CN1068867A - The improvement method of black liquid - Google Patents

The improvement method of black liquid Download PDF

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Publication number
CN1068867A
CN1068867A CN 91106757 CN91106757A CN1068867A CN 1068867 A CN1068867 A CN 1068867A CN 91106757 CN91106757 CN 91106757 CN 91106757 A CN91106757 A CN 91106757A CN 1068867 A CN1068867 A CN 1068867A
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filtrate
lignin
pulp
black liquid
causticization
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CN 91106757
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CN1041450C (en
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龙邵发
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Abstract

The present invention relates to a kind of improvement method and comprehensive utilization technique of alkali paper-making black liquor.Its technological process comprises lignin separation, main process such as sulfate conversion, solution causticization.It is characterized in that, add a kind of barium compound in the filtrate after lignin separation, sulfate radical is converted into precipitation separates out, in filtrate, add the quantitative sodium carbonate and the lime of amount of calculation 100~200% again and carry out causticization, both reclaim lignin, active alkali, and made the black liquor after the processing can become pulp cooking liquid again again, formed the totally enclosed type circulatory system, do not efflux, free from environmental pollution.

Description

The improvement method of black liquid
The present invention relates to a kind of improvement method of alkali paper-making black liquor.
Paper-making industrial waste water pollutes classifies one of the world's five big public hazards as.China's paper industry total displacement is only second to chemical industry and steel and iron industry, occupies the 3rd, accounts for 1/10 of industrial wastewater total release, accounts for BOD 51/4 of discharge capacity.Alkaline process (comprising soda processes and sulfate process) slurrying accounts for 55.4% of paper pulp total output, accounts for 78.8% of chemical pulp total output, so the improvement of alkaline pulp black liquor is the emphasis that industrial pollution caused by paper manufacturing is administered, the improvement of black liquor then is the emphasis in the emphasis.Because its content of organics height, color is dark, foam is many, alkalescence is strong, environmental pollution is very serious.
The main method that solves the alkaline pulping black liquor pollution at present is that the organic matter in the black liquor is burnt with the elimination organic contamination, and reaches the purpose that reclaims heat energy and alkali.Its complex process, equipment investment is big, and running expense height, organic matter only act as a fuel and are burnt, and only are applicable to the big-and-middle-sized paper plant that produces paper pulp more than 10,000 tons per year.Small paper mill (there are nearly ten thousand families in China) to a large amount of existence can't be suitable for.For solving the improvement of small paper mill black liquor, the relevant expert has carried out long-term extensive studies both at home and abroad, has proposed many improvement methods, as acid-precipitation method, flocculent precipitation, electroosmose process etc.Acid-precipitation method and flocculent precipitation are only removed most of lignin, can not reclaim alkali; Electroosmose process power consumption is big, and dialyser is very easily poisoned.Some other method mostly exists equipment investment big, the disposal cost height, and problem such as can't be born at by enterprise.As No. 87102058, Chinese patent disclosed " comprehensive harnessing method of black liquid in making pulp of paper-making and self-excited type of absorption column of gas with turbulent balls ", its essence also is that separating lignin discharges after diluting, and does not reclaim alkali, the processing cost height.
The object of the present invention is to provide that a kind of technology is simple, easy to operate, small investment, running expense be low, can reclaim lignin, recyclable again active alkali, and the also totally enclosed type black liquid comprehensive processing method of reproducible utilization of waste residue.
The objective of the invention is to realize by the following method.
At first use the acid-precipitation method separating lignin, the lignin in the black liquor exists in the solution with hydrophily sodium salt (RONa), precipitation not, in acid with the time electrophilic substitution then takes place, make lignin become insoluble precipitate and separate out: RONa+H → ROH ↓+Na.Be adjusted to PH≤5.0, lignin becomes fine and close precipitation to separate out and obtains separating its yield 〉=85%.
The compound that adds a kind of barium then in the filtrate of separating lignin as oxide, hydroxide, sulfide or carbonate etc., separates out the sulfate ion precipitation in the filtrate, and sodium ion is converted into NaOH, and vulcanized sodium or sodium carbonate etc. is stored in solution.Precipitation regeneration after suitably handling is used.
The barium compound addition is to determine according to the amount of contained sulfate in the filtrate.
Causticization is according to the required naoh concentration of different paper pulp raw materials, adds quantitative sodium carbonate and dissolving in solution, adds milk of lime by amount of calculation 100~200% then, makes sodium carbonate be converted into caustic soda.For making the alkali lye of cooking of pulp desired concn, also need again in treatment fluid, to add an amount of caustic soda sometimes, like this, black liquor reuse just capable of circulation and not effluxing.
The controlled quentity controlled variable of naoh concentration is a timber slurry 15~28% in the causticization liquid, bamboo wood reed pulp 13~18%, bagasse pulp 11~15%, straw pulp of rice and wheat 8~15%.
Major advantage of the present invention is: technology is simple, and is easy to operate, treatment effeciency height, lignin removing rate 〉=85%, silica clearance 〉=90%, sulfate conversion ratio 〉=95%, causticizing efficiency 〉=95%; Both reclaimed lignin, inorganic salts, caustic soda and waste residue make the black liquor after the processing become pulp cooking liquid again again, form a totally enclosed type circulatory system, do not efflux, free from environmental pollution, equipment is simple, small investment, running expense is low, has tangible environment, economic and social benefit.
Embodiment 1:
Black liquid 200ml adds 1: 1 sulfuric acid 9ml, agitation and filtration, and the precipitation oven dry gets lignin 18.84 grams, and filtrate recording contains sodium oxide molybdena 25g/l, adds oxide 10 grams of barium, precipitate and separate salt.Add sodium carbonate 15 grams to filtrate, lime 13 grams (making milk of lime, down together) enter former cooking procedure after the causticization.
Embodiment 2:
Black liquid 200ml adds 1: 1 sulfuric acid 9ml, the agitation and filtration delignification, and the hydroxide 20 that adds barium restrains, and precipitate and separate adds sodium carbonate 12 grams, and lime 11 grams enter former cooking procedure after the causticization.
Embodiment 3:
Get black liquid 200ml, add 1: 1 sulfuric acid 9ml, agitation and filtration, the carbonate 12 that adds barium in filtrate restrains, and precipitate and separate adds sodium carbonate 18 grams, and lime 15 grams enter former cooking procedure after the causticization.
Embodiment 4:
Black liquid 200ml adds 1: 1 sulfuric acid 9ml, stirs separating lignin, adds the sulfide of barium, precipitate and separate.Add sodium carbonate 15 grams, enter former cooking procedure after the lime 12 gram causticizations.

