin material or lignin component is filtered at a pH of about 10 and then the sulfuric acid can be saved in the acid wash. [124] In one embodiment, additional oxidation is carried out after filtration in which an acid filtrate is further oxidized. In one embodiment, the lignin component is further oxidized during the acid treatment stage. The additional oxidation can be carried out by means of air, oxygen, another oxidizing agent or their combinations, to stabilize the structure of the lignin component, to increase the purity of lignin and to remove the odor. [125] The lignin component (3) that can be obtained by the method of the present invention can be used as a component in the manufacture of a final product selected from activated carbon, carbon fiber, lignin composite, for example, composite of lignin-plastic or lignin fiber composite, binder material, phenolic component, dispersing agent and their combinations. [126] The final product or product comprises the lignin component of the present invention. Preferably, a pure lignin component is required according to the present invention in the manufacture of carbon fibers and activated carbon. [127] The method according to the present invention provides the lignin component with good quality. By improving the purification and increasing the dry solids content of the lignin component, then better properties of the lignin product and the final product can be provided. [128] The present invention provides an industrial, simple and inexpensive application for producing the lignin component from the lignin material. The method according to the present invention is simple and easy to carry out as a production process. The method according to the present invention is suitable for use in the manufacture of the different components of lignin from different lignin materials. [129] In addition, the invention is described in more detail by the following examples 7 - 8, with reference to the attached figures 6 - 8. Example 7 [130] In this example and in Figure 6, a lignin component (3) is formed by an acid treatment on a laboratory scale. [131] A lignin starting material (1), which was flash-precipitated lignin, was resuspended and treated by an acid wash stage (2). The process conditions were as follows in the acid wash stage: temperature of about 87 ° C, retention time of about 12 hours and pH level of about 5.6. The acid wash was carried out with an acidic composition containing H2SO4 and sodium sesquisulfate (SSS) so that the mixture of H2SO4: SSS was 1: 6. SSS was 20% liquid. [132] The lignin component (3) was filtered after the acid wash stage (2) by means of pressure filtration (4). Temperature was about 82 ° C and the pH was 6.5 - 7 during filtration. The filtration rate was about 207 kg / m3 / h. The dry solids content of the filter cake was about 78%. [133] In these tests, it was discovered that the lignin component can be produced with good properties. It was found that the dry solids content of the final lignin component cake and the filterability and time required for the filtration rate were at a good level. In addition, sulfuric acid can be saved by means of the invention. [134] In addition, the lignin structure in the lignin component cake was found to be in the form of single large particles. This explains the good filterability and high dry solids content. Example 8 [135] In this example, a lignin component (3) is formed by an acidic wash according to figure 6, on a pilot scale. [136] A lignin starting material (1), which was flash-precipitated lignin, was resuspended and treated in an acid wash stage (2) by an acidic composition to produce a lignin component. The acid wash was carried out with a composition containing H2SO4 acid and sodium sesquisulfate (SSS) so that the mixture of H2SO4: SSS was 1: 6. [137] The lignin component (3) was filtered after the acid wash stage (2) by means of pressure filtration (4). The temperature was about 82 ° C and the pH was 6.5 - 7 during filtration. [138] The process conditions are described in table 4. Table 4
where T1 is the acid wash temperature t1 is the acid wash retention time [139] The results of the process are described in table 5. Table 5
where DS is dry solid [140] The filtration rate is set during feeding. [141] In the tests, it was surprisingly found that the filterability of the lignin component was good although the lignin component was treated at a high pH level in the acid wash. In the tests, it was found that to allow the practical filtration rate, the suspension of the lignin material (1) must remain at a pH of 5 - 6 for a sufficiently long time, for 6 hours and at a sufficiently high temperature, above 70 ° C, in acid wash. In addition, it has been found that the lignin component can be produced with good dry solids of the cake and with quality. In addition, it has been found that the high concentration of sodium in the acid wash generally improves filtration, but generally raises the final ash content in the lignin component. However, the ash content was at an appropriate level. [142] In addition, the lignin structure in the lignin component cake was found to be in the form of single large particles. A lignin component from test 2 is shown in figure 8, SEM image. [143] Of all the tests in examples 7, it was found that it is important for the invention that the long retention time and high temperature together with the high pH level be used in the acid wash stage. In addition, it is important that at least part of the sulfuric acid is replaced by another acid or other acidifying chemical with