WO2006038863A1 - Method for separating lignin from a lignin containing liquid/slurry - Google Patents

Method for separating lignin from a lignin containing liquid/slurry Download PDF

Info

Publication number
WO2006038863A1
WO2006038863A1 PCT/SE2005/001453 SE2005001453W WO2006038863A1 WO 2006038863 A1 WO2006038863 A1 WO 2006038863A1 SE 2005001453 W SE2005001453 W SE 2005001453W WO 2006038863 A1 WO2006038863 A1 WO 2006038863A1
Authority
WO
WIPO (PCT)
Prior art keywords
lignin
level
slurry
liquid
dewatering
Prior art date
Application number
PCT/SE2005/001453
Other languages
French (fr)
Inventor
Fredrik ÖHMAN
Hans Theliander
Magnus Norgren
Per Tomani
Peter AXEGÅRD
Original Assignee
Lignoboost Ab
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Lignoboost Ab filed Critical Lignoboost Ab
Priority to BRPI0517543A priority Critical patent/BRPI0517543B1/en
Priority to US11/661,412 priority patent/US8815052B2/en
Priority to CA2580834A priority patent/CA2580834C/en
Priority to AT05788548T priority patent/ATE513082T1/en
Priority to EP05788548A priority patent/EP1797236B1/en
Priority to JP2007535638A priority patent/JP4887299B2/en
Publication of WO2006038863A1 publication Critical patent/WO2006038863A1/en

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for

Definitions

  • This invention concerns the technical field of lignin separation.
  • the present invention relates to a method for lignin separation from a lignin containing liquid/slurry, such as process liquors in a mill containing lignin, preferably black liquor.
  • the invention relates to lignin products obtainable by the above mentioned method and use of said products.
  • lignin Separation of lignin from black liquor is an interesting solution to these problems.
  • the energy surplus can be withdrawn from the process in the form of a solid biofuel and can be exported to e.g. a power station, where the fuel can be used more efficiently than in the recovery boiler of the pulp mill.
  • This lignin is also a valuable material for production of "green chemicals”.
  • lignin extraction leaves a black liquor for combustion with a lower thermal value, which in turn leads to a lower load on the recovery boiler. This gives in a short term perspective possibilities for increased pulp production. In the long perspective lower instrument cost for the recovery boiler is expected.
  • the suspension is taken to a storage vessel for conditioning of the precipitate after which the solid lignin is separated and washed (with acidic wash water) on a band filter, and is finally processed to the desired state.
  • acidifying chemicals for separating lignin, which in turn may be used for fuel.
  • Such procedures are thus very expensive and it would accordingly be of great benefit if it would be possible to reduce the amount of acidifying chemicals necessary for separating lignin. Accordingly, there is a need for a method where lignin can be separated using small amounts of acidifying chemicals, e.g. sulphuric acid or carbon dioxide.
  • the present invention solves one or more of the above problems by providing according to a first aspect a method for precipitating (separation) of lignin, using small amounts of acidifying agents, whereby lignin is obtained which can be used as fuel (or as a chemical feed stock; or as a chemical or a raw material for further refining), from a lignin containing liquid/slurry, such as black liquor, comprising the following steps: a) addition of one or more compounds comprising sulphate or sulphate ions, or a mixture comprising said compound, to said liquid/slurry, b) adjustment of the pH level of said liquid/slurry by acidifying, and c) dewatering of said liquid/slurry whereby a lignin product or an intermediate lignin product is obtained.
  • the present invention also provides according to a second aspect a method for separation of lignin from a lignin containing liquid/slurry, such as black liquor, comprising the following steps: i) precipitating of lignin by the adding of one or more compounds comprising sulphate or sulphate ions, or a mixture comprising said compound, to said liquid/slurry, and by acidifying said liquid/slurry, and thereupon dewatering, ii) suspending the lignin filter cake whereupon a second suspension is obtained and adjusting the pH level to approximately the pH level of the washing water, iii) dewatering of the second suspension, iv) addition of washing water and performing a displacement washing at more or less constant conditions without any dramatic gradients in the pH, and v) dewatering of the filter cake produced in step iv) into a high dryness and displacement of the remaining washing liquid in said filter cake, whereby a lignin product or an intermediate lignin product is obtained.
  • the present invention also provides according to a third aspect a lignin product or an intermediate lignin product obtainable by the method according to the first aspect.
  • the present invention also provides according to a fourth aspect a lignin product or an intermediate lignin product obtainable by the method according to the second aspect.
  • the present invention also provides according to a fifth aspect use, preferably for the production of heat or as chemical feed stock, of the lignin product or the intermediate lignin product of the third or fourth aspects.
  • the present invention is based upon that it has been found that sulphate ions precipitate/coagulate lignin unexpectedly efficiently compared with e.g. chloride.
  • the previously available knowledge according to the so-called Hofmeister series - lyotropic series - says that chloride precipitates proteins from albumen better than sulphate.
  • lignin containing liquid/slurry is any liquid or slurry, which contains lignin.
  • This liquid or slurry may be a process liquor, containing lignin, in a mill, preferably said liquid or slurry is a black liquor.
  • compound comprising sulphate or a sulphate ion embraces any compound comprising sulphate or a sulphate ion.
  • This compound may be Na-, K- , (Al-), Ca-, Mg-, Fe- or organic sulfate, CaSO 4 ,
  • K 2 SO 4 , AI 2 SO 4 , iron sulfates or MgSO 4 may also be comprised in recovery boiler ashes, which is a mixture, or it may be essentially pure Na 2 SO-J-
  • the expression "acidifying” embraces any means for acidifying the lignin containing liquid/slurry, such as black liquor.
  • the acidifying is performed by adding SO 2 (g) , organic acids, HCI, HNO 3 , carbon dioxide or sulphuric acid (in the form of fresh sulfuric acid or a so called “spent acid” from a chlorine dioxide generator) or mixtures thereof to said liquid/slurry (preferably black liquor) most preferred by adding carbon dioxide or sulphuric acid.
  • the expression "dewatering” embraces any means for dewatering.
  • the dewatering is performed by using centrifugation, a filter press apparatus, a band filter, a rotary filter, such as a drum filter, or a sedimentation tank, or similar equipment, most preferred a filter press apparatus is used.
  • a filter press apparatus a filter press apparatus, a band filter, a rotary filter, such as a drum filter, or a sedimentation tank, or similar equipment, most preferred a filter press apparatus is used.
  • the dewatering of step c) is performed in a filter press apparatus.
  • step a) is done by adding recovery boiler ashes, i.e. ashes emanating from a soda recovery unit, which is a steam generator combined with a smelting furnace for the utilization of the heat of combustion of the black liquor and the recovery of the greater part of its inorganic components, or Na 2 SO-J, CaSO 4 , K 2 SO 4 , AI 2 SO 4 , iron sulfates or MgSO 4 .
  • recovery boiler ashes i.e. ashes emanating from a soda recovery unit, which is a steam generator combined with a smelting furnace for the utilization of the heat of combustion of the black liquor and the recovery of the greater part of its inorganic components, or Na 2 SO-J, CaSO 4 , K 2 SO 4 , AI 2 SO 4 , iron sulfates or MgSO 4 .
  • Na 2 S ⁇ 4 is used.
  • mixing is performed after the adjustment of the pH level in step b).
  • the pH level is adjusted to below approximately pH 9.5 in step b), preferably below approximately pH 6, most preferred the pH level is a pH from 1 to 4.
  • the pH level is adjusted whereby using CO 2 .
  • the temperature is varied from 20 to 100° C depending on the nature of the liquid/slurry containing lignin, such as black liquor.
  • the filtrate from step c) is re-circulated directly to a recovery system, preferably after re-alkalization.
  • the addition of step i) is done by adding recovery boiler ashes or Na 2 S ⁇ 4 ,CaSO 4 , K 2 SO 4 , AI 2 SO 4 , iron sulfates and/or MgSO 4 .
  • Na 2 S ⁇ 4 is used.
  • mixing is performed after the acidifying in step i).
  • the pH level is adjusted in step i) through acidifying whereby using CO 2 .
  • the temperature in step i) is varied from 20 to 100° C depending on the nature of the liquid/slurry containing lignin, such as black liquor.
  • the dewatering of step i) and/or step iii) is performed in a filter press apparatus where the filter cake may be blown through by gas or a mixture of gases, preferably flue gases, air or vapor, most preferred air or overheated vapor, in order to dispose of the remaining lignin containing liquid/slurry such as black liquor (which is preferred).
  • the pH level is adjusted to below approximately pH 9.5 in step i), preferably below approximately pH
  • pH level is a pH from 1 to 3.5.
  • the washing water has a pH level of below approximately pH 9.5, preferably below approximately pH 6, most preferred the pH level is a pH from 1 to 3.5.
  • the filter cake obtained in step i) is blown through by using gas or a mixture of gases, including e.g. flue gases, air and vapor (which preferably can be air or overheated vapor) before suspending said cake as set out in step ii).
  • the pH level adjustment is combined with an adjustment of the ion strength, preferably by using multivalent alkaline earth metal ions, most preferred calcium ions.
  • the lignin is stabilized during the washing, as set out above earlier in the preferred embodiment of the second aspect of the present invention, whereby a pH-decrease is combined with an adjustment of the ionic strength in the slurry stage, preferably with multivalent alkaline earth metal ions (e.g. calcium ions).
  • multivalent alkaline earth metal ions e.g. calcium ions.
  • the ionic strength and pH of the wash water essentially corresponds to the conditions in the slurry stage to avoid gradients during the washing process.
  • a higher ionic strength in the slurry and in the wash water gives a stable lignin even at high pH-values.
  • divalent calcium ions can be introduced into the lignin, which in the combustion of the lignin can bind sulfur in the form of calcium sulphate (Aarsrud et al 1990, WO 9006964).
  • the pH level adjustment combined with an adjustment of the ion strength corresponds to the pH level and ion strength of the washing liquid.
  • the filtrate from the first dewatering stage step i) is re-circulated directly to a recovery system, preferably after re-alkalization.
  • the remaining washing liquor in the filter cake in step v) is removed with air or flue gases, preferably flue gases from a recovery boiler, a lime kiln or a bark boiler.
  • the washing liquor and a part of the filtrate from the second dewatering in step iii) is returned to the re-slurrying stage step ii) to further reduce the consumption of acid and water.
  • one or more compounds comprising sulphate or a sulphate ion, or a mixture comprising said compound such as recovery boiler ashes is added during step a) (or step i)) in the method according to the first aspect (or the method according to the second aspect) to increase the ionic strength in the lignin containing liquid/slurry, such as black liquor, and thus be able to precipitate with a lower acid consumption or alternatively achieve a greater lignin precipitation with the same amount of added acid.
  • the sulfate ion would, as indicated in the appended Figure 1 , itself have an effect on the precipitation in addition to the fact that it increases the ionic strength.
  • Fig. 1 shows results that suggest that sulfate is better at precipitating/ coagulating lignin than expected according to the literature. Here, chloride and sulfate are compared.