Claims (3)

1, a kind of improvement method of black liquid, it comprises lignin separation, sulfate transforms, processes such as solution causticization, the invention is characterized in, add a kind of barium compound in the filtrate behind regulator solution PH≤5 lignin by acid separation and sulfate radical is converted into precipitation separates out, in filtrate, add quantitative sodium carbonate again and the milk of lime of amount of calculation 100~200% carries out causticization according to different paper making raw material institute alkali needed, make pulp cooking liquid, form closed circulatory system.
2, administration of papermaking black liquid method according to claim 1, it is characterized in that adding in the filtrate barium compound can be oxide, hydroxide, sulfide, carbonate etc., its addition is to determine according to the amount of contained sulfate radical in the solution.
3, administration of papermaking black liquid method according to claim 1 and 2, it is characterized in that: the amount that adds sodium carbonate in filtrate is determined according to the required concentration of lye of different paper making raw materials, the timber slurry is 15~28%, the bamboo wood reed pulp is 13~18%, bagasse pulp is 11~15%, and straw pulp of rice and wheat is 8~15%.
CN 91106757 1991-07-25 1991-07-25 Method for treating paper-making black liquor Expired - Fee Related CN1041450C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 91106757 CN1041450C (en) 1991-07-25 1991-07-25 Method for treating paper-making black liquor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 91106757 CN1041450C (en) 1991-07-25 1991-07-25 Method for treating paper-making black liquor

Publications (2)

Publication Number Publication Date
CN1068867A true CN1068867A (en) 1993-02-10
CN1041450C CN1041450C (en) 1998-12-30

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CN 91106757 Expired - Fee Related CN1041450C (en) 1991-07-25 1991-07-25 Method for treating paper-making black liquor

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1109659C (en) * 1999-04-29 2003-05-28 中国科学院化工冶金研究所 Method for recovering alkali from paper-making black liquor by using ammonium hydrogen carbonate as solvent
CN100420790C (en) * 2007-10-29 2008-09-24 山东泉林纸业有限责任公司 Alkali process and iminium process straw pulp black liquor hybrid dry matter and preparation method thereof
CN101831827A (en) * 2010-04-30 2010-09-15 中国科学院广州能源研究所 Preparation method of paper making black liquid semi-coke
CN101845766A (en) * 2010-04-30 2010-09-29 中国科学院广州能源研究所 Method and device for gasifying pulping black liquor and reclaiming directly causticized alkali
CN103496821A (en) * 2013-09-18 2014-01-08 广西丽桂环保科技有限公司 Papermaking black liquid treatment and recycling method
CN106865892A (en) * 2017-03-07 2017-06-20 轻工业环境保护研究所 Reducing rules black liquor by wet method alkali reclaiming method
CN108842452A (en) * 2018-07-11 2018-11-20 广东泓睿科技有限公司 A kind of textile-pretreating agent
CN115491917A (en) * 2022-08-29 2022-12-20 黄山市凝霜文化发展有限公司 Processing method of papermulberry paper

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1109659C (en) * 1999-04-29 2003-05-28 中国科学院化工冶金研究所 Method for recovering alkali from paper-making black liquor by using ammonium hydrogen carbonate as solvent
CN100420790C (en) * 2007-10-29 2008-09-24 山东泉林纸业有限责任公司 Alkali process and iminium process straw pulp black liquor hybrid dry matter and preparation method thereof
CN101831827A (en) * 2010-04-30 2010-09-15 中国科学院广州能源研究所 Preparation method of paper making black liquid semi-coke
CN101845766A (en) * 2010-04-30 2010-09-29 中国科学院广州能源研究所 Method and device for gasifying pulping black liquor and reclaiming directly causticized alkali
CN101831827B (en) * 2010-04-30 2012-05-23 中国科学院广州能源研究所 Preparation method of paper making black liquid semi-coke
CN103496821A (en) * 2013-09-18 2014-01-08 广西丽桂环保科技有限公司 Papermaking black liquid treatment and recycling method
CN103496821B (en) * 2013-09-18 2015-12-09 广西丽桂环保科技有限公司 Administration of papermaking black liquid recoverying and utilizing method
CN106865892A (en) * 2017-03-07 2017-06-20 轻工业环境保护研究所 Reducing rules black liquor by wet method alkali reclaiming method
CN108842452A (en) * 2018-07-11 2018-11-20 广东泓睿科技有限公司 A kind of textile-pretreating agent
CN115491917A (en) * 2022-08-29 2022-12-20 黄山市凝霜文化发展有限公司 Processing method of papermulberry paper

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