CN1085757C - Process for removing lignin from black liquor in making paper by soda pulping - Google Patents
Process for removing lignin from black liquor in making paper by soda pulping Download PDFInfo
- Publication number
- CN1085757C CN1085757C CN99116492A CN99116492A CN1085757C CN 1085757 C CN1085757 C CN 1085757C CN 99116492 A CN99116492 A CN 99116492A CN 99116492 A CN99116492 A CN 99116492A CN 1085757 C CN1085757 C CN 1085757C
- Authority
- CN
- China
- Prior art keywords
- black liquor
- lignin
- soda pulping
- making paper
- removing lignin
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Fee Related
Links
- 229920005610 lignin Polymers 0.000 title claims abstract description 26
- 238000004537 pulping Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims description 11
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 7
- 239000003337 fertilizer Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 229920000620 organic polymer Polymers 0.000 claims description 8
- 239000005518 polymer electrolyte Substances 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 3
- 229920000058 polyacrylate Polymers 0.000 abstract 2
- 229920000867 polyelectrolyte Polymers 0.000 abstract 2
- 150000002484 inorganic compounds Chemical class 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
The present invention relates to a technology for removing lignin in paper-making black liquor by an alkaline pulping process. Organic polyelectrolyte (A), polyacrylamide, polyacrylate and substitutive derivatives thereof, etc. are directly added into the alkaline black liquor; an acidic material (B) is added into the alkaline black liquor after the organic polyelectrolyte (A), the polyacrylamide, the polyacrylate and the substitutive derivatives thereof, etc. are dissolved. The pH value of the black liquor is regulated and is less than or equal to 5, lignin is immediately aggregated and precipitated, separated solid objects are used as industrial raw materials to produce organic compound fertilizers and inorganic compound fertilizers, and recovering liquor is back used for a pulping system. The present invention has the advantages of simple technology, convenient operation, reliable running, low expenses, little disposable investment, thorough lignin separation, pollution treatment and resource comprehensive utilization, and has obvious environment benefit, social benefit and economic benefit.
Description
The present invention relates to paper-making pulping black liquor and handle, particularly black paper-making liquid of alkali pulping thoroughly removes the treatment process of lignin.
Paper-making industrial waste water pollutes and is one of the world's five big public hazards, black paper-making liquid of alkali pulping accounts for about 80% of paper-making pollution total amount, the improvement of black liquor pollution is the most important thing that the soda pulping process paper-making pollution is administered, and the improvement key of black paper-making liquid of alkali pulping is the thorough separation of lignin.
The main method of administering at present black liquor pollution is a Silvola recovery, and Silvola recovery is in the world at the slurrying enterprise that is raw material with timber, and development is improved and a kind of successful technology of coming, and is mainly used in large enterprise.And to be used for careless class be the slurrying enterprise of raw material, though through continuous exploration, improvement for many years, but because the characteristic of the high silicon of straw pulp black liquor, high viscosity, low heat value, actual macroscopical alkali recovery is paced up and down below 60% always, and one-time investment is big, defectives such as energy consumption height and secondary pollution can't be carried out operation normally and efficiently.
The relevant expert is through studying for a long period of time both at home and abroad, recognize the pollution control of black paper-making liquid of alkali pulping, key is the thorough separation of its lignin, many separation methods such as CN 1068867A have been proposed, CN 1060128A, CN1037183A, CN 1037560A, related acid-precipitation method, flocculent precipitation, electroosmose process or the like among the CN 1057079A.
But for various reasons, such as equipment investment is big, the operating cost height, and disposal ability is minimum, or it is still very difficult to handle back lignin separation, and up to the present the straw pulp papermaking enterprise does not have the industrialization facility normal operation input of isolated lignin as yet.
The objective of the invention is at solving above-mentioned drawback, it is few to seek a kind of one-time investment, and operating cost is low, and is easy to operate, and equipment is simple, and key is thoroughly to remove the method for black paper-making liquid of alkali pulping lignin.
The objective of the invention is to be achieved through the following technical solutions.