Abstract

The present invention provides a method for precipitating (separation) of lignin, using small amounts of acidifying agents, whereby a lignin product or an intermediate lignin product is obtained which can be used as fuel or chemical feed stock (or as a chemical or a raw material for further refining), from a lignin containing liquid/slurry, such as black liquor. The present invention also provides a method for separation of lignin from a lignin containing liquid/slurry, such as black liquor, whereby a more pure lignin is obtained. The present invention also provides a lignin product or an intermediate lignin product obtainable by the above methods. The present invention also provides use, preferably for the production of heat or for use as chemical, of said lignin product or intermediate lignin product.

Description

Method for separating lignin from a lignin containing liquid/slurry
This invention concerns the technical field of lignin separation. In particular the present invention relates to a method for lignin separation from a lignin containing liquid/slurry, such as process liquors in a mill containing lignin, preferably black liquor. Further the invention relates to lignin products obtainable by the above mentioned method and use of said products.
Background
In a modem, energy-optimized pulp mill, there is a surplus of energy. With today's process, bark can be exported while the remaining energy surplus, in the form of mixtures comprising other burnable residues , is burned in the recovery boiler, with a relatively low efficiency with regard to electricity production. There is also often a problem that the heat transfer capacity in the recovery boiler is a narrow sector, which limits the production of pulp in the mill. The recovery boiler is the most expensive (instrument) unit in the pulp mill.
Separation of lignin from black liquor is an interesting solution to these problems. In this way, the energy surplus can be withdrawn from the process in the form of a solid biofuel and can be exported to e.g. a power station, where the fuel can be used more efficiently than in the recovery boiler of the pulp mill. This lignin is also a valuable material for production of "green chemicals". Further, lignin extraction leaves a black liquor for combustion with a lower thermal value, which in turn leads to a lower load on the recovery boiler. This gives in a short term perspective possibilities for increased pulp production. In the long perspective lower instrument cost for the recovery boiler is expected.
There are several possible procedures for such a separation, and industrial applications have been known for a long time. Already in 1944, Tomlinson and Tomlinson Jr were granted a patent (US Patent 66481 1) for improvements to such a method. The separation method used today is to acidify the black liquor so that the lignin is precipitated in the form of a salt. The solid phase is separated from the liquor and can thereafter be cleaned or modified. There are industrial applications in operation today where lignin is separated from black liquor for use as special chemicals. One example of such a process is the precipitation of lignin from black liquor by acidification with carbon dioxide. The suspension is taken to a storage vessel for conditioning of the precipitate after which the solid lignin is separated and washed (with acidic wash water) on a band filter, and is finally processed to the desired state. However, the present methods make use of high amounts of acidifying chemicals for separating lignin, which in turn may be used for fuel. Such procedures are thus very expensive and it would accordingly be of great benefit if it would be possible to reduce the amount of acidifying chemicals necessary for separating lignin. Accordingly, there is a need for a method where lignin can be separated using small amounts of acidifying chemicals, e.g. sulphuric acid or carbon dioxide.
Summary of the invention
The present invention solves one or more of the above problems by providing according to a first aspect a method for precipitating (separation) of lignin, using small amounts of acidifying agents, whereby lignin is obtained which can be used as fuel (or as a chemical feed stock; or as a chemical or a raw material for further refining), from a lignin containing liquid/slurry, such as black liquor, comprising the following steps: a) addition of one or more compounds comprising sulphate or sulphate ions, or a mixture comprising said compound, to said liquid/slurry, b) adjustment of the pH level of said liquid/slurry by acidifying, and c) dewatering of said liquid/slurry whereby a lignin product or an intermediate lignin product is obtained.
In this above way lignin is separated more efficiently from e.g. black liquor and the filterability increases in the liquid where the precipitated lignin earlier was present.
The present invention also provides according to a second aspect a method for separation of lignin from a lignin containing liquid/slurry, such as black liquor, comprising the following steps: i) precipitating of lignin by the adding of one or more compounds comprising sulphate or sulphate ions, or a mixture comprising said compound, to said liquid/slurry, and by acidifying said liquid/slurry, and thereupon dewatering, ii) suspending the lignin filter cake whereupon a second suspension is obtained and adjusting the pH level to approximately the pH level of the washing water, iii) dewatering of the second suspension, iv) addition of washing water and performing a displacement washing at more or less constant conditions without any dramatic gradients in the pH, and v) dewatering of the filter cake produced in step iv) into a high dryness and displacement of the remaining washing liquid in said filter cake, whereby a lignin product or an intermediate lignin product is obtained.
By using said method of the second aspect a more pure lignin is obtained. The present invention also provides according to a third aspect a lignin product or an intermediate lignin product obtainable by the method according to the first aspect. The present invention also provides according to a fourth aspect a lignin product or an intermediate lignin product obtainable by the method according to the second aspect. The present invention also provides according to a fifth aspect use, preferably for the production of heat or as chemical feed stock, of the lignin product or the intermediate lignin product of the third or fourth aspects.
The present invention is based upon that it has been found that sulphate ions precipitate/coagulate lignin unexpectedly efficiently compared with e.g. chloride. The previously available knowledge according to the so-called Hofmeister series - lyotropic series - (F. Hofmeister 1888) says that chloride precipitates proteins from albumen better than sulphate.
The anion series according to Hofmeister:
SCN" > NO3" > Cf > citrate > CH3COO" > PO43" > SO42"
From above it is evident according to Hofmeister that chloride precipitates proteins from albumen better than sulphate.
The cation series according to Hofmeister: Ca2+ > Mg2+ > Na+ = K+ > NH4 + > N(CH3)/
Detailed description of the invention
It is intended throughout the present description that the expression "lignin containing liquid/slurry" is any liquid or slurry, which contains lignin. This liquid or slurry may be a process liquor, containing lignin, in a mill, preferably said liquid or slurry is a black liquor.
It is intended throughout the present description that the expression "compound comprising sulphate or a sulphate ion" embraces any compound comprising sulphate or a sulphate ion. This compound may be Na-, K- , (Al-), Ca-, Mg-, Fe- or organic sulfate, CaSO4,
K2SO4, AI2SO4, iron sulfates or MgSO4. Said compound may also be comprised in recovery boiler ashes, which is a mixture, or it may be essentially pure Na2SO-J-
It is intended throughout the present description that the expression "acidifying" embraces any means for acidifying the lignin containing liquid/slurry, such as black liquor. Preferably the acidifying is performed by adding SO2(g) , organic acids, HCI, HNO3, carbon dioxide or sulphuric acid (in the form of fresh sulfuric acid or a so called "spent acid" from a chlorine dioxide generator) or mixtures thereof to said liquid/slurry (preferably black liquor) most preferred by adding carbon dioxide or sulphuric acid. It is intended throughout the present description that the expression "dewatering" embraces any means for dewatering. Preferably the dewatering is performed by using centrifugation, a filter press apparatus, a band filter, a rotary filter, such as a drum filter, or a sedimentation tank, or similar equipment, most preferred a filter press apparatus is used. According to a preferred embodiment of the first aspect of the invention the dewatering of step c) is performed in a filter press apparatus.
According to a preferred embodiment of the first aspect of the invention the addition of step a) is done by adding recovery boiler ashes, i.e. ashes emanating from a soda recovery unit, which is a steam generator combined with a smelting furnace for the utilization of the heat of combustion of the black liquor and the recovery of the greater part of its inorganic components, or Na2SO-J, CaSO4, K2SO4, AI2SO4, iron sulfates or MgSO4. Preferably Na2Sθ4 is used.
According to a preferred embodiment of the first aspect of the invention mixing is performed after the adjustment of the pH level in step b). According to a preferred embodiment of the first aspect of the invention the pH level is adjusted to below approximately pH 9.5 in step b), preferably below approximately pH 6, most preferred the pH level is a pH from 1 to 4.
According to a preferred embodiment of the first aspect of the invention the pH level is adjusted whereby using CO2. According to a preferred embodiment of the first aspect of the invention the temperature is varied from 20 to 100° C depending on the nature of the liquid/slurry containing lignin, such as black liquor.
According to a preferred embodiment of the first aspect of the invention the filtrate from step c) is re-circulated directly to a recovery system, preferably after re-alkalization. According to a preferred embodiment of the second aspect of the invention the addition of step i) is done by adding recovery boiler ashes or Na2Sθ4 ,CaSO4, K2SO4, AI2SO4, iron sulfates and/or MgSO4. Preferably Na2Sθ4 is used.
According to a preferred embodiment of the second aspect of the invention mixing is performed after the acidifying in step i). According to a preferred embodiment of the second aspect of the invention the pH level is adjusted in step i) through acidifying whereby using CO2.
According to a preferred embodiment of the second aspect of the invention the temperature in step i) is varied from 20 to 100° C depending on the nature of the liquid/slurry containing lignin, such as black liquor. According to a preferred embodiment of the second aspect of the invention the dewatering of step i) and/or step iii) is performed in a filter press apparatus where the filter cake may be blown through by gas or a mixture of gases, preferably flue gases, air or vapor, most preferred air or overheated vapor, in order to dispose of the remaining lignin containing liquid/slurry such as black liquor (which is preferred).
According to a preferred embodiment of the second aspect of the invention the pH level is adjusted to below approximately pH 9.5 in step i), preferably below approximately pH
6, most preferred the pH level is a pH from 1 to 3.5.
According to a preferred embodiment of the second aspect of the invention the washing water has a pH level of below approximately pH 9.5, preferably below approximately pH 6, most preferred the pH level is a pH from 1 to 3.5. According to a preferred embodiment of the second aspect of the invention the filter cake obtained in step i) is blown through by using gas or a mixture of gases, including e.g. flue gases, air and vapor (which preferably can be air or overheated vapor) before suspending said cake as set out in step ii).
According to a preferred embodiment of the second aspect of the invention the pH level adjustment is combined with an adjustment of the ion strength, preferably by using multivalent alkaline earth metal ions, most preferred calcium ions. In this preferred embodiment the lignin is stabilized during the washing, as set out above earlier in the preferred embodiment of the second aspect of the present invention, whereby a pH-decrease is combined with an adjustment of the ionic strength in the slurry stage, preferably with multivalent alkaline earth metal ions (e.g. calcium ions). At a given pH, a higher ionic strength in the suspension stage reduces the lignin yield losses. Here also the ionic strength and pH of the wash water essentially corresponds to the conditions in the slurry stage to avoid gradients during the washing process. A higher ionic strength in the slurry and in the wash water gives a stable lignin even at high pH-values. Besides making the washing easier, divalent calcium ions can be introduced into the lignin, which in the combustion of the lignin can bind sulfur in the form of calcium sulphate (Aarsrud et al 1990, WO 9006964).
According to a preferred embodiment of the second aspect of the invention the pH level adjustment combined with an adjustment of the ion strength corresponds to the pH level and ion strength of the washing liquid. According to a preferred embodiment of the second aspect of the invention the filtrate from the first dewatering stage step i) is re-circulated directly to a recovery system, preferably after re-alkalization.
According to a preferred embodiment of the second aspect of the invention the remaining washing liquor in the filter cake in step v) is removed with air or flue gases, preferably flue gases from a recovery boiler, a lime kiln or a bark boiler. According to a preferred embodiment of the second aspect of the invention the washing liquor and a part of the filtrate from the second dewatering in step iii) is returned to the re-slurrying stage step ii) to further reduce the consumption of acid and water.
Accordingly, one or more compounds comprising sulphate or a sulphate ion, or a mixture comprising said compound such as recovery boiler ashes, is added during step a) (or step i)) in the method according to the first aspect (or the method according to the second aspect) to increase the ionic strength in the lignin containing liquid/slurry, such as black liquor, and thus be able to precipitate with a lower acid consumption or alternatively achieve a greater lignin precipitation with the same amount of added acid. This is particularly interesting since the sulfate ion would, as indicated in the appended Figure 1 , itself have an effect on the precipitation in addition to the fact that it increases the ionic strength. From a systems engineering perspective, it is to be expected that the sulfidity of the mill (the Na/S- balance) is influenced in a way which would require attention. Burkeite precipitation in the black liquor evaporation would also be affected and the requirements for the handling of this material would increase. On the other hand, the results show that it would be possible to reduce both the investment costs (the filtration surface) and the operating costs (reduced C02-costs) for removing lignin from e.g. black liquor significantly.
Preferred features of each aspect of the invention are as for each of the other aspects mutatis mutandis. The prior art documents mentioned herein are incorporated to the fullest extent permitted by law. The invention is further described in the following examples in conjunction with the appended figure, which do not limit the scope of the invention in any way. Embodiments of the present invention are described in more detail with the aid of examples of embodiments and figure, the only purpose of which is to illustrate the invention and are in no way intended to limit its extent.
Short description of the figure
Fig. 1 shows results that suggest that sulfate is better at precipitating/ coagulating lignin than expected according to the literature. Here, chloride and sulfate are compared.
Examples
Tests in laboratory, whereby studies of a separation of lignin have been performed, have shown positive results, in the form of both a yield increase and a better filterability. In the test, black liquor from Varo Mill was used (30% DS, Dry Substance). To two liters of this liquor, 10Og Na2Sθ4 was added - which should be a reasonable quantity if it is assumed that 30% of the black liquor flow is treated in the lignin precipitation stage and that all the recovery boiler ashes are added to this flow. The black liquor was acidified with CO2 to a pH of ca. 9.6 at 80°C. After the acidification, the slurry was allowed to stand with continuous stirring for 30 minutes, after which it was filtered. A reference test without the addition of Na2Sθ4 was carried out in the same way.
For these two tests (with and without Na2Sθ4-addition), the yield in the precipitation stage was determined (according to previously known methods). With Na2Sθ4- addition, the yield increased by 6.3 percentage points (from 60.5 to 66.8 % at the same precipitation-pH of ca. 9.6). The filterability, expressed as the specific filter resistance, was also improved dramatically from 1.6-1010 for the reference test to 6.9-108 with the addition of Na2SO4.
Various embodiments of the present invention have been described above but a person skilled in the art realizes further minor alterations, which would fall into the scope of the present invention. The breadth and scope of the present invention should not be limited by any of the above-described exemplary embodiments, but should be defined only in accordance with the following claims and their equivalents. For example, any of the above- noted methods can be combined with other known methods e.g. for separating lignin from a lignin containing liquid/slurry, such as black liquor. Other aspects, advantages and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.

Claims

Claims
1. Method for precipitating lignin from a ligπin containing liquid/slurry, such as black liquor, comprising the following steps: a) addition of one or more compounds comprising sulphate or sulphate ions, or a mixture comprising said compound, to said liquid/slurry; b) adjustment of the pH level of the said liquid/slurry by acidifying, and c) dewatering of said liquid/slurry whereby a lignin product, or an intermediate lignin product, is obtained.
2. A method according to claim 1 wherein the dewatering of step c) is performed in a filter press apparatus.
3. A method according to claim 1 wherein the addition of step a) is done by adding recovery boiler ashes or Na2Sθ4, CaSO4, K2SO4, AI2SO4, iron sulfates and/or MgSO4, preferably Na2Sθ4 .
4. A method according to claim 1 wherein mixing is performed after the adjustment of the pH level in step b).
5. A method according to claim 1 wherein the pH level is adjusted to below approximately pH 9.5 in step b), preferably below approximately pH 6, most preferred the pH level is a pH from 1 to 4.
6. A method according to claim 1 wherein the pH level is adjusted whereby using CO2.
7. A method according to claim 1 wherein the temperature is varied from 20 to 100° C depending on the nature of the lignin containing liquid/slurry, such as black liquor.
8. A method according to claim 1 wherein the filtrate from step c) is re-circulated directly to a recovery system, preferably after re-alkalization.
9. Method according for separation of lignin from a lignin containing liquid/slurry such as black liquor, comprising the following steps: i) precipitating of lignin by the adding of one or more compounds comprising sulphate or sulphate ions, or a mixture comprising said compound, to said liquid/slurry, and by acidifying said liquid/slurry, and thereupon dewatering, ii) suspending the lignin filter cake whereupon a second suspension is obtained and adjusting the pH level to approximately the pH level of the washing water, iii) dewatering of the second suspension, iv) addition of washing water and performing a displacement washing at more or less constant conditions without any dramatic gradients in the pH, and v) dewatering of the filter cake produced in step d) into a high dryness and displacement of the remaining washing liquid in said filter cake, whereby a lignin product or an intermediate lignin product is obtained.
10. A method according to claim 9 wherein the addition of step i) is done by adding recovery boiler ashes or Na2Sθ4, CaSO4, K2SO4, AI2SO4, iron sulfates and/or
MgSO4 .preferably Na2SO.;.
1 1. A method according to claim 9 wherein mixing is performed after the acidifying in step i).
12. A method according to claim 9 wherein the pH level is adjusted in step i) through acidifying whereby using CO2.
13. A method according to claim 9 wherein the temperature in step i) is varied from 20 to 100° C depending on the nature of the lignin containing liquid/slurry, such as black liquor.
14. A method according to claim 9 wherein the dewatering of step i) and/or step iii) is performed in a filter press apparatus where the filter cake is blown through by gas or a mixture of gases, preferably flue gases, air or vapor, most preferred air or overheated vapor, in order to dispose of the remaining lignin containing liquid/slurry such as black liquor
15. A method according to claim 9 wherein the pH level is adjusted to below approximately pH 9.5 in step i), preferably below approximately pH 6, most preferred the pH level is a pH from 1 to 3.5.
16. A method according to claim 9 wherein the washing water has a pH level of below approximately pH 9.5, preferably below approximately pH 6, most preferred the pH level is a pH from 1 to 3.5.
17. A method according to claim 9 wherein the filter cake obtained in step i) is blown through by using gas or a mixture of gases, including e.g. flue gases, air and vapor, which preferably can be air or overheated vapor, before suspending said cake as set out in step ii).
18. A method according to claim 9 wherein the pH level adjustment is combined with an adjustment of the ion strength, preferably by using multivalent alkaline earth metal ions, most preferred calcium ions.
19. A method according to claim 18 wherein the pH level adjustment combined with an adjustment of the ion strength corresponds to the pH level and ion strength of the washing liquid.
20. A method according to claim 9 wherein the filtrate from the first dewatering stage step i) is re-circulated directly to a recovery system, preferably after re-alkalization.
21 . A method according to claim 9 wherein the remaining washing liquor in the filter cake in step v) is removed with air or flue gases, preferably flue gases from a recovery boiler, a lime kiln or a bark boiler.
22. A method according to claim 9 wherein the washing liquor and a part of the filtrate from the second dewatering in step iii) is returned to the re-slurrying stage step ii) to further reduce the consumption of acid and water.
23. A lignin product or an intermediate lignin product obtainable by a method according to any one of claims 1 to 8.
24. A lignin product or an intermediate lignin product obtainable by a method according to any one of claims 9 to 22.
25. Use of a lignin product or an intermediate lignin product according to claim 23 or 24 for the production of heat or as chemical feed stock.
PCT/SE2005/001453 2004-10-07 2005-10-03 Method for separating lignin from a lignin containing liquid/slurry WO2006038863A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
BRPI0517543A BRPI0517543B1 (en) 2004-10-07 2005-10-03 method for lignin precipitation from a lignin-containing liquid or sludge
US11/661,412 US8815052B2 (en) 2004-10-07 2005-10-03 Method for separating lignin from a lignin containing liquid/slurry
CA2580834A CA2580834C (en) 2004-10-07 2005-10-03 Method for separating lignin from a lignin containing liquid/slurry
AT05788548T ATE513082T1 (en) 2004-10-07 2005-10-03 METHOD FOR SEPARATING LIGNIN FROM A LIQUID CONTAINING LIGNIN OR SLURRY
EP05788548A EP1797236B1 (en) 2004-10-07 2005-10-03 Method for separating lignin from a lignin containing liquid/slurry
JP2007535638A JP4887299B2 (en) 2004-10-07 2005-10-03 Method for separating lignin from liquid / slurry containing lignin

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE0402437A SE0402437D0 (en) 2004-10-07 2004-10-07 Method for separating lignin from a lignin containing liquid / slurry
SE0402437-8 2004-10-07

Publications (1)

Publication Number Publication Date
WO2006038863A1 true WO2006038863A1 (en) 2006-04-13

Family

ID=33434212

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE2005/001453 WO2006038863A1 (en) 2004-10-07 2005-10-03 Method for separating lignin from a lignin containing liquid/slurry

Country Status (11)

Country Link
US (1) US8815052B2 (en)
EP (1) EP1797236B1 (en)
JP (1) JP4887299B2 (en)
AT (1) ATE513082T1 (en)
BR (1) BRPI0517543B1 (en)
CA (1) CA2580834C (en)
ES (1) ES2368553T3 (en)
PT (1) PT1797236E (en)
SE (1) SE0402437D0 (en)
WO (1) WO2006038863A1 (en)
ZA (2) ZA200701627B (en)