salt. The consumption of sulfuric acid can be decreased due to the high pH level and the substitution of sulfuric acid. [144] One embodiment of the method of the present invention is shown in figure 9. Another embodiment of the method of the present invention is shown in figure 10. One embodiment of the device of the present invention is shown in figure 11. [145] In the method of the present invention , a lignin component is produced from the lignin material (1) by an acid treatment. According to the invention, a lignin component (3) is formed from lignin material (1) by treating the lignin material by means of an acidic composition in at least one acid treatment stage (2); and the lignin component is washed and neutralized (6) by a pH buffer during filtration (4), after treatment with acid, and the pH in the pH buffer is between 4 - 10. [146] In this context, the Lignin material refers to any material or composition that contains lignin. The lignin material can contain one or more material components. In one embodiment, suitable and desired additives can be added to the lignin material to form a desired lignin component. [147] In one embodiment, the lignin material includes material that is selected from a group consisting of lignin from the alkaline pulping process, Kraft lignin, lignin from the soda process, lignin from a process in which the lignin it is separated from the raw material by a solution that includes suitable chemicals and their combinations. [148] In one embodiment, the lignin material includes flash-precipitated lignin. In one embodiment, the precipitated lignin in flash is obtained after precipitation with CO2. Preferably, the flash-precipitated lignin is formed as described in patent application PCT / FI2011 / 050896. [149] In one embodiment, lignin is precipitated from the black liquor by a continuous process with CO2 at 6 - 10 bar (600 - 1000 kPa) overpressure. In one embodiment, lignin is separated by a flash precipitation lignin separation method, as disclosed in patent application PCT / FI2011 / 050896. In one embodiment of the present invention, lignin is flash-precipitated lignin. The term "flash precipitated lignin" should be understood in this specification as the lignin that was precipitated from black liquor in a continuous process by lowering the pH in a black liquor flow, under the influence of an overpressure of 200 - 1000 kPa, up to the level of precipitation of lignin using an acidifying agent based on carbon dioxide, preferably carbon dioxide, and suddenly releasing pressure to precipitate the lignin. The residence time in the above method is less than 300 s. The flash-precipitated lignin particles, having a particle diameter of less than 2 μm, form agglomerates, which can be separated from the black liquor, for example, using filtration. Flash-precipitated lignin can be purified and / or activated, if necessary for further processing. Flash precipitated lignin has many advantages, for example, activity, dispersibility, solubility, drainability and preservability. In one embodiment of the present invention, the lignin component is a flash precipitated kraft lignin. Preferably, the flash precipitated kraft lignin is undrained. Therefore, lignin has greater activity, and lignin can be redissolved. Lignin needs only a very simple redispersion stage when it is added, for example, in an adhesive mixture. In addition, controlling the amount of water in the lignin-based composition is easier when redispersion is easier. In addition, lignin is easier to handle in the process because lignin is not dusty. Preferably, the flash-precipitated kraft lignin has a dry matter content of 50 - 80%. [150] In one embodiment, the lignin material is treated chemically and / or mechanically before at least one acid treatment stage of the present invention. In one embodiment, the lignin material is precipitated before at least one acid treatment stage. In one embodiment, the lignin material is resuspended before at least one acid treatment. [151] In this context, a lignin component means the product formed from lignin material in one or more stages. The term "lignin component" is already used after the first stage of treatment. [152] In one embodiment, the at least one acid treatment stage (2) is selected from a group consisting of acid washing, acid hydrolysis and combinations thereof. The treatment with acid (2) is carried out in one stage or alternatively in more than one stage. In one embodiment, the at least one acid treatment stage (2) is the acid wash. In one embodiment, the at least one acid treatment stage (2) is acid hydrolysis. In one embodiment, the lignin material (1) is treated in two stages of acid treatment (2) in which one phase is acid washing and one phase is acid hydrolysis. [153] In this context, acid washing refers to any acid washing method. In one embodiment, the acid wash is carried out with an acidic composition containing sulfuric acid (H2SO4), another acid or other suitable acidifying chemical or combination thereof. The optimization of the process positively affects the consumption of H2SO4 or another acid or other acidifying chemical. [154] In this context, acid hydrolysis refers to any method of acid hydrolysis. In one embodiment, acid hydrolysis is carried out using H2SO4, or other suitable acidifying chemicals, typically in the presence of water. [155] In one embodiment, the acidic composition includes H2SO4 which can be either virgin acid or recycled acid. In one embodiment, the acidic composition includes acidifying chemical. [156] Preferably, in the acid treatment