With the process route of intermittence or continuous operation, directly drop into organic polymer electrolyte A, i.e. nonionic, anionic, anion-nonionic and cationic-type polyacrylamide, Sodium Polyacrylate and substitutive derivative [CH thereof in the alcaliotropism black liquor
2-CHR
1R-] n, alkali metal ion), acid amides [CONH R refers to cyano group (CN), carboxyl (COOH), carboxylate (COOM, M: in the formula
2,-CONHR
1,-CON (R
1)
2], R
1Finger-H ,-CH
3,-C
2H
5-OH etc. and polyethylene imines, carboxymethyl cellulose etc., or the mixture of these materials or its aqueous solution, after stirring and dissolving, add acidic materials B again, comprise sulfuric acid, phosphoric acid, formic acid, acetate, oxalic acid and carbon atom are the monoacid below 4, binary acid or its mixture or its aqueous solution, wherein preferably sulfuric acid and phosphoric acid, regulate black liquor pH value≤5, solid contents such as the lignin in the black liquor are assembled at once, separate out, and the solid content drainability is fabulous, with conventional method such as simple filtration, vacuum filtration, centrifugation, press filtrations etc. all can thoroughly separate solid-liquid at an easy rate mutually, and solid contents such as isolated lignin are as the raw material of industry, make active carbon or organic-inorganic compound fertilizer etc.; The recovery liquid of isolated no suspended substance, direct reuse is in the black wash treatment system; Or merge with middle section water, handle back up to standard through biochemical materialization and discharge.
The weight ratio of black liquor, organic polymer electrolyte A and acidic materials B is advisable in following scope:
Black liquor: organic polymer electrolyte A: acidic materials B=1: 0.00001-0.008: 0.005-0.05.
Major advantage of the present invention is:
1. both administer the pollution of black paper-making liquid of alkali pulping, fully utilized resource again.
2. technology is simple, and equipment, facility are few, and one-time investment is little, and is reliable, and operating cost is low, and lignin separates thoroughly, and drainability is good.
3. isolated lignin can be produced active carbon, organic-inorganic compound fertilizer as the raw material of industry; Reclaiming liquid is back to the black wash treatment system or merges processing with middle section water.The present invention can be widely used in large, medium and small type soda pulping process papermaking enterprise, has significant environment, society, economic benefit.
Below be illustrated with instantiation:
Embodiment one
Under the normal temperature and pressure, with 25Kg 1
#Polyacrylamide evenly adds 10m
3PH=12COD: in 86000mg/L Baume degrees 7.08 black liquor, stirring and dissolving, add aqueous sulfuric acid again, regulate pH=4, lignin is separated out behind the continuation stirring reaction 10min., through vacuum suction filter, after the solid content drying, get the lignin 360Kg of moisture≤10%, the recovery liquid of gained no suspended substance, be back to the black wash treatment system, papermaking is not had obvious influence.
Embodiment two
In reactor, pump into 10m
3The black liquor of pH=12 adds 2
#Polyacrylamide 1Kg, stir treated its dissolving in 20 minutes after, add 500 liters in sulfuric acid again, continue to stir after 5 minutes, with 1m
3The amount of/min. is sent into homemade solid-liquid separating machine continuously and is finished Separation of Solid and Liquid.
Embodiment three
The 2g carboxymethyl cellulose is dissolved in the 1000ml black liquor, adds 27 gram glacial acetic acid again, transfer pH≤5, continue to stir 20 minutes, filter, finish Separation of Solid and Liquid, solid drying gets 35 grams such as the lignin of moisture≤10%.
Embodiment four
In 1000 milliliters of black liquor, add Sodium Polyacrylate 1.5 grams, after the stirring and dissolving,, regulate pH=4.5, continue to stir two minutes with mechanical agitator with 15 gram phosphoric acid, suction filtration, the result is with example three.
Embodiment five
(reactor volume is 20m with the homemade two reactors that connect with pump
3, and the stirring of being furnished with certain rotating speed) as flow reactor.Pump into the alkali paper-making black liquor of pulp making of pH=12 at inlet with the amount of 1000 liters/min., and add 1 with the amount of 1.5 kilograms/min.
#Polyacrylamide is in 1
#Still is pumped into 2 by connection after mixing
#Reactor, simultaneously, 2
#The reactor inlet adds aqueous sulfuric acid with the amount of 52 liters/min., and reactant is through 2
#The reactor outlet flows to homemade continuous solid-liquid separating machine, finishes Separation of Solid and Liquid.Reclaim liquid and return the pulp and paper production use, after the several reuse, merge, handle qualified discharge through biochemical materialization with middle section water; The solid lignin is used to make composite fertilizer.
Claims (6)
1. process for removing lignin from black liquor in making paper by soda pulping is characterized in that:
1.1 under alkali condition, in black paper-making liquid of alkali pulping, directly add organic polymer electrolyte A;
1.2 regulate pH value≤5 of black liquor with acidic materials B;
1.3 separate the solid content lignin of separating out etc. with general separation method, can be used as the raw material of industry, produce composite organic-inorganic fertilizer or active carbon;
1.4 isolated clear liquid direct reuse is in the black wash treatment system, reuse repeatedly back merges the processing qualified discharge with middle section water;
1.5 the weight ratio of black liquor and organic polymer electrolyte A and acidic materials B is: black liquor: A: B=1: 0.00001～0.008: 0.005～0.05.
2. process for removing lignin from black liquor in making paper by soda pulping according to claim 1 is characterized in that described alkali condition, is meant that the black liquor that soda pulping process obtains does not add any processing, directly adds organic polymer electrolyte A.
3. process for removing lignin from black liquor in making paper by soda pulping according to claim 1 is characterized in that described organic polymer electrolyte A is meant nonionic, anionic, anion-nonionic and cationic-type polyacrylamide, Sodium Polyacrylate and substitutive derivative [CH thereof
2CHR
1R-] n, alkali metal ion), acid amides [CONH R refers to cyano group (CN), carboxyl (COOH), carboxylate (COOM, M: in the formula
2,-CONHR
1,-CON (R
1)
2], R
1Finger-H ,-CH
3,-C
2H
5,-OH etc. and polyethylene imines, carboxymethyl cellulose, these materials can use or mix use separately.
4. process for removing lignin from black liquor in making paper by soda pulping according to claim 1 is characterized in that described organic polymer electrolyte A is solid granulates shape, Powdered or its solution.
5. process for removing lignin from black liquor in making paper by soda pulping according to claim 1 is characterized in that described acidic materials B is meant that sulfuric acid, phosphoric acid, formic acid, acetate, oxalic acid and carbon atom are monoacid, binary acid or its mixed acid or its aqueous solution below 4.
6. process for removing lignin from black liquor in making paper by soda pulping according to claim 1 is characterized in that processing procedure is intermittently operated or operation continuously.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116492A CN1085757C (en) | 1999-05-27 | 1999-05-27 | Process for removing lignin from black liquor in making paper by soda pulping |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99116492A CN1085757C (en) | 1999-05-27 | 1999-05-27 | Process for removing lignin from black liquor in making paper by soda pulping |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1249373A CN1249373A (en) | 2000-04-05 |
| CN1085757C true CN1085757C (en) | 2002-05-29 |
Family
ID=5279299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99116492A Expired - Fee Related CN1085757C (en) | 1999-05-27 | 1999-05-27 | Process for removing lignin from black liquor in making paper by soda pulping |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1085757C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI117507B (en) * | 2004-07-09 | 2006-11-15 | Kemira Oyj | Procedure for removing lignin from water |
| 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 |
| CN101736638B (en) * | 2009-11-19 | 2011-09-14 | 张仲伦 | Processing method of paper-making pulping black liquor |
| CN101935955B (en) * | 2010-08-26 | 2013-05-01 | 中国农业大学 | Method for pretreating biomass raw materials |
| CN103061179B (en) * | 2012-12-25 | 2015-06-17 | 济南圣泉集团股份有限公司 | Comprehensive utilization process for lignocellulose biomass |
| FI20135842L (en) | 2013-08-19 | 2015-02-20 | Valmet Technologies Oy | Method and system for treating lignin |
| CN111774534B (en) * | 2020-07-23 | 2021-08-24 | 宝鸡华光铸造材料科技有限公司 | A kind of manufacturing method of paper sprue pipe for metal casting |
| CN112111311A (en) * | 2020-09-30 | 2020-12-22 | 桃江县新辉生物质颗粒有限公司 | Biomass granular fuel and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059644C (en) * | 1996-01-31 | 2000-12-20 | 迁安县华丰造纸厂 | Treatment method of papermaking black liquor |
-
1999
- 1999-05-27 CN CN99116492A patent/CN1085757C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059644C (en) * | 1996-01-31 | 2000-12-20 | 迁安县华丰造纸厂 | Treatment method of papermaking black liquor |
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| Publication number | Publication date |
|---|---|
| CN1249373A (en) | 2000-04-05 |
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