Cited By (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007120091A1 (en) * 2006-03-16 2007-10-25 Stfi-Packforsk Ab Method for separating polymeric pentose from a liquid/slurry
WO2009104995A1 (en) 2008-02-21 2009-08-27 Lignoboost Ab A method for separating lignin from black liquor, a lignin product, and use of a lignin product for the production of fuels or materials
WO2010143997A1 (en) 2009-06-10 2010-12-16 Metso Power Ab Method for precipitating lignin from black liquor by utilizing waste gases
WO2011005174A1 (en) * 2009-07-07 2011-01-13 Sveaskog Förvaltnings AB Slow-release fertilizer
WO2011005175A1 (en) * 2009-07-07 2011-01-13 Sveaskog Förvaltnings AB Method for preparing slow release fertilizers
WO2011007369A1 (en) * 2009-07-13 2011-01-20 Chemtex Italia S.R.L. High temperature lignin separation process
WO2011138357A1 (en) 2010-05-07 2011-11-10 Basf Se Method for producing at least one low-molecular-weight aromatic valuable material from a lignin-containing starting material
WO2011138356A1 (en) 2010-05-07 2011-11-10 Basf Se Process for preparing synthesis gas and at least one organic, liquid or liquefiable value product
WO2011138355A2 (en) 2010-05-07 2011-11-10 Basf Se Method for producing pulp and at least one organic liquid or liquefiable valuable material with exhaust gas recycling
WO2012013735A1 (en) 2010-07-29 2012-02-02 Basf Se Composition comprising catalyst and lignin and its use for producing an aromatic composition
US8172981B2 (en) * 2004-09-14 2012-05-08 Lignoboost Ab Separating lignin from black liquor by precipitation, suspension and separation
WO2012160072A1 (en) 2011-05-24 2012-11-29 Basf Se Process for preparing polyisocyanates from biomass
WO2012177198A1 (en) 2011-06-22 2012-12-27 Metso Power Ab Method for lignin separation from black liquor comprising multiple acidification steps
WO2013002687A1 (en) * 2011-06-28 2013-01-03 Metso Power Ab Method for lignin separation from black liquor comprising removal of sulphur compounds from formed water effluent
US8404355B2 (en) 2010-12-09 2013-03-26 Virdia Ltd Methods and systems for processing lignocellulosic materials and related compositions
WO2013070130A1 (en) 2011-11-11 2013-05-16 Metso Power Ab Method for lignin separation from black liquor involving multiple acidification steps
US8465558B2 (en) 2008-02-14 2013-06-18 Ecotraffic Erd3 Ab Biofuel
DE112011102202T5 (en) 2010-06-30 2013-06-27 Weyerhaeuser Nr Company Lignin / polyacrylonitrile-containing spinning solutions, fibers and processes for their preparation
DE102012102327B3 (en) * 2012-03-12 2013-08-01 Brandenburgische Technische Universität Cottbus Preparing water-insoluble lignin agglomerate from the waste liquor of cellulose extraction process, useful e.g. to produce bioplastics, comprises granulating the waste liquor and treating the obtained lignin agglomerates with an acid
WO2014116150A1 (en) 2013-01-24 2014-07-31 Valmet Power Ab Method for producing high purity lignin
EP2591166A4 (en) * 2010-07-07 2014-10-08 Stora Enso Oyj Process for production of precipitated lignin from black liquor and precipitated lignin produced by the process
US8933262B2 (en) 2011-05-24 2015-01-13 Basf Se Process for preparing polyisocyanates from biomass
DE102013112499A1 (en) * 2013-11-13 2015-05-13 Brandenburgische Technische Universität Cottbus-Senftenberg Apparatus and method for agglomerating the spent liquor of a cellulose recovery process
US9115467B2 (en) 2010-08-01 2015-08-25 Virdia, Inc. Methods and systems for solvent purification
US9139606B2 (en) 2010-10-15 2015-09-22 Upm-Kymmene Corporation Continuous method for the precipitation of lignin from black liquor
WO2015150626A1 (en) * 2014-04-03 2015-10-08 Andritz Oy Method for handling spent wash solution of a lignin-recovery process
WO2016001490A1 (en) 2014-07-04 2016-01-07 Metsä Fibre Oy Method of utilizing lignin contained in black liquor
US9410216B2 (en) 2010-06-26 2016-08-09 Virdia, Inc. Sugar mixtures and methods for production and use thereof
US9476106B2 (en) 2010-06-28 2016-10-25 Virdia, Inc. Methods and systems for processing a sucrose crop and sugar mixtures
US9512495B2 (en) 2011-04-07 2016-12-06 Virdia, Inc. Lignocellulose conversion processes and products
US9617608B2 (en) 2011-10-10 2017-04-11 Virdia, Inc. Sugar compositions
US9663836B2 (en) 2010-09-02 2017-05-30 Virdia, Inc. Methods and systems for processing sugar mixtures and resultant compositions
US9828726B2 (en) 2013-08-19 2017-11-28 Valmet Technologies Oy Method and system for treating lignin
US10035957B2 (en) 2015-02-06 2018-07-31 Valmet Technologies Oy Method for treating lignin-based material
WO2020013112A1 (en) 2018-07-09 2020-01-16 日本製紙株式会社 Organic anti-shrinkage agent for lead storage battery
EP3494256A4 (en) * 2011-05-24 2020-03-18 Liquid Lignin Company, LLC Process for treating lignin
DE102018220946A1 (en) 2018-12-04 2020-06-04 Suncoal Industries Gmbh Particulate carbon materials and methods for their separation
EP3693508A1 (en) 2019-02-08 2020-08-12 Scitech-service OY Method for lignin production
WO2020169809A2 (en) 2019-02-21 2020-08-27 Suncoal Industries Gmbh Method for reducing the odour in particle-forming carbon materials
WO2021110933A1 (en) 2019-12-06 2021-06-10 Basf Se Method for preparation of lignin oligomers
US11078548B2 (en) 2015-01-07 2021-08-03 Virdia, Llc Method for producing xylitol by fermentation
EP3960816A1 (en) 2020-08-25 2022-03-02 Indian Oil Corporation Limited A method to valorize 2g bioethanol waste streams
WO2022043470A1 (en) 2020-08-26 2022-03-03 Suncoal Industries Gmbh Modified fine particulate carbon materials and method for producing same
WO2022122575A1 (en) 2020-12-07 2022-06-16 Basf Se Aqueous lactam solution of lignin
WO2022136613A1 (en) 2020-12-23 2022-06-30 Basf Se Binder composition comprising polyamine(s) as well as 1,3 -dihydroxyacetone, glycolaldehyde and/or glyceraldehyde for composite articles
WO2022136614A1 (en) 2020-12-23 2022-06-30 Basf Se Binder composition comprising polyamine(s) and hydroxyacetone for composite articles
WO2022190829A1 (en) 2021-03-08 2022-09-15 日本製紙株式会社 Organic anti-shrinkage agent for lead-acid batteries
WO2023277774A1 (en) 2021-06-30 2023-01-05 Valmet Ab Method and system for producing lignin

