CN1068867A - The improvement method of black liquid - Google Patents
The improvement method of black liquid Download PDFInfo
- 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
- Authority
- CN
- China
- Prior art keywords
- filtrate
- lignin
- pulp
- black liquid
- causticization
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000007788 liquid Substances 0.000 title claims abstract description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 21
- 229920005610 lignin Polymers 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 9
- 238000010411 cooking Methods 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 6
- 150000001553 barium compounds Chemical class 0.000 claims abstract description 4
- 238000004364 calculation method Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241000744472 Cinna Species 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 241000209140 Triticum Species 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract description 5
- 235000011941 Tilia x europaea Nutrition 0.000 abstract description 5
- 239000004571 lime Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 229910052788 barium Inorganic materials 0.000 description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 238000003916 acid precipitation Methods 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000202567 Fatsia japonica Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009993 causticizing Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Paper (AREA)
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 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%.
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 |
Family
ID=4908137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91106757 Expired - Fee Related CN1041450C (en) | 1991-07-25 | 1991-07-25 | Method for treating paper-making black liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1041450C (en) |
Cited By (8)
| 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 | A kind of mixed dry product of alkali method and ammonium method straw pulp black liquor 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 |
-
1991
- 1991-07-25 CN CN 91106757 patent/CN1041450C/en not_active Expired - Fee Related
Cited By (10)
| 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 | A kind of mixed dry product of alkali method and ammonium method straw pulp black liquor 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 papermaking black liquor 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1041450C (en) | 1998-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI585267B (en) | Chemical pulping method | |
| US4302281A (en) | Method for producing pulp | |
| US3833464A (en) | Method of decolorizing paper mill effluent liquid | |
| CA2150243C (en) | A method of producing green liquor in chemical recovery in sulfate and sulfite pulp mills | |
| CN1068867A (en) | The improvement method of black liquid | |
| US3833462A (en) | Process of removing sodium chloride from kraft pulping process chemical recovery systems | |
| AU754885B2 (en) | Increasing causticizing efficiency of alkaline pulping liquor by borate addition | |
| US5705031A (en) | Process for removing and washing dregs from green liquor in a kraft pulp mill | |
| EP0296198A1 (en) | PROCESS FOR WASHING ALKALINE PASTA. | |
| CA2224765C (en) | Method of producing oxidized white liquor from black liquor | |
| CN100557123C (en) | Less Chlorine Bleaching of Straw Pulp by Alkaline Sodium Sulfite Process and Fully Sealed Middle Water Reuse Technology | |
| CN1381645A (en) | Process and equipment for treating black pulping liquid | |
| CA1064206A (en) | Method of recovering substances in the extraction of spent liquors from the delignification of lignocellulosic material by means of chloride-producing bleaching agents | |
| CN104556183A (en) | Improved technology for preparing lime mud calcium carbonate filler through causticization of straw pulp green liquor | |
| WO1992020856A1 (en) | White liquor preparation and pulping process | |
| CN1247248A (en) | Full-circulation pollution-free pulping and papermaking process by using waste water | |
| CA1244605A (en) | Method for causticizing green liquor in an alkaline pulping process | |
| AU657003B2 (en) | Ozone bleaching of pulp | |
| US11655589B2 (en) | Method and a system for adjusting PH of green liquor dregs | |
| EP0151097A1 (en) | A method for removing resin from a paper pulp process liquor | |
| CN1120026A (en) | Processing of four-time recovery and two-stage treatment of paper pulping waste liquid | |
| Magnusson et al. | Integrating prehydrolysis kraft pulping of softwood and viscose fibre manufacturing | |
| CN1358900A (en) | Method and equipment for treating black liquor of pulp making | |
| CN1156694A (en) | Comprehensive draining treating technique for black liquor and midcourse water from caustic soda process straw pulp paper mill | |
| RU1773270C (en) | Closed water circulation method for production of cellulose and board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |