CN1077179A - Alkaline straw pulp paper black liquid and sewage treatment technology of intermediate section - Google Patents
Alkaline straw pulp paper black liquid and sewage treatment technology of intermediate section Download PDFInfo
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- CN1077179A CN1077179A CN92106464A CN92106464A CN1077179A CN 1077179 A CN1077179 A CN 1077179A CN 92106464 A CN92106464 A CN 92106464A CN 92106464 A CN92106464 A CN 92106464A CN 1077179 A CN1077179 A CN 1077179A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
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Abstract
The present invention is the comprehensive treatment technique of a kind of alkaline straw pulp paper black liquid and stage casing sewage.It comprises the papermaking wastewater process for comprehensively treating that acid out Separation and Recovery xylogen, anaerobic digestion, coagulating treatment and aerobic biological treatment four-stage combine.1. present technique has can produce lignin products and by-product biogas; 2. mix with stage casing sewage again after the black liquor pollution load being reduced significantly and carry out the comprehensive regulation; Characteristics such as intersect to use that 3. chemistry-biological means is handled.This technical process is simpler, and total investment of engineering is few, and working cost is low, and final outflow water water quality can reach the index of the primary standard among the national sewage comprehensive emission standard GB8978-88.
Description
The invention belongs to industrial sewage treatment technology, the integrated conduct method of say so in more detail a kind of alkaline straw pulp paper black liquid and stage casing sewage.
On our times, paper industry is one of industry that investment is big, energy consumption is high, environmental pollution is serious, and its features of pollution is that wastewater discharge is big, contains a large amount of organic classes and mineral-type pollutent color heavy, and contains many toxic pollutant matter.In China's paper industry, because the straw pulp fibrous material is than great, scope of the enterprise is little, production technique and equipment are relatively backward, again because of reason, starting material and energy expenditure height such as enterprise management level is relatively poor, the unit product water consumption is big, causes the pollution of China's pulp and paper industry especially serious.Because abroad, the raw material of pulping and paper-making has and is to use timber more than 95%, and particularly the country of paper industry prosperity seldom uses grass as raw material, thereby, aspect the Processing Technology Research of carrying out straw pulp black liquor and other waste water, make progress slowlyer, report also seldom.Our national conditions are that the ratio with straw fiber raw material papermaking weighs 60～70%.And adopt straw fiber raw material papermaking to have a series of shortcomings, causing is having particular difficulty aspect paper pulp and paper product production and the Pollution abatement.Particularly aspect the improvement that accounts for the cooking waste liquor (black liquor) of paper-making process pollution generation total amount more than 80%, lacking processing recovery and the comprehensive utilization technique that is suitable for, so most papermaking enterprise is directly black liquor to be entered rivers, lake under the situation of unprocessed and recycling.Like this, both water body environment is caused severe contamination, wasted the wherein organism that comprehensive utilization value is arranged and the pharmaceutical chemicals of millions of ton of meter again.
Since the meeting of the whole nations in 1978 light industry for the first time environmental protection work; the industrial pollution caused by paper manufacturing preventing and controlling begin to put on agenda; the pulp and paper waste_water investigative technique is also classified " the Seventh Five-Year Plan " national science and technology research project as, bears the research topic that emphasizes particularly on different fields by relevant R﹠D institution respectively.From present case, this improvement technology, particularly in, the improvement technology of small straw plant waste water is in the exploratory stage, roughly carries out exploratory development aspect following three.
The alkali recovery technology aspect.Alkali recovery technology is one of major technique means of external Processing Paper Wastewater, can reduce effectively and pollute and utilize resources synthetically, some R﹠D institutions of China are abroad on the alkali recovery technology basis, characteristics in conjunction with straw pulp black liquor, doing some research work aspect alkali recovery process and the equipment, obtained encouraging progress, but because the investment of the alkali recycling engineering of black liquid of straw pulp paper-making is too big, and the viscosity of black liquid of straw pulp paper-making is big, the silicon content height, unfavorable factors such as " silicon interference " causes treatment project working cost height, and efficient is also lower.Though indivedual producers carried out demonstration test, but as want to carry out actual applying at medium and small straw pulp and paper mill, also have a lot of difficulties, the particularly difficulty in the investment-to the straw pulp and paper mill of 10,000 tons of year slurrying, the investment of alkali recycling engineering has restricted the generally employing that alkali reclaims up to 1,400 ten thousand yuan.Both made in the huge investment of being expense the large and medium-sized paper mill of minority of chemical recovery system,, and still had thousands of stage casing sewage every day, because of technology with investment problem is unresolved is also entering environment, continued to cause water pollution though handled black liquor pollution.