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE0402201D0 (en) * 2004-09-14 2004-09-14 Stfi Packforsk Ab Method for separating lignin from black liquor
JP4316536B2 (en) * 2005-06-07 2009-08-19 独立行政法人科学技術振興機構 Method for separating and recovering lignin derivatives
EP3778717A1 (en) * 2008-07-16 2021-02-17 Renmatix Inc. Nano-catalytic-solvo-thermal technology platform bio-refineries
US8546560B2 (en) * 2008-07-16 2013-10-01 Renmatix, Inc. Solvo-thermal hydrolysis of cellulose
US9260464B2 (en) * 2009-09-25 2016-02-16 Michael A. Lake Process for recovering lignin
US9879119B2 (en) 2009-09-25 2018-01-30 Michael A. Lake Lignin product and process for making same
CN105525043B (en) 2010-01-19 2021-03-19 瑞恩麦特克斯股份有限公司 Production of fermentable sugars and lignin from biomass using supercritical fluids
CN103154097B (en) * 2010-06-03 2017-01-18 Fp创新研究中心 method for separating lignin from black liquor
WO2011162420A1 (en) * 2010-06-25 2011-12-29 ロペスアンドエヌティ有限会社 Method for recovering lignin in the neutral range from spent pulp cooking liquor
RU2602068C2 (en) 2011-05-04 2016-11-10 Ренмэтикс, Инк. Producing lignin from lignocellulose biomass
US8801859B2 (en) 2011-05-04 2014-08-12 Renmatix, Inc. Self-cleaning apparatus and method for thick slurry pressure control
US9790641B2 (en) 2011-05-24 2017-10-17 Liquid Lignin Company, Llc Process for treating lignin
US8759498B2 (en) 2011-12-30 2014-06-24 Renmatix, Inc. Compositions comprising lignin
FI127010B (en) * 2012-08-24 2017-09-29 Upm Kymmene Corp A method for recovering low molecular weight lignin from a filtrate
DE102012112231B4 (en) * 2012-10-15 2014-05-28 Brandenburgische Technische Universität Cottbus-Senftenberg Process for the preparation of acid-resistant biopolymer lignin membranes
WO2014144746A1 (en) 2013-03-15 2014-09-18 Renmatix, Inc. High purity lignin, lignin compositions, and higher structured lignin
FI128419B (en) * 2014-01-13 2020-04-30 Upm Kymmene Corp A method for separating lignocellulose particle fraction and lignin particle fraction
FI126369B (en) * 2014-06-06 2016-10-31 Andritz Oy Procedure for using lignin separated from black liquor as a blast furnace fuel
CA2962611A1 (en) 2014-09-26 2016-03-31 Renmatix, Inc. Adhesive compositions comprising type-ii cellulose
FI128045B (en) * 2016-11-17 2019-08-30 Upm Kymmene Corp A method and an apparatus for recovering chemicals from an alkaline lignin material
CN108610490A (en) * 2018-05-30 2018-10-02 谭亚 A kind of high-valued lignin purification process
JP6662423B1 (en) * 2018-09-06 2020-03-11 日本製紙株式会社 How to separate lignin
BR102019011474A2 (en) * 2019-06-03 2019-09-10 Suzano Papel E Celulose S A black liquor lignin extraction processes

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US664811A (en) 1899-09-13 1900-12-25 Lippy Mfg Company Screen or riddle for separators.
US2541058A (en) * 1948-06-16 1951-02-13 Wood Conversion Co Processing of lignocellulose materials
US3895996A (en) * 1972-08-01 1975-07-22 Betz Laboratories Beneficiation of lignin solutions and pulp mill wastes
US4674597A (en) 1986-06-17 1987-06-23 Humphrey Denver L Tree climbing device
WO1990006964A1 (en) 1988-12-12 1990-06-28 Holmen Lignotech Ab A lignin preparation and a method for its manufacture
US5811527A (en) * 1995-10-11 1998-09-22 Nippon Paper Industries Co., Ltd. Lignin composition, method of producing the same and dispersing agent for cement used the same
US20020059994A1 (en) 1998-09-24 2002-05-23 Kurple Kenneth R. Pulping process without a recovery furnace

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR485412A (en) * 1916-05-13 1918-01-09 Erik Oman Treatment of sulphite detergent residues to allow their reuse
US2228976A (en) * 1936-07-11 1941-01-14 Mead Corp Molding material and method of producing the same
US2470764A (en) * 1943-09-23 1949-05-24 Dunbar Thomas Leonidas Method of treating waste sulfite liquor
US2464828A (en) * 1944-02-22 1949-03-22 West Virginia Pulp & Paper Co Method of producing lignin from black liquor
US2541127A (en) * 1948-06-17 1951-02-13 Weyerhaeuser Timber Co Process for producing dehydroperillic acid
US2541059A (en) * 1948-06-17 1951-02-13 Weyerhaeuser Timber Co Process for producing lignin products
US2701255A (en) * 1949-07-29 1955-02-01 Weyerhaeuser Timber Co Organic products from lignocellulose
US2680113A (en) * 1949-12-22 1954-06-01 Svenska Cellulosaforeningens C Method of producing water-soluble products from black liquor lignin
US2623040A (en) * 1950-07-06 1952-12-23 West Virginia Pulp & Paper Co Method of coagulating colloidal lignates in aqueous dispersions
US2697701A (en) * 1951-02-09 1954-12-21 Weyerhaeuser Timber Co Fractionation of lignocellulose materials
US2727028A (en) * 1951-03-14 1955-12-13 Lignosol Chemicals Ltd Treatment of waste sulphite liquor and products thereof
US2849314A (en) * 1953-03-02 1958-08-26 Permanente Cement Company Process of treatment and products from waste sulfite liquors
US2772965A (en) * 1953-06-02 1956-12-04 Rayonier Inc Recovery of chemicals in wood pulp preparation
FR1112129A (en) * 1953-11-19 1956-03-08 Inventa Ag Process for the preparation of lignin from black liquors
US2913310A (en) * 1956-05-14 1959-11-17 Crossett Chemical Company Chemical recovery process
US2994633A (en) * 1958-08-21 1961-08-01 Crossett Company Process for separating lignin solids from used neutral sulfite pulping liquors
US2976273A (en) * 1958-09-10 1961-03-21 West Virginia Pulp & Paper Co Treatment of kraft black liquor and product
US3048576A (en) * 1958-11-04 1962-08-07 West Virginia Pulp & Paper Co Continuous acidulation and coagulation of lignin in black liquor
US2997466A (en) * 1958-11-04 1961-08-22 West Virginia Pulp & Paper Co Decantation of lignin
US3038834A (en) * 1959-05-06 1962-06-12 Alfred M Thomsen Method of carbonizing spent cooking liquor from pulp making
US3095409A (en) * 1960-04-01 1963-06-25 Puget Sound Pulp & Timber Co Acid treated sulfonated lignin-containing material and process for the production thereof
US3130115A (en) * 1961-10-27 1964-04-21 Alfred M Thomsen Method of processing lignified cellulose
NL300131A (en) * 1962-11-15
US3404063A (en) * 1964-12-28 1968-10-01 Owens Illinois Inc By-product recovery from kraft black liquor
US3428520A (en) * 1965-08-12 1969-02-18 Scott Paper Co Pulping process with lignin recovery
US3546200A (en) * 1968-06-18 1970-12-08 Union Camp Corp Lignin precipitation from black liquor in the presence of chloro,bromo or nitro containing hydrocarbons
US3806403A (en) * 1972-03-27 1974-04-23 Nyanza Inc Process for treating black liquor to precipitate organic materials therefrom
US4007004A (en) * 1974-07-05 1977-02-08 Westvaco Corporation Dyestuff filler derived from kraft black liquor
CA1172808A (en) * 1981-07-23 1984-08-21 Marc F. Beaupre Kraft overload recovery process
US4470876A (en) * 1982-07-22 1984-09-11 Beaupre Marc F Kraft overload recovery process
US4891070A (en) * 1987-04-13 1990-01-02 Westvaco Corporation Lignin amine salt as binder for aqueous printing ink composition
US4764597A (en) * 1987-06-15 1988-08-16 Westvaco Corporation Method for methylolation of lignin materials
FI883934A (en) * 1987-08-27 1989-02-28 Holmens Bruk Ab SAETT ATT GENOMFOERA EN SULFATCELLULOSAPROCESS OCH EN ANLAEGGNING FOER GENOMFOERING AV SAETTET.
US5034094A (en) * 1987-11-06 1991-07-23 Kurple Kenneth R Method of converting inorganic materials from kraft pulping liquor into pulping chemicals without passing them through a recovery furnace
EP0364632A1 (en) * 1988-10-17 1990-04-25 Zeneca Limited Production of lignin
US5288857A (en) * 1988-12-12 1994-02-22 Ligno Tech Sweden Ab Lignin preparation and method for its manufacture
CA1335976C (en) * 1989-05-31 1995-06-20 Mahmoud Kamran Azarniouch Recovery of naoh and other values from spent liquors and bleach plant effluents
US5096540A (en) * 1990-04-06 1992-03-17 Sell Nancy J Method for recycling sulfur dioxide from sulfite pulping liquors
FI102395B (en) * 1991-11-26 1998-11-30 Ahlstrom Machinery Oy Method for energy recovery from pulp process effluents
US5635024A (en) * 1993-08-20 1997-06-03 Bountiful Applied Research Corporation Process for separating lignins and dissolved organic compounds from kraft spent liquor
FI961930A (en) * 1996-05-07 1997-11-08 Ahlstrom Machinery Oy Process and apparatus for streamlining an alkaline process for the production of cellulose
WO1998042912A1 (en) * 1997-03-20 1998-10-01 Granit S.A. Method for preparing alkaline solutions containing aromatic polymers
US5777086A (en) * 1997-05-12 1998-07-07 Thermo Fibergen, Inc. Method of recovering lignin from pulp and paper sludge
US6589427B2 (en) * 2001-02-28 2003-07-08 Council Of Scientific & Industrial Research Process for treatment of mixture of spent wash from distillery and black liquor from pulp and paper industry
US20020129910A1 (en) * 2001-03-14 2002-09-19 Lightner Gene E. Separation of black liquor to produce lignins substantially free of sodium
EP1302529A1 (en) * 2001-10-09 2003-04-16 Linde AG Brine separation in tall soap oil preparation
US7189306B2 (en) * 2002-02-22 2007-03-13 Gervais Gibson W Process of treating lignocellulosic material to produce bio-ethanol
US20030221804A1 (en) * 2002-06-03 2003-12-04 Lightner Gene E. Lignins derived from black liquor
AU2003291874A1 (en) * 2003-06-03 2005-01-21 David Tarasenko Method for producing pulp and lignin
FI117507B (en) * 2004-07-09 2006-11-15 Kemira Oyj Procedure for removing lignin from water
SE0402201D0 (en) * 2004-09-14 2004-09-14 Stfi Packforsk Ab Method for separating lignin from black liquor
US8172981B2 (en) * 2004-09-14 2012-05-08 Lignoboost Ab Separating lignin from black liquor by precipitation, suspension and separation
WO2007120091A1 (en) * 2006-03-16 2007-10-25 Stfi-Packforsk Ab Method for separating polymeric pentose from a liquid/slurry