stage of the invention, a suitable combination of temperature, retention time and pH level is selected. The selected combination varies based on the acid washing or hydrolysis method, the lignin material, the acidic composition and the desired product. [157] Any acid treatment process can be used in connection with the present invention, for example, the acid treatment process as in disclosed patent application FI20116253 or FI20125703 or another suitable acid treatment method can be used. [158] In one embodiment, a lignin component is produced from lignin material (1) by a mild acid treatment, so that the lignin material (1) is treated in at least one acid treatment stage (2) and at least one acid treatment stage is optimized through a combination of process parameters comprising the retention time, for example, long retention time, the temperature, for example, high temperature, and pH level, for example, low enough pH, to decrease the ash and / or carbohydrates in the lignin component, and preferably to remove the undesirable substance from the lignin component and to purify the lignin component. In one embodiment, the lignin component is formed as described in patent application FI 20116253. [159] In one embodiment, the method comprises: optimizing the process conditions in the acid treatment stage so that at high temperature, Long retention and low pH are used during treatment with acid. [160] Preferably, the long retention time is used in the acid treatment stage, in at least one acid treatment stage. In this context, the retention time means the time of the acid treatment stage. The retention time does not include a filtration time. [161] In one embodiment, the retention time, which is more than 6 hours, is used during treatment with acid. Preferably, a lignin component is produced from lignin material, by an acid treatment, the method comprising: forming a lignin component of lignin material, by treating the lignin material in at least one treatment stage with acid; and optimize the process conditions, through a combination of the process parameters comprising the retention time, temperature and pH level in the acid treatment stage so that the retention time is 6 hours, for at least one stage acid treatment. [162] In one embodiment, the retention time, which is more than 8 hours, is used during treatment with acid. In one embodiment, the retention time, which is more than 10 hours, is used during treatment with acid. In one embodiment, the retention time, which is more than 16 hours, is used during treatment with acid. [163] In one embodiment, a temperature that is higher than 70 ° C is used during treatment with acid. In one embodiment, the temperature is greater than 72 ° C, more preferably, greater than 73 ° C, and more preferably, greater than 75 ° C. [164] In one embodiment, the pH level, which is between 0.5 - 4, is used during treatment with acid. In one embodiment, the preferred pH level is low enough during the treatment stage. In one embodiment, the pH level is less than 3.5, preferably between 2 - 3. In one embodiment, the pH level is less than 2.0, preferably between 0.5 - 1.5. In one embodiment, the pH level, which is between 2 - 4, can be used. [165] In one embodiment, the method comprises a pre-treatment step before at least one acid treatment step. In one embodiment, the lignin material is resuspended in the pre-treatment step. In a preferred embodiment, the pretreatment step is a lignin softening step, in which the lignin is softened and the structure of the lignin is modified. [166] It is important for the invention that the long retention time is used in at least one acid treatment stage. Alternatively, the long retention time can be used in more than one stage. The long retention time can be used in the acid treatment stage, for example, in the acid wash and / or acid hydrolysis, and / or in the pre-treatment step. [167] With increasing retention time and / or temperature, the dry solid content and filterability can be improved. The improved dry solid content of the filter cake leads to less energy consumption in drying and a decrease in the consumption of washing liquid in washing to achieve good purification. [168] In one embodiment, the pH in the pH buffer is between 5 - 9. In one embodiment, the pH in the pH buffer is between 6 - 8 In one embodiment, the pH in the pH buffer is greater than 4, so preferably, greater than 5, and more preferably, greater than 6. In one embodiment, the pH in the pH buffer is less than 10, preferably less than 9, and more preferably less than 8. The washing liquid highly alkaline, where the pH is greater than 10, increases the dissolution of lignin quickly. [169] In one embodiment, the pH buffer is in the form of a solution. [170] The pH buffer can include one or more of a component. Preferably, the pH buffer contains at least one buffering agent. In one embodiment, the pH buffer includes the buffering agent selected from a group consisting of citrate, acetate, carbonate and combinations thereof. In one embodiment, the pH buffer includes an alkaline-based compound, for example, NaOH. In one embodiment, the alkaline-based compound is used to adjust the pH level in the pH buffer. In one embodiment, the pH buffer includes citrate as a buffering agent. In one embodiment, the pH buffer includes alkali-based compounds and citrate and water, and the pH of the pH buffer is between 5 - 7. Alternatively, the pH can include any suitable buffering agent. In one embodiment, the pH buffer includes water. Composition of the pH buffer can be optimized taking into account the requirements of the processes and the final products. [171] Preferably, the method of the invention comprises filtering (4) the lignin component after treatment with acid. In one embodiment, the formed lignin component (3) is filtered in the filtration stage (4) after at least the last acid treatment stage (2). [172] In this context, filtration refers to any filtration method that can be used to filter lignin. Preferably, in filtration, the lignin component is filtered, washed and pressed and optionally air-dried. Filtration can be carried out by any suitable filtration device. In one embodiment, the formed lignin component is filtered by filtration under pressure or filtration under vacuum. In one embodiment, the pressure is between 10 - 20 bar (1000 - 2000 kPa), preferably 13 - 17 bar (1300 - 1700 kPa) and more preferably, about 15 bar (1500 kPa) in pressure filtration. [173] Filtration comprises a filtration step, which contains the supply of the lignin component, to form a filter cake and a washing step, such as a cake washing step, to wash the filter cake, to decrease the ash content of the lignin product. In addition, filtration may comprise a pre-pressing step, before the washing step and a final pressing step, after the washing step. [174] Preferably, the lignin component is neutralized during filtration, preferably in connection with the washing step, such as the cake washing step. Preferably, the washing of the lignin component is produced by means of the pH buffer. At the same time, the lignin component is neutralized. The pH buffer is used instead of clean water to wash the filter cake. [175] In the present invention, the filtration device (10) comprises lignin feeding equipment for feeding the lignin component (7) from an acid treatment stage to the filtration device, and a filtration step filtration to form a cake of the lignin component and a washing step for washing the cake, and a pH buffer feeding equipment (9) for feeding the pH buffer (8) into the washing step. In the washing step, the lignin component is washed and neutralized with the pH buffer. Alternatively, the filtration device may comprise a pre-pressing step between the filtration step, and the washing step and / or a final pressing step after the washing step. The pH buffer feeding equipment (9) may contain one or more than one device selected from the group consisting of a tank, pipe, pipe, tube, pump and combination thereof, or the like, to feed the pH buffer into the washing step. [176] In one embodiment, the filtration device (10) comprises at least one feed tank from which the pH buffer or pH buffer component is fed in the washing step, into the pH buffer feeding equipment. or in a mixing device. In one embodiment, the pH buffer is fed from the feed tank in the washing step, using the pH buffer feeding equipment. In one embodiment, the pH buffer feeding equipment contains at least one feed tank. In one embodiment, the pH buffer is fed from the feed tank to the washing step. [177] In one embodiment, the filtration device (10) comprises a mixing device (11). In one embodiment, the mixing device contains at least one mixing tank or at least one mixer, for example, static mixer, in a container or pipe, to form the pH buffer. The pH buffer can be formed in the mixing device, for example, in the mixing tank, by combining the components of the pH buffer together and / or by mixing. The pH buffer is fed from the mixing device in the washing step via the pH buffer feeding equipment or via the pH buffer feeding equipment. Alternatively, the formation or mixing of the pH buffer can be done in the pH buffer feeding equipment, such as in the tubing. In one embodiment, the components of the pH buffer are fed from the tanks to the feeding equipment for the combination of the components in the feeding equipment. In one embodiment, the pH buffer feeding equipment comprises the mixing device, for example, the static mixer in the pipeline. [178] In one embodiment, the filtration device (10) comprises an adjustment device for adjusting the pH of the pH buffer between 4 and 10, preferably before the washing step. In one embodiment, the pH of the pH buffer is analyzed by an analysis device. In one embodiment, the filtration device (10) comprises a control means for determining the pH of the pH buffer and / or adjusting the pH of the pH buffer between 4 and 10, preferably before the washing step. In one embodiment, the control means comprise at least one analysis device. In one embodiment, the control means comprises at least one adjustment device. In one embodiment, the control means comprises at least one analysis device and at least one adjustment device. The control means, adjustment device or analysis device can be arranged in connection with the pH buffer feeding equipment or mixing device. Alternatively, the control means, adjustment device or analysis device can be arranged before the pH buffer feeding equipment. In one embodiment, the adjustment device contains means for the addition of pH buffer in the washing step and / or means for the addition of buffer agent in the pH buffer. In one embodiment, the adjustment device contains at least one adjustable valve for adjusting the pH buffer feed in the wash step. In one embodiment, the pH buffer feeding equipment contains at least one adjustable valve to adjust the pH buffer feeding in the washing step, where the adjustable valve can be adjusted, for example, by means of control elements, or manually. [179] In one embodiment, the formation of the pH buffer is carried out as a batch process. In one embodiment, the formation of the pH buffer is carried out as a continuous process. [180] In one embodiment, the filtration device comprises feed tanks, a mixing device containing a mixing tank and a static mixer, and pH buffer feeding equipment containing a pipe and pump, and the buffer components pH of the feed and water tanks are fed into the mixing tank, where the batch of the pH buffer is formed by mixing with the mixture with the static mixer, and the pH buffer is fed from the mixing device in the washing step using pH buffer feeding equipment. [181] In one embodiment, the filtration device comprises feed tanks, pH buffer feed equipment containing a pipe and pump, and a mixing device containing a static mixer in connection with the feed buffer equipment. pH, and the pH buffer components of the feed and water tanks are fed into the piping of the pH buffer feeding equipment where the pH buffer is formed by mixing with the static mixer, and the pH buffer is provided in the washing step through the pump. Alternatively, the pH buffer and water components are not mixed in the pipeline when the pH buffer is formed. [182] In one embodiment, the pH buffer is fed directly, for example, into a feed tank, in the washing step by means of the pH buffer feeding equipment containing tubing and pump. [183] In one embodiment, the temperature is higher than 50 ° C during filtration (4). [184] Preferably, improved filterability, especially a better filtration rate, achieved through optimization, leads to a lower pressure requirement on the filtration medium and shorter filtration times. Then, cheaper filters, for example, based on the size and type of device, can be used. [185] Preferably, the pH of the lignin component is between 4 - 8 after filtration (4), in one embodiment, between 5 - 7. In one embodiment, the pH of the lignin component is greater than 5, in one modality, greater than 6. In one embodiment, the pH of the lignin component is less than 8, in one embodiment, less than 7. In a preferred embodiment, the pH of the lignin component is about 7. [186] In one embodiment, the lignin component is dried after filtration. [187] In addition, the invention relates to the lignin component that has specific properties, such as the high particle size. Preferably, the lignin component has a specific surface area between 0.1 - 1.0 m2 / g, preferably between 0.2 - 0.7 m2 / g, and more preferably between 0.3 - 0.6 m2 / g. In the tests it was found that the particle size correlates with a specific surface area. Preferably, the lignin component has a particle size, which is larger than in typical lignin products. [188] In one embodiment, the lignin component is dried and / or ground, after filtration. In one embodiment, the lignin component which is dried and ground into fine particles has a bulk density between 200 - 800 g / cm3, preferably between 300 - 700 g / cm3, more preferably between 400 - 600 g / cm3 , and in a modality about 500 g / cm3. In one embodiment, the mass density is determined so that the lignin component is dried and ground into fine particles, and after that, the ground lignin component is placed in the flexible intermediate dough container, from which a sample is taken, and the mass density of the lignin component is measured from the sample. Preferably, the mass density of the lignin component of the present invention is greater than that of typical lignin products known in the art. [189] In addition, the invention relates to the lignin component that is formed from lignin material, by an acid treatment, in which the lignin component is formed from lignin material so that the lignin material it is treated by means of an acidic composition in at least one acid treatment stage; and the lignin component is washed and neutralized by a pH buffer during filtration after treatment with acid, and the pH in the pH buffer is between 4 - 10. [190] Preferably, the ash content of the lignin component is low. [191] In addition, the invention relates to the use of the lignin component that can be obtained by the method of the invention, in which the lignin component is used as a component in the manufacture of a final product selected from a group consisting of activated carbon, carbon fiber, lignin, binder material, phenolic component, dispersing agent and their combinations. [192] In addition, the invention relates to a product that includes the lignin component that can be obtained by the method of the invention. In one embodiment, the product is selected from a group consisting of activated carbon, carbon fiber, lignin composite, for example, lignin-plastic composite or fiber-lignin composite, binder material, phenolic component, dispersing agent and their combinations. [193] The invention is based especially on improving the properties of the lignin component. When the lignin material is treated with acid in one or more stages of acid treatment, by optimizing the retention time, temperature and pH level, then the properties, for example, purity, dry solids content, filtration, quantities of carbohydrates and ashes, of the lignin component can be improved. In addition, the odor in the lignin component can be reduced. In addition, when the lignin component is neutralized, then the neutral lignin component can be achieved. Next, the lignin component is provided which is suitable for use in typical and special applications. [194] The method according to the present invention provides the neutral lignin component with good quality, such as purification and dry solids content. By improving the