Aspect biochemical treatment, anaerobic fermentation technology has been successfully used to the wastewater treatment of sludge treatment and alcohol, foodstuffs industry abroad, be applied to also to have obtained some progress aspect the paper waste processing, but still less to the improvement research report that is used for alkaline straw pulp paper sewage.Domestic some R﹠D institution has also carried out anaerobic biochemical and has handled the papermaking wastewater Study on Technology, but still belongs to the starting stage at present.
In addition, aspect other comprehensive utilizations of black liquid, domesticly some discussions have also been carried out respectively.
Still be in exploration and local conceptual phase aspect the Study on treatment technology of alkaline straw-pulp black liquid in view of domestic, do not have a kind of suitable as yet, in particularly being applicable to, small paper mill practical application process for comprehensively treating, therefore carrying out the research of alkaline straw pulp paper black liquid and sewage treatment technology of intermediate section, is to press for one of difficult problem of solution most in China water prevention and cure of pollution field.
The objective of the invention is with the comprehensive utilization is prerequisite, serve as theme with the comprehensive regulation, adopting Separation and Recovery xylogen and biologic treating technique is main means, but the treatment technology of medium and small alkaline straw pulp paper black liquid of a kind of practicable comprehensive regulation and stage casing sewage is provided, and guarantees that it reaches the ultimate aim of sewage recycling.
Comprehensive treatment technique provided by the present invention is combination and the integrated use that acid out-anaerobic digestion-coagulation-aerobe is handled four step treatment technology means.
1), acid out: utilize acidic oxide and sulfuric acid in the stack gas that black wash is carried out the acid out processing, separate and also reclaim xylogen;
2), anaerobic digestion: after the clear liquid behind the separating lignin added the dilution of sewage of a certain amount of stage casing, carry out the anaerobically fermenting digestion process and reclaim biogas;
3), coagulation: add remaining whole stage casings sewage in the sewage after anaerobic digestion, and the adding flocculation agent carries out the chemical coagulation processing.
4), aerobe is carried out in the coagulation water outlet behind coagulating treatment and elimination mud handle, and qualified discharge.
The technical process of above-mentioned comprehensive treatment technique sees accompanying drawing 1 for details.
The concrete processing condition of comprehensive treatment technique of the present invention are as follows:
1) acid out and Separation and Recovery xylogen:
Alkaline straw pulp paper black liquid generally contains xylogen 20～40 grams per liters, BOD
525000～30000mg/L, COD80000～110000mg/L, PH are 11～13.Beginning feeds the stack gas after wet dust removal earlier in this black liquor, make the PH of black liquor be reduced to 8～10, then to the H that wherein adds 5～10%
2SO
4Solution (hydrochloric acid soln also can) is also tested the PH of black liquor at any time, reach at 3.5～4.0 o'clock up to pH value, stop to add acid, this moment, the solid-liquid separating equipment separating lignin is separated out and adopted to xylogen, the temperature of acid out and settlement separate xylogen is 20～70 ℃, time is 1～5 hour, and after acid out was handled, lignin removing rate can reach 90%.The xylogen of institute's Separation and Recovery can sell or carry out deep processing and becomes other product application.
