CN109251322A - Utilize the method for sulfate pulping black liquor production sodium lignin sulfonate - Google Patents
Utilize the method for sulfate pulping black liquor production sodium lignin sulfonate Download PDFInfo
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- CN109251322A CN109251322A CN201811365371.4A CN201811365371A CN109251322A CN 109251322 A CN109251322 A CN 109251322A CN 201811365371 A CN201811365371 A CN 201811365371A CN 109251322 A CN109251322 A CN 109251322A
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- black liquor
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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Abstract
The invention discloses a kind of methods using sulfate pulping black liquor production sodium lignin sulfonate, belong to pulping and paper-making, environmental protection and comprehensive utilization of resources field.This technique, through techniques such as filtering, evaporation and concentration, sulfonation modifying, spray drying, produces sodium lignin sulfonate using sulfate pulping black liquor as primary raw material.Black liquor is turned waste into wealth, resource makes full use of, and produces the fine chemical product of high added value, reduces the wasting of resources.This method sodium lignin sulfonate product produced is used for cement water reducing agent, and performance indexes reaches the requirement of concrete high efficiency water reducing agent standard type.
Description
Technical field
The invention belongs to pulping and paper-making, environmental protection and comprehensive utilization of resources fields.It is black to be related to sulfate pulping papermaking
The comprehensive utilization of resources of liquid, and in particular to a method of sodium lignin sulfonate is produced using sulfate pulping black liquor.
Background technique
Sulfate pulping is a kind of current pulping process with the most use, and steaming preparation used is NaOH and Na2S,
Contain a small amount of Na2SO4, digestion system pH value 13-14, medical fluid active constituent is OH-And HS-.Sulfate pulping is that Germany exists
It invents within 1884, the U.S. realizes the industrialization that alkali collection is carried out to its cooking waste liquor in 1928-1934 first, so that sulfuric acid
Salt method slurrying develops rapidly.Over more than 100 years, sulfate pulping process reform is little, but its operating unit, equipment, from
The technologies such as control, alkali collection have significant progress.Its paper output accounts for about the 70% of paper pulp total output, occupies the master of pulp manufacture
Want status.The technique has the advantages that the adaptable of fibrous raw material, can be applicable in all paper pulp fiber raw materials；Paper is strong
It spends, is less than various paper pulp；Energy consumption is few, and the sulfate pulp-making factory of very well equipped can reach power self-support；Alkali collection
The pollution problem of technical perfection, black liquor has been basically solved.
Sulfate pulping enterprise is equipped with greatly mature black liquor alkali recovery process, and the entire flow of alkali recovery technology is divided into
The extraction of black liquor, evaporation, burning, causticization.Basic principle is will to burn in combustion furnace after Black Liquor Concentration, by Organic Sodium Salt
It is converted into inorganic sodium, lime is then added by its causticization, to achieve the purpose that recycle alkali and thermal energy.Alkali recovery process consumption is big
The lime of amount, and a large amount of white clay is generated, the disposition of white clay and the pollution problem of green liquor become the weight under current Environmental Protection Situation
Big project.But alkali collection burns Liginon Resource valuable in black liquor as fuel low value, causes the tight of Liginon Resource
It wastes again.And calorific value caused by black-liquor combustion is well below calorific value needed for being concentrated by evaporation.How will be wooden in black liquor
Element extracts, and modified processing, produces the lignin series chemical product of high added value, solves environmental issue and new for enterprise
Increase point of economic increase, becomes the hot subject of current techniques research and development.
Summary of the invention
It is an object of that present invention to provide a kind of methods using sulfate pulping black liquor production sodium lignin sulfonate, by sulphur
Hydrochlorate method black liquor of pulp making is used as a kind of resource of preciousness, reduces the wasting of resources, avoids environmental pollution, increases enterprise and produces
Value and profit.