purification and increasing the dry solids content of the lignin component, then, better properties of the lignin product and the final product can be provided. The filterability of the lignin component and operating costs in the following stages of the process, for example, in drying, are improved. [195] It is important that the neutral lignin component with purity properties is achieved. The neutral lignin component is non-corrosive. Then, additional process steps are not necessary to neutralize the lignin, when the clean water is replaced by the pH buffer during washing. Neutralization of the lignin product at the additional stage of the process is extremely difficult, since after the separate neutralization stage it is difficult to dehydrate the lignin product. The production of neutral lignin is a necessity for most applications. In addition, even the burning of the lignin component benefits from the non-corrosive nature of this biofuel. The non-corrosive lignin component can be fed in the application process, without the need for stainless steel / acid-proof steel as a material in feed systems. In addition, the standard material can be used in storage containers. In addition, neutral lignin is less harmful to health. [196] The present invention provides an industrially applicable, simple and inexpensive way to produce the lignin component from the lignin material. The method according to the present invention is simple and easy to carry out as a production process. The method according to the present invention is suitable for use in the manufacture of the different lignin components from different lignin materials. [197] In addition, the invention is described in more detail by the following examples 9 - 12 with reference to the attached figures 9 - 11. Example 9 [198] In this example and in Figure 9, a lignin component (3) is formed by an acid treatment. [199] A lignin starting material (1), which is flash-precipitated lignin, is treated by an acid treatment stage (2), which is an acid wash stage. The process conditions are as follows: the temperature is around 70 ° C, the retention time is over 6 hours and the pH level is around 3. The acid wash is carried out with H2SO4. [200] The lignin component (3) is filtered after the acid wash (2) by means of pressure filtration (4). The temperature is above 50 ° C during filtration. During filtration (4), washing and neutralization (6) of the lignin component is carried out by the pH buffer solution (8) containing citrate, acetate and / or carbonate as a buffering agent. The pH of the pH buffer solution is about 5 - 7. [201] The neutral lignin component is achieved. The lignin component has a specific surface area between 0.1 - 1.0 m2 / g. Example 10 [202] In this example and in Figure 10, a lignin component (3) is formed by an acid treatment. [203] A lignin starting material (1), which is flash-precipitated lignin, is treated, first, in a pre-treatment stage 5, in which a resuspension and filtration stage is performed and, in followed by an acid treatment stage (2), which is an acid wash stage. The process conditions are as follows: the temperature is about 70 ° C, the retention time is over 6 hours and the pH level is about 3. The acid wash is carried out with H2SO4. [204] The lignin component (3) is filtered after the acid wash (2) by means of pressure filtration (4). The temperature is above 50 ° C during filtration. During filtration (4), washing and neutralization (6) of the lignin component is carried out by the pH buffer solution (8) containing citrate, acetate and / or carbonate as a buffering agent. The pH of the pH buffer solution is about 6 - 7. [205] The neutral lignin component is achieved. The lignin component has a specific surface area between 0.2 - 0.7 m2 / g. Example 11 [206] In this example and in Figure 11, a lignin component (7) formed by an acid treatment is filtered by filtration under pressure (4). The temperature is above 50 ° C during filtration. During filtration (4), washing and neutralization (6) of the lignin component is carried out by the pH buffer solution containing citrate as a buffering agent. The pH of the pH buffer solution is about 6 - 7. [207] Filtration, washing and neutralization are carried out in a filtration device (10). The filtration device (10) comprises a lignin feeding equipment for feeding the lignin component into the device, a filtration step for the formation of a lignin component cake, a washing step for washing the cake and a step of final pressing for pressing. Alternatively, the filtration device can comprise a pre-pressing step between the filtration step and the washing step. A product of the lignin component (3) is formed during filtration. [208] The pH buffer solution is formed from the buffer agent (12a) containing the citrate agent, NaOH (12b) and water (13) by mixing in a mixing device (11) comprising a mixing tank or in a mixer in a container or a pipe. The pH buffer solution (8) is fed by a pH buffer feeding device (9) containing a supply pipe and a pump in a washing step of the filtration device (10) for washing and neutralizing a cake of the lignin component (7). Alternatively, mixing of the pH buffer solution can be done in the feed equipment, such as in the tubing. [209] The lignin component (3) can be dried and ground. Example 12 [210] In this example, the pH of the product of the lignin component is determined after filtration. The pH is measured from the lignin components of the present invention and reference samples. [211] The lignin components of the present invention were formed by means of examples 9 and 11. During filtration, the lignin products were washed by the pH buffer where the pH was 6. The pH buffer contained citrate agent ( 2.1 g / l of citric acid), NaOH (pH 6) and water. [212] The reference samples were formed by means similar to those of the evaluation points. During filtration, the lignin products were washed with clean water. [213] In the filtration feed, the compression and washing times of the cake were similar when compared to the water and pH buffer when washing the cake. The pH of the lignin-based feed was about 2.5 before filtration. Finally, a filter cake formed during filtration was suspended in water (ds 25%), mixed for 1 hour at 60 ° C, cooled to 25 ° C and the pH was measured. [214] The results are described in table 6. Table 6