2) anaerobic digestion
Clear liquid PH behind the acid out separating lignin is about 4, for making its suitable next step digestion process of carrying out, should under normal temperature and pressure conditions, neutralize with milk of lime, PH is reached about 7.0, for improving wastewater treatment rate, should add the stage casing sewage of 3～5 times of amounts, mix, send into anaerobic digestion device then.For making full use of equipment and improving digestive efficiency, anaerobic digestion process is divided into two sections to carry out, leading portion mainly is the anaerobic acidification stage, back segment is mainly the anaerobically fermenting stage, in anaerobic acidification reactor and anaerobic fermentation reactor, carry out respectively, the former is the upflowing multiple-hearth, and the latter is the mixed structure device of upflow sludge blanket and anaerobic filter.Anaerobic digestion temperature is generally 35～40 ℃, and the time is 5～9 days, and the biogas that is produced is recycled after the desulfurization through gas-liquid separation.After two phase anaerobic digestion, COD and BOD
5Clearance all be significantly improved, the COD clearance reaches 60%, BOD
5Clearance reaches 80%, generally speaking, and the BOD of anaerobic digestion solution
5Be 800～1000mg/L, COD is 4000～6000mg/L.Factor of created gase is more than the 300L/mgCOD.
3) coagulation
Above-mentioned anaerobic digestion solution is mixed (generally remaining whole stage casings sewage can being mixed), BOD in the mixed solution with 20～30 times stage casing sewage
5Be 210～300mg/L, COD is 700～1000mg/L, adds inorganic polymer flocculant in the ratio of 0.5～1.0g/L in combined sewage, as add polymerize aluminum chloride etc., and make that pollutent carries out coagulating sedimentation in the sewage, sewage is further purified, general COD clearance is 30～50%, BOD
5Clearance be 15～30%,
4) aerobe is handled
With the coagulation water outlet behind coagulating treatment and the elimination mud, sending into two sections biology aerobic treatment unit handles, leading portion is the biological acidification section, under the anoxybiotic condition, carry out biological acidification, the treatment stage that back segment being catalytic oxidation, the effective volume ratio of acidizing device and aerobic device is 1: (2～3), the operating procedure condition is: PH7～8,25～30 ℃ of water temperatures, the gas-water ratio of aerobic treatment is (10～20): 1, and 10～20 hours residence time, final outflow water water quality can reach the index of highest level standard among the national sewage comprehensive emission standard GB8978-88 after aerobic biochemical is handled, be COD≤100mg/L, BOD
5≤ 30mg/L, SS≤70mg/L, in this standard to the COD≤450mg/L of paper industry defined, BOD
5≤ 200mg/L, the sewage drainage standard of SS≤250mg/L.
This technology has following characteristics and advantage:
1, separation and recycling xylogen.Because xylogen under general condition is difficult to the purification that is degraded by microorganisms, and this technology at first adopts acid-precipitation method to remove the xylogen in the black liquor.Can reclaim xylogen so on the one hand, it is sold as product, obtain considerable economic.On the other hand, make the organic pollution load of black liquor reduce 60% after the lignin separation, xylogen itself also has been removed more than 90%, has cleared away the obstacle when time step, employing was carried out a biological disposal upon basically, can significantly reduce the time of biological treatment, improve the purification rate of biological treatment.
2, after black liquor pollution load is reduced significantly, mixing with stage casing sewage again, the mode of combined sewage being carried out the comprehensive regulation during than individual curing black liquor or stage casing sewage processing step lack reduced investment.The black liquor pollution load accounts for more than 80% of the total organic pollution load of papermaking wastewater greatly, and (slurry per ton is approximately arranged 10M but its ton slurry quantity discharged is little
3Black liquor), though and sewage pollution load in stage casing is lower, big (the about row of the slurry per ton 200～300M of quantity discharged
3Stage casing sewage), as independent improvement, also need great amount of investment, this technology is adopting acid out and anaerobic digestion to greatly reduce under the condition of black liquor pollution load level, mix mutually with stage casing sewage again, the pollution load level is obviously improved, combined sewage is carried out the comprehensive regulation, can shorten the improvement technical process, reduce abatement equipment and investment and administer working cost.
3, intersect to use the chemical-biological means that black liquor and black liquor and stage casing sewage mixed solution are handled, can make BOD
5The ratio of/COD is in the condition suitable to biochemical treatment all the time, thereby helps improving the biological treatment clearance.