To achieve the above object, technical solution of the present invention is realized especially by following steps:
(1), it is firstly added polyacrylamide flocculant, centrifuge separation removal is insoluble using the water in sulfate pulping black liquor
Object；(2), then 75-90 DEG C at a temperature of, by black liquor of pulp making filtering and concentrating to solid content be 20-30% with ceramic super-filtering film.
Wherein: filter liquor be mainly containing sodium hydroxide, vulcanized sodium, sodium sulphate pulp liquor, be back to pulping by cooking；Concentrated black liquor master
Will for containing lignin, hemicellulose, sodium hydroxide, vulcanized sodium, sodium sulphate aqueous solution；(3), over cure is added in concentrated black liquor
Sour sodium is evaporated into multi-effect evaporator, after 1-2 effect evaporation, is added sodium sulfite or sodium hydrogensulfite, is continued to be concentrated by evaporation simultaneously
Synchronous sulfonation modifying, being concentrated by evaporation to solid content is 50-60%；(4), spray drying obtains sodium lignin sulfonate product.
Wherein: the centrifuge separation of water-insoluble is using method described in CN 102561085A in step (1) black liquor of pulp making.
The ceramic super-filtering film pore size filter is 10-20nm, penetrates the sodium hydroxide in black liquor, vulcanized sodium, sodium sulphate
Film filter layer recycles and is back to kraft cooking slurrying；The macromolecular substances envelope filter layer such as lignin, hemicellulose is cut
It stays, for producing sodium lignin sulfonate after filtering and concentrating.
Black liquor after ceramic membrane filter concentration synchronizes in further be concentrated by evaporation and carries out sulfonation to the lignin in black liquor
It is modified.The progress synchronous with the evaporation and concentration of black liquor of the sulfonation modifying of lignin is simplified the production of sodium lignin sulfonate by this method
Step and energy saving.Wherein, in every 1000kg concentrated black liquor, sodium peroxydisulfate additional amount is 15-40kg, sodium sulfite or sulfurous
The additional amount of sour hydrogen sodium is 40-100kg.
The invention is characterized in that: sodium lignin sulfonate is produced using sulfate pulping black liquor.In kraft cooking
OH when slurrying, in cooking liquor-And HS-Lignin in pulping raw material is acted on, plays the role of removing lignin, meanwhile,
S2-、HS-Necleophilic reaction occurs with lignin, the positive center of attack lignin methylene quinone intermediate makes wooden in black liquor
Element vulcanization, plays excitation and activation to the sulfonation modifying of lignin of the present invention.Before sulfonation modifying, to black liquor of pulp making
The water-insolubles such as removal silt, fiber are centrifuged, improve the quality of lignin.Using two-stage concentration method to slurrying
Black liquor is concentrated.Primary concentration use ceramic membrane ultrafitration technique, black liquor of pulp making 75-90 DEG C at a temperature of viscosity relatively
It is low, using heat-resist ceramic membrane, there is biggish membrane flux in the range of pore size filter is 10-20nm, is conducive to UF membrane
Progress, the method be organic film and other filtering and separating technology institute it is inaccessiable.Filter liquor predominantly contain sodium hydroxide,
The pulp liquor of vulcanized sodium, sodium sulphate, is back to pulping by cooking, recycles, save the cost.Ceramic super-filtering film filtering simultaneously is dense
The energy consumption of contracting saves the concentration expense of black liquor of pulp making far below being concentrated by evaporation；Secondary concentration uses multiple-effect evaporation concentration technology, steams
Stripping temperature is further concentrated up to 130 DEG C, to black liquor of pulp making, while providing item to the sulfonation modifying of this method lignin
Part.And S when due to kraft cooking slurrying2-、HS-Necleophilic reaction occurs with lignin, the sulfonation modifying of lignin is played
Excitation and activation, the addition of sodium peroxydisulfate in this method, in 1-2 effect evaporator with the S in black liquor and lignin2-、HS-
Reaction, is easier to carry out the sulfonation modifying of lignin, effectively increases the sulphonation rate of subsequent lignin, make the sulfonation of lignin