[215] It has been found that the pH of the lignin component can be increased by the method according to the present invention, in comparison with the reference samples. [216] Even when the pH of the pH buffer was only 6, thus lower than the pH of clean water, the pH in the final lignin component was higher when the pH buffer was used. This shows the functionality of the invention. The ash and dry solids content of the filter cake, the time required for washing the cake and the time required for final pressing were similar to those for washing with clean water. [217] In these tests of examples 9-12 it was found that the neutral lignin component can be produced with good properties, such as purity. It was found that the dry solids content of the final lignin component and filterability and the required filtration rate time were at good levels. [218] Furthermore, the lignin structure in the lignin component cake was found to be in the form of single large particles. This explains the good filterability and the high dry solids content. [219] In addition, the invention relates to the lignin component that has specific properties, such as the high particle size. Preferably, the lignin component has a specific surface area between 0.1 - 1.0 m2 / g, preferably between 0.2 - 0.7 m2 / g, and more preferably between 0.3 - 0.6 m2 / g. In the tests it was found that the particle size correlates with a specific surface area. Preferably, the lignin component has a particle size, which is larger than in typical lignin products. [220] In one embodiment, the lignin component is dried. [221] In one embodiment, the lignin component is dried and / or ground after filtration. In one embodiment, the lignin component which is dried and ground into fine particles has a density between 200 - 800 g / cm3, preferably between 300 - 700 g / cm3, more preferably between 400 - 600 g / cm3, and in a modality, of about 500 g / cm3. In one embodiment, the mass density is determined so that the lignin component is dried and ground into fine particles, and after that, the ground lignin component is placed in the flexible intermediate dough container, from which a sample, and the mass density of the lignin component is measured from the sample. Preferably, the mass density of the lignin component of the present invention is greater than that of typical lignin products known in the art. Example 13 [222] In this example, the specific surface areas of the lignin components are determined from the lignin component of the present invention and reference samples. [223] The lignin components of the present invention were formed by means of an acid treatment according to the present invention in which the long retention time, greater than 6 h, and the temperature greater than 70 ° C is used. [224] The reference samples were formed through a typical acid treatment process, in which low temperature and short retention time are used. [225] The results are described in Table 7. Table 7
[226] The lignin component of the present invention has a particle size that is larger than in typical lignin products. [227] A particle size has been found to correlate with a specific surface area. [228] In the present invention it has been found that ash content and carbohydrate content can be reduced during acid hydrolysis without much influence on the structure of lignin. It is well known in the prior art that carbohydrates can be removed from lignin using strong acid hydrolysis, but this will result in the carbonization of lignin. Thanks to the invention, carbohydrates can be removed from lignin using mild conditions in acid hydrolysis. [229] If the lignin product has a pH of 2.5, then an additional process stage may be required to neutralize the lignin product when close to the neutral lignin in some downstream processing or applications. The separate neutralization stage would bring a significant additional cost to the process, since the filtration close to the neutral lignin suspension is extremely slow, using standard methods. The lower dry solids content of the filter cake clearly obtained after the standard neutralization stage has a greater effect on the high operating costs. Thanks to the modalities of the invention, the neutral lignin product can be formed, without separate neutralization steps. [230] The method according to the present invention is suitable in different modalities to be used for the production of the most different species of lignin components from different lignin materials. The lignin component according to the present invention is suitable in different modalities for use in different end products. [231] The invention is not limited to the aforementioned examples; instead, many variations are possible within the scope of the idea of the invention defined by the claims.