4, anaerobic digestion operation is divided into acidifying and two stages of fermenting implement, the one, can give full play to the functional characteristics of " acidifying section ", make the organic macromolecule of difficult degradation be degraded to small molecules, the 2nd, improved the total clearance that digests operation, the 3rd, reasonable use equipment, also can obtain biogas simultaneously, serve multiple, both purified pollution, the economic benefit of getting back.
5, acidifying of aerobe treatment process decomposing biological and catalytic oxidation two stages of handling implement, has the advantage that improves plant efficiency and performance functions of the equipments characteristics equally, how much power Duan Buxu consumes because of acidifying, thereby can reduce the energy expenditure that aerobe is handled.
6, this process for comprehensively treating difficulty is little, and technical process is simple, and total investment of engineering is few, and working cost is low, helps applying in middle or small paper mill.
7, this process for comprehensively treating final outflow water reaches the standard of one-level new extension enterprise in the national sewage comprehensive emission standard.Can realize the ultimate aim of sewage recycling.
Embodiment: 1, the black liquor and the stage casing waste water treatment project in 10,000 tons of alkaline wheat straw pulp paper mills produced in the somewhere, Shandong per year
1) gross investment: 7,000,000 yuan
2) day output: black liquor 420M
3
Stage casing sewage 10000M
3
3) treatment process
Adopt aforementioned four to go on foot the comprehensive management of technology that combines, its concrete processing condition are: 70 ℃ of acid out temperature, 2 hours time, 40 ℃ of anaerobic digestion temperature, 5 days time, coagulation operation stage casing sewage add-on is 23 times, polymerize aluminum chloride add-on 0.5g/L, the volume ratio of stage apparatus is 1: 2 before and after the aerobe treatment process, gas-water ratio 20: 1,10 hours residence time.
4) drainage index: COD≤100mg/L, BOD
5≤ 30mg/LSS≤70mg/L.
5) economic benefit
1. year recovery xylogen is 2160 tons, rolls over 864000 yuan.
2. year recovery biogas 614400M rolls over 30720 yuan.
Two amount to about 900,000 yuan, and have exempted from the effluent charge that exceed standard.
6) environmental benefit
1. young row COD10000 ton.
2. young row BOD
52840 tons.
3. 2160 tons in young row's xylogen.
The black liquor and the stage casing waste water treatment project of 7000 tons of alkaline straw pulp paper factories produced in embodiment 2, somewhere per year
1) gross investment is 5,000,000 yuan
2) day output: black liquor 276M
3
Stage casing sewage 7750M
3
3) treatment process
Adopt aforementioned four to go on foot the comprehensive management of technology that combines, its concrete processing condition are: 25 ℃ of acid outs, 5 hours time, 35 ℃ of anaerobic digestion temperature, 9 days time, coagulation operation stage casing sewage add-on is 22 times, polymerize aluminum chloride add-on 1g/L, aerobic treatment operation leading portion stage apparatus volume ratio is 1: 3, gas-water ratio 10: 1,20 hours residence time.
4) drainage index:
COD≤100mg/L，BOD≤30mg/L，SS≤70mg/L
5) economic benefit
1. year recovery xylogen is 1500 tons, rolls over 600000 yuan.
2. year recovery biogas 430000M rolls over 21500 yuan.
Two amount to about 620,000 yuan, and have exempted from the effluent charge that exceed standard.
6) environmental benefit
1. young row COD7000 ton.
2. young row BOD
52000 tons.
3. 1500 tons in young row's xylogen.
Claims (10)
1, a kind of is main means and alkaline straw pulp paper black liquid that combines with chemical treatment method and sewage treatment technology of intermediate section with biologic treating technique, it is characterized in that the combination and the comprehensive regulation of following each treatment process:
1.1 acid out separates and the recovery xylogen;
1.2 acid out is separated clear liquid to carry out Anaerobic Digestion and reclaims biogas;
Carry out the chemical coagulation processing 1.3 in anaerobic digestion solution, add stage casing sewage and flocculation agent;
1.4 aerobe is carried out in the coagulation water outlet to be handled.
2, sewage disposal technology according to claim 1 is characterized in that said 12 Anaerobic Digestion operations are divided into anaerobic acidification stage and anaerobically fermenting stage and carry out respectively in two reactors.