Rate improves 20% or more, and optimizes the sulfonating reaction parameter of lignin, saves sulfonation cost.Black liquor adds after 1-2 effect evaporation
Enter sodium sulfite or sodium hydrogensulfite, continues to be evaporated black liquor concentration and synchronous sulfonation modifying, wherein Sulphonation of Lignin is anti-
90% or more should can be completed within 1h.After evaporation and concentration, the sulphonation rate of lignin reaches 99% or more.(4) present invention simplifies
Sulfate pulping black liquor produces the production stage of high-quality sodium lignin sulfonate, and energy saving 50% improves the sulfonation of lignin
Rate 20%.When this method sodium lignin sulfonate product produced is used for cement water reducing agent, performance indexes reaches coagulation
Native high efficiency water reducing agent standard type requirement.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
It is as follows for embodiment for the present invention is better described:
Embodiment 1:
The sulfate pulping black liquor that solid content is 10%:The sun of mass fraction 0.1% is added in every 1000kg black liquor of pulp making
Cationic polyacrylamide aqueous solution 20kg, hybrid reaction, centrifuge separation removal water-insoluble；75 DEG C at a temperature of, it is used
It is 20% that the ceramic super-filtering film that filter opening diameter is 10nm, which is filtered black liquor of pulp making and is concentrated into solid content, and filter liquor is back to boiling
Slurrying；(3), it is added sodium peroxydisulfate in concentrated black liquor, in every 1000kg concentrated black liquor, sodium peroxydisulfate additional amount is 15kg, into
Multi-effect evaporator is concentrated by evaporation, reacts.Sodium sulfite 40kg is added after 1-2 effect evaporator evaporation, is concentrated by evaporation and synchronizes sulphur
Change and is modified.Being concentrated by evaporation again through 3-4 effect evaporator to black liquor solid content is 50%；(4), spray drying obtains sodium lignin sulfonate
Product, sulfomethylated lignin rate are 99.5%.
Embodiment 2:
The sulfate pulping black liquor that solid content is 15%:The yin of mass fraction 0.2% is added in every 1000kg black liquor of pulp making
Cationic polyacrylamide aqueous solution 30kg, hybrid reaction, centrifuge separation removal water-insoluble；85 DEG C at a temperature of, it is used
It is 30% that the ceramic super-filtering film that filter opening diameter is 10nm, which is filtered black liquor of pulp making and is concentrated into solid content, and filter liquor is back to boiling
Slurrying；(3), it is added sodium peroxydisulfate in concentrated black liquor, in every 1000kg concentrated black liquor, sodium peroxydisulfate additional amount is 30kg, into
Multi-effect evaporator is concentrated by evaporation, reacts.Sodium hydrogensulfite 65kg is added after 1-2 effect evaporator evaporation, is concentrated by evaporation and synchronous
Sulfonation modifying, then being concentrated by evaporation through 3-4 effect evaporator to black liquor solid content is 55%；(4), spray drying obtains lignin sulfonic acid
Sodium product, sulfomethylated lignin rate are 99.7%.
Embodiment 3:
The sulfate pulping black liquor that solid content is 20%:The sun of mass fraction 0.2% is added in every 1000kg black liquor of pulp making
Cationic polyacrylamide aqueous solution 40kg, hybrid reaction, centrifuge separation removal water-insoluble；90 DEG C at a temperature of, it is used
It is 40% that the ceramic super-filtering film that filter opening diameter is 20nm, which is filtered black liquor of pulp making and is concentrated into solid content, and filter liquor is back to boiling
Slurrying；(3), it is added sodium peroxydisulfate in concentrated black liquor, in every 1000kg concentrated black liquor, sodium peroxydisulfate additional amount is 40k.Into more
Evaporator is imitated to be concentrated by evaporation, react.Sodium sulfite 95kg is added after 1-2 effect evaporator evaporation, is concentrated by evaporation and synchronizes sulfonation
It is modified, then being concentrated by evaporation through 3-4 effect evaporator to black liquor solid content is 60%.(4), spray drying obtains sodium lignin sulfonate production
Product, sulfomethylated lignin rate are 99.8%.
Application examples:
Sodium lignin sulfonate product produced by the present invention is used for cement water reducing agent, and performance indexes reaches concrete high-efficiency
The requirement of water-reducing agent standard type, is shown in Table 1.
Table 1: concrete high efficiency water reducing agent standard type performance indexes and product of the present invention are examined for cement water reducing agent
Test result
Claims (3)
1. utilizing the method for sulfate pulping black liquor production sodium lignin sulfonate, it is characterised in that: realized by following steps:
(1), polyacrylamide flocculant, the water-insoluble in centrifuge separation removal sulfate pulping black liquor are firstly added；
(2), then 75-90 DEG C at a temperature of, by black liquor of pulp making filtering and concentrating to solid content be 20-30% with ceramic super-filtering film, filter out
Liquid is back to pulping by cooking；(3), sodium peroxydisulfate is added in concentrated black liquor, is evaporated into multi-effect evaporator, after 1-2 effect evaporation,
Sodium sulfite or sodium hydrogensulfite are added, continues to be concentrated by evaporation and synchronous sulfonation modifying, evaporation and concentration to solid content is 50-
60%；(4), spray drying obtains sodium lignin sulfonate product；
The ceramic super-filtering film pore size filter is 10-20nm.
2. the method according to claim 1 using sulfate pulping black liquor production sodium lignin sulfonate, feature exist
In: the water-insoluble in black liquor of pulp making is centrifuged using the method for CN 102561085A.
3. the method according to claim 1 using sulfate pulping black liquor production sodium lignin sulfonate, feature exist
In: in every 1000kg concentrated black liquor, sodium peroxydisulfate additional amount is 15-40kg, and the additional amount of sodium sulfite or sodium hydrogensulfite is
40-100kg。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811365371.4A CN109251322A (en) | 2018-11-16 | 2018-11-16 | Utilize the method for sulfate pulping black liquor production sodium lignin sulfonate |
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| CN201811365371.4A CN109251322A (en) | 2018-11-16 | 2018-11-16 | Utilize the method for sulfate pulping black liquor production sodium lignin sulfonate |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759856A (en) * | 2009-10-21 | 2010-06-30 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing sodium lignin sulfonate water reducer |
| CN102561085A (en) * | 2012-01-19 | 2012-07-11 | 河南省科学院化学研究所有限公司 | Technology for removing water insoluble matter in pulping black liquor |
| CN103145998A (en) * | 2013-03-15 | 2013-06-12 | 浙江捷发科技有限公司 | Method for preparing lignin by utilizing papermaking black liquid |
| CN105601943A (en) * | 2015-11-13 | 2016-05-25 | 浙江捷发科技有限公司 | Method used for preparing sulfonated lignin from sulfate papermaking waste water |
-
2018
- 2018-11-16 CN CN201811365371.4A patent/CN109251322A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759856A (en) * | 2009-10-21 | 2010-06-30 | 安徽丰原发酵技术工程研究有限公司 | Method for preparing sodium lignin sulfonate water reducer |
| CN102561085A (en) * | 2012-01-19 | 2012-07-11 | 河南省科学院化学研究所有限公司 | Technology for removing water insoluble matter in pulping black liquor |
| CN103145998A (en) * | 2013-03-15 | 2013-06-12 | 浙江捷发科技有限公司 | Method for preparing lignin by utilizing papermaking black liquid |
| CN105601943A (en) * | 2015-11-13 | 2016-05-25 | 浙江捷发科技有限公司 | Method used for preparing sulfonated lignin from sulfate papermaking waste water |
Non-Patent Citations (1)
| Title |
|---|
| 谷萸英编著: "《制浆造纸废水处理技术》", 31 December 1995, 云南科学技术出版社 * |
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