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US664811A (en) 1899-09-13 1900-12-25 Lippy Mfg Company Screen or riddle for separators.
US2541058A (en) * 1948-06-16 1951-02-13 Wood Conversion Co Processing of lignocellulose materials
US3895996A (en) * 1972-08-01 1975-07-22 Betz Laboratories Beneficiation of lignin solutions and pulp mill wastes
US4674597A (en) 1986-06-17 1987-06-23 Humphrey Denver L Tree climbing device
WO1990006964A1 (en) 1988-12-12 1990-06-28 Holmen Lignotech Ab A lignin preparation and a method for its manufacture
US5811527A (en) * 1995-10-11 1998-09-22 Nippon Paper Industries Co., Ltd. Lignin composition, method of producing the same and dispersing agent for cement used the same
US20020059994A1 (en) 1998-09-24 2002-05-23 Kurple Kenneth R. Pulping process without a recovery furnace

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DAVY M F ET AL: "Economic evaluation of black liquor treatment processes for incremental kraft pulp production.", 83RD ANNUAL MEETING, TECHNICAL PULP PRODUCTION., 28 January 1997 (1997-01-28) - 31 January 1997 (1997-01-31), pages 1 - 8, XP002993835 *
See also references of EP1797236A4

Cited By (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8172981B2 (en) * 2004-09-14 2012-05-08 Lignoboost Ab Separating lignin from black liquor by precipitation, suspension and separation
WO2007120091A1 (en) * 2006-03-16 2007-10-25 Stfi-Packforsk Ab Method for separating polymeric pentose from a liquid/slurry
US8465558B2 (en) 2008-02-14 2013-06-18 Ecotraffic Erd3 Ab Biofuel
WO2009104995A1 (en) 2008-02-21 2009-08-27 Lignoboost Ab A method for separating lignin from black liquor, a lignin product, and use of a lignin product for the production of fuels or materials
US9382389B2 (en) 2008-02-21 2016-07-05 Valmet Aktiebolag Method for separating lignin from black liquor, a lignin product, and use of a lignin product for the production of fuels or materials
WO2010143997A1 (en) 2009-06-10 2010-12-16 Metso Power Ab Method for precipitating lignin from black liquor by utilizing waste gases
WO2011005174A1 (en) * 2009-07-07 2011-01-13 Sveaskog Förvaltnings AB Slow-release fertilizer
WO2011005175A1 (en) * 2009-07-07 2011-01-13 Sveaskog Förvaltnings AB Method for preparing slow release fertilizers
WO2011007369A1 (en) * 2009-07-13 2011-01-20 Chemtex Italia S.R.L. High temperature lignin separation process
CN102575422B (en) * 2009-07-13 2016-08-03 贝塔可再生资源公司 The separating at high temperature method of lignin
CN102575422A (en) * 2009-07-13 2012-07-11 贝塔可再生资源公司 High temperature lignin separation process
KR101554934B1 (en) 2009-07-13 2015-09-22 베타 리뉴와블레스 에스.페.아. High temperature lignin separation process
JP2012532757A (en) * 2009-07-13 2012-12-20 ベータ リニューアブルス エス・ピー・エー High temperature separation method of lignin
TWI500632B (en) * 2009-07-13 2015-09-21 Beta Renewables Spa High temperature lignin separation process
WO2011138355A2 (en) 2010-05-07 2011-11-10 Basf Se Method for producing pulp and at least one organic liquid or liquefiable valuable material with exhaust gas recycling
WO2011138357A1 (en) 2010-05-07 2011-11-10 Basf Se Method for producing at least one low-molecular-weight aromatic valuable material from a lignin-containing starting material
WO2011138356A1 (en) 2010-05-07 2011-11-10 Basf Se Process for preparing synthesis gas and at least one organic, liquid or liquefiable value product
US10752878B2 (en) 2010-06-26 2020-08-25 Virdia, Inc. Sugar mixtures and methods for production and use thereof
US9410216B2 (en) 2010-06-26 2016-08-09 Virdia, Inc. Sugar mixtures and methods for production and use thereof
US9963673B2 (en) 2010-06-26 2018-05-08 Virdia, Inc. Sugar mixtures and methods for production and use thereof
US9476106B2 (en) 2010-06-28 2016-10-25 Virdia, Inc. Methods and systems for processing a sucrose crop and sugar mixtures
US10760138B2 (en) 2010-06-28 2020-09-01 Virdia, Inc. Methods and systems for processing a sucrose crop and sugar mixtures
DE112011102202T5 (en) 2010-06-30 2013-06-27 Weyerhaeuser Nr Company Lignin / polyacrylonitrile-containing spinning solutions, fibers and processes for their preparation
DE112011102202B4 (en) 2010-06-30 2019-09-12 Weyerhaeuser Nr Company Lignin / polyacrylonitrile-containing spinning solutions, fibers and processes for their preparation
EP2591166A4 (en) * 2010-07-07 2014-10-08 Stora Enso Oyj Process for production of precipitated lignin from black liquor and precipitated lignin produced by the process
WO2012013735A1 (en) 2010-07-29 2012-02-02 Basf Se Composition comprising catalyst and lignin and its use for producing an aromatic composition
US9115467B2 (en) 2010-08-01 2015-08-25 Virdia, Inc. Methods and systems for solvent purification
US11242650B2 (en) 2010-08-01 2022-02-08 Virdia, Llc Methods and systems for solvent purification
US9663836B2 (en) 2010-09-02 2017-05-30 Virdia, Inc. Methods and systems for processing sugar mixtures and resultant compositions
US10240217B2 (en) 2010-09-02 2019-03-26 Virdia, Inc. Methods and systems for processing sugar mixtures and resultant compositions
US9719210B2 (en) 2010-10-15 2017-08-01 Upm-Kymmene Corporation Continuous method for the precipitation of lignin from black liquor
US9139606B2 (en) 2010-10-15 2015-09-22 Upm-Kymmene Corporation Continuous method for the precipitation of lignin from black liquor
US8404355B2 (en) 2010-12-09 2013-03-26 Virdia Ltd Methods and systems for processing lignocellulosic materials and related compositions
US9512495B2 (en) 2011-04-07 2016-12-06 Virdia, Inc. Lignocellulose conversion processes and products
US10876178B2 (en) 2011-04-07 2020-12-29 Virdia, Inc. Lignocellulosic conversion processes and products
US11667981B2 (en) 2011-04-07 2023-06-06 Virdia, Llc Lignocellulosic conversion processes and products
EP3494256A4 (en) * 2011-05-24 2020-03-18 Liquid Lignin Company, LLC Process for treating lignin
WO2012160072A1 (en) 2011-05-24 2012-11-29 Basf Se Process for preparing polyisocyanates from biomass
US8933262B2 (en) 2011-05-24 2015-01-13 Basf Se Process for preparing polyisocyanates from biomass
US9266917B2 (en) 2011-06-22 2016-02-23 Valmet Ab Method for lignin separation from black liquor having multiple acidification steps
WO2012177198A1 (en) 2011-06-22 2012-12-27 Metso Power Ab Method for lignin separation from black liquor comprising multiple acidification steps
WO2013002687A1 (en) * 2011-06-28 2013-01-03 Metso Power Ab Method for lignin separation from black liquor comprising removal of sulphur compounds from formed water effluent
US9475833B2 (en) 2011-06-28 2016-10-25 Valmet Power Ab Method for lignin separation from black liquor comprising removal of sulfur compounds from formed water effluent
US10041138B1 (en) 2011-10-10 2018-08-07 Virdia, Inc. Sugar compositions
US9617608B2 (en) 2011-10-10 2017-04-11 Virdia, Inc. Sugar compositions
US9976194B2 (en) 2011-10-10 2018-05-22 Virdia, Inc. Sugar compositions
US9845514B2 (en) 2011-10-10 2017-12-19 Virdia, Inc. Sugar compositions
WO2013070130A1 (en) 2011-11-11 2013-05-16 Metso Power Ab Method for lignin separation from black liquor involving multiple acidification steps
WO2013135485A1 (en) * 2012-03-12 2013-09-19 Brandenburgische Technische Universität Cottbus Method for producing water-insoluble lignin agglomerates
DE102012102327B3 (en) * 2012-03-12 2013-08-01 Brandenburgische Technische Universität Cottbus Preparing water-insoluble lignin agglomerate from the waste liquor of cellulose extraction process, useful e.g. to produce bioplastics, comprises granulating the waste liquor and treating the obtained lignin agglomerates with an acid
WO2014116150A1 (en) 2013-01-24 2014-07-31 Valmet Power Ab Method for producing high purity lignin
US9828726B2 (en) 2013-08-19 2017-11-28 Valmet Technologies Oy Method and system for treating lignin
DE102013112499A1 (en) * 2013-11-13 2015-05-13 Brandenburgische Technische Universität Cottbus-Senftenberg Apparatus and method for agglomerating the spent liquor of a cellulose recovery process
WO2015150626A1 (en) * 2014-04-03 2015-10-08 Andritz Oy Method for handling spent wash solution of a lignin-recovery process
WO2016001490A1 (en) 2014-07-04 2016-01-07 Metsä Fibre Oy Method of utilizing lignin contained in black liquor
US11078548B2 (en) 2015-01-07 2021-08-03 Virdia, Llc Method for producing xylitol by fermentation
US10035957B2 (en) 2015-02-06 2018-07-31 Valmet Technologies Oy Method for treating lignin-based material
WO2020013112A1 (en) 2018-07-09 2020-01-16 日本製紙株式会社 Organic anti-shrinkage agent for lead storage battery
US11251434B2 (en) 2018-07-09 2022-02-15 Nippon Paper Industries Co., Ltd. Organic expander for lead storage battery
WO2020115143A1 (en) 2018-12-04 2020-06-11 Suncoal Industries Gmbh Particulate carbon materials and method for the separation thereof
DE102018220946A1 (en) 2018-12-04 2020-06-04 Suncoal Industries Gmbh Particulate carbon materials and methods for their separation
EP3693508A1 (en) 2019-02-08 2020-08-12 Scitech-service OY Method for lignin production
WO2020169809A2 (en) 2019-02-21 2020-08-27 Suncoal Industries Gmbh Method for reducing the odour in particle-forming carbon materials
WO2021110933A1 (en) 2019-12-06 2021-06-10 Basf Se Method for preparation of lignin oligomers
US11623937B2 (en) 2020-08-25 2023-04-11 Indian Oil Corporation Limited Method to valorize 2G bioethanol waste streams
EP3960816A1 (en) 2020-08-25 2022-03-02 Indian Oil Corporation Limited A method to valorize 2g bioethanol waste streams
WO2022043470A1 (en) 2020-08-26 2022-03-03 Suncoal Industries Gmbh Modified fine particulate carbon materials and method for producing same
WO2022122575A1 (en) 2020-12-07 2022-06-16 Basf Se Aqueous lactam solution of lignin
WO2022136613A1 (en) 2020-12-23 2022-06-30 Basf Se Binder composition comprising polyamine(s) as well as 1,3 -dihydroxyacetone, glycolaldehyde and/or glyceraldehyde for composite articles
WO2022136614A1 (en) 2020-12-23 2022-06-30 Basf Se Binder composition comprising polyamine(s) and hydroxyacetone for composite articles
WO2022190829A1 (en) 2021-03-08 2022-09-15 日本製紙株式会社 Organic anti-shrinkage agent for lead-acid batteries
WO2023277774A1 (en) 2021-06-30 2023-01-05 Valmet Ab Method and system for producing lignin

Also Published As

Publication number Publication date
ZA200802400B (en) 2009-04-29
BRPI0517543A (en) 2008-10-14
JP4887299B2 (en) 2012-02-29
EP1797236A1 (en) 2007-06-20
EP1797236B1 (en) 2011-06-15
BRPI0517543B1 (en) 2017-02-07
JP2008516100A (en) 2008-05-15
SE0402437D0 (en) 2004-10-07
ES2368553T3 (en) 2011-11-18
EP1797236A4 (en) 2010-04-28
US8815052B2 (en) 2014-08-26
ATE513082T1 (en) 2011-07-15
ZA200701627B (en) 2008-07-30
CA2580834A1 (en) 2006-04-13
CA2580834C (en) 2013-10-01
US20080051566A1 (en) 2008-02-28
PT1797236E (en) 2011-08-31

Similar Documents

Publication Publication Date Title
EP1797236B1 (en) Method for separating lignin from a lignin containing liquid/slurry
EP1794363B2 (en) Method for separating lignin from black liquor
US9382389B2 (en) Method for separating lignin from black liquor, a lignin product, and use of a lignin product for the production of fuels or materials
US8172981B2 (en) Separating lignin from black liquor by precipitation, suspension and separation
CN103154097B (en) method for separating lignin from black liquor
JP6363596B2 (en) Chemical pulp manufacturing method
CN105555793A (en) Method and system for treating lignin
CA2920702C (en) Method for extracting lignin from black liquor and products produced thereby
US3366535A (en) Process for regenerating waste liquor for reuse in kraft pulping operation
US2238456A (en) Purification of magnesium base liquors
WO2007120091A1 (en) Method for separating polymeric pentose from a liquid/slurry
CN114364841B (en) Process for extracting lignin from black liquor
JP2713429B2 (en) Method and apparatus for performing a sulfate pulp process
JP2008115052A (en) Method of producing calcium carbonate
Björk et al. Successful start-up of lignin extraction at Stora Enso Sunila mill
CA2291722C (en) Process for treating spent, waste, alkaline digestion liquor from paper pulping operations and product

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

DPEN Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2007/01627

Country of ref document: ZA

WWE Wipo information: entry into national phase

Ref document number: 2580834

Country of ref document: CA

Ref document number: 2007535638

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2005788548

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2005788548

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 11661412

Country of ref document: US

ENP Entry into the national phase

Ref document number: PI0517543

Country of ref document: BR