3, sewage disposal technology according to claim 1 is characterized in that said 14 aerobe treatment process are divided into biological acidification and two stages of catalytic oxidation, and carries out in two devices respectively.
4, sewage disposal technology according to claim 1 is characterized in that the concrete processing condition of said 11 acid out operations are as follows:
20～70 ℃ of 1～5 hour times of temperature
Sulfuric acid concentration 5～10% acid out PH3.5～4.0
5, sewage disposal technology according to claim 1 is characterized in that the concrete processing condition of said 12 anaerobic digestion operations are as follows:
35～40 ℃ of 5～9 days times of temperature
6, sewage disposal technology according to claim 1 is characterized in that the concrete processing condition of said 13 coagulation operations are as follows:
Anaerobic digestion solution and stage casing sewage blending ratio are 1: (20～30), inorganic polymer flocculant add-on are every liter of combined sewage 0.5～1 gram.
7, as sewage disposal technology as described in claim 1 and 6, it is characterized in that said inorganic polymer flocculant is a polymerize aluminum chloride.
8, sewage disposal technology according to claim 1 is characterized in that the concrete processing condition of said 14 aerobe treatment process are as follows:
PH7～8, water temperature 25～30,10～20 hours residence time, the gas-water ratio of aerobic treatment is (10～20): 1
9, as claim 1 and 2 described sewage disposal technologies, it is characterized in that said used reactor of anaerobic acidification stage is the upflowing multiple-hearth, used reactor of anaerobically fermenting stage is the mixed structure device of upflow sludge blanket and anaerobic filter.
10,, it is characterized in that the volume ratio of said living biological acidification device and catalytic oxidation device is 1: (2～3) as claim 1 and 3 described sewage disposal technologies.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92106464A CN1077179A (en) | 1992-04-11 | 1992-04-11 | Alkaline straw pulp paper black liquid and sewage treatment technology of intermediate section |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92106464A CN1077179A (en) | 1992-04-11 | 1992-04-11 | Alkaline straw pulp paper black liquid and sewage treatment technology of intermediate section |
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| Publication Number | Publication Date |
|---|---|
| CN1077179A true CN1077179A (en) | 1993-10-13 |
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ID=4942135
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92106464A Pending CN1077179A (en) | 1992-04-11 | 1992-04-11 | Alkaline straw pulp paper black liquid and sewage treatment technology of intermediate section |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305783C (en) * | 2004-02-27 | 2007-03-21 | 华中科技大学 | Biological treatment method for paper making black liquor |
| CN104478165A (en) * | 2014-12-10 | 2015-04-01 | 中国宣纸股份有限公司 | Treatment method for secondary black liquor |
| CN104478164A (en) * | 2014-12-10 | 2015-04-01 | 中国宣纸股份有限公司 | Treatment system for secondary black liquor |
| CN104944708A (en) * | 2015-06-26 | 2015-09-30 | 浙江凯恩特种材料股份有限公司 | Papermaking pulping black liquor treatment system |
| CN105016571A (en) * | 2015-06-26 | 2015-11-04 | 浙江凯恩特种材料股份有限公司 | Processing method of paper-pulping black liquor |
| CN109095729A (en) * | 2018-09-30 | 2018-12-28 | 广西大学 | The alkaline defibrination wastewater treatment and circulation utilization method of reverse osmosis membrane apparatus are installed |
| CN109111055A (en) * | 2018-09-30 | 2019-01-01 | 广西大学 | A kind of processing method of chemi-mechanical pulp preparation process wastewater zero discharge |
| CN109205940A (en) * | 2018-09-30 | 2019-01-15 | 广西大学 | A kind of processing of alkalinity defibrination waste water and circulation utilization method |
| CN110092547A (en) * | 2019-05-28 | 2019-08-06 | 宁波三素生物技术研究合伙企业(有限合伙) | Bamboo pulping sewage water treatment method |
-
1992
- 1992-04-11 CN CN92106464A patent/CN1077179A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1305783C (en) * | 2004-02-27 | 2007-03-21 | 华中科技大学 | Biological treatment method