权利要求:
Claims (14)
[0001]
1. Method for producing a lignin component from lignin material, by an acid treatment, the method characterized by the fact that it comprises: - pre-treating the lignin material by resuspension of the lignin material in a step of pre-treatment, in which the lignin material is resuspended at a temperature of 55 - 70 ° C for less than 2 hours; - forming a lignin component of lignin material by treating the lignin material in an acid treatment stage, by means of an acidic composition; - optimize the process conditions in the acid treatment stage so that the high temperature exceeds 70 ° C, the long retention time exceeds 6 hours, preferably exceeds 10 hours, and the pH level between 4.5 - 7 are used during acid treatment; - filter the acid-treated lignin material at a temperature of 50 ° C or higher and at a pH between 5 - 7; and - where the specific surface area of the lignin component is between 0.1 - 1.0 m2 / g.
[0002]
2. Method according to claim 1, characterized by the fact that the acid treatment stage is acid washing.
[0003]
Method according to claim 1 or 2, characterized in that the acidic composition includes H2SO4 and / or salt containing acidifying chemical.
[0004]
Method according to any one of claims 1 to 3, characterized in that the acidic composition includes sodium sesquisulfate.
[0005]
Method according to any one of claims 1 to 4, characterized by the fact that the pH level is between 5 and 6.
[0006]
Method according to any one of claims 1 to 5, characterized in that the temperature is above 80 ° C.
[0007]
Method according to any one of claims 1 to 6, characterized in that the lignin component is filtered by filtration under pressure or filtration under vacuum.
[0008]
8. Method according to any one of claims 1 to 7, characterized in that the pH level is readjusted shortly before filtration.
[0009]
Method according to any one of claims 1 to 8, characterized in that the method comprises: precipitating the lignin material before the acid treatment stage.
[0010]
Method according to any one of claims 1 to 9, characterized in that the lignin material includes flash-precipitated lignin.
[0011]
11. Lignin component, characterized by the fact that it is formed from lignin material, by an acid treatment, in which a lignin component is formed from lignin material so that the lignin material is pre-treated by resuspension in a pretreatment step, in which the lignin material is resuspended at a temperature of 55 - 70 ° C for less than 2 hours, treated in an acid treatment stage, using an acidic composition, and the acid treatment stage is optimized through process conditions, so that the high temperature above 70 ° C, long retention time over 6 hours, preference, over 10 hours, and the pH level between 4 , 5 - 7 are used during acid treatment, with the acid-treated lignin material going through a filtration step at a temperature of 50 ° C or higher and at a pH between 5 - 7, and in which the area The specific surface area of the lignin component is between 0.1 - 1.0 m2 / g.
[0012]
12. Use of the lignin component obtainable by the method as defined in any of claims 1 to 9, characterized by the fact that the lignin component is used as a component in the manufacture of a final product selected from a group consisting of activated carbon , carbon fiber, lignin composite, binder material, phenolic component, dispersing agent and their combinations.
[0013]
13. Product, characterized by the fact that it includes the lignin component obtainable by the method as defined in any one of claims 1 to 9.
[0014]
14. Product, according to claim 13, characterized by the fact that the product is selected from a group consisting of activated carbon, carbon fiber, lignin composite, binder material, phenolic component, dispersing agent and its combinations.

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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|

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2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-07-21| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|

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2020-12-01| B09A| Decision: intention to grant|

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2021-01-19| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 05/12/2012, 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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FI20116253A|FI20116253A|2011-12-09|2011-12-09|A process for the preparation of a lignin component, a lignin component and its use, and a product|

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FI20116253|2011-12-09|

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FI20125703|2012-06-25|

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FI20125703A|FI126765B|2012-06-25|2012-06-25|A process for the preparation of a lignin component, a lignin component and its use, and a product|

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PCT/FI2012/051210|WO2013083876A2|2011-12-09|2012-12-05|A method for making a lignin component, a lignin component and its use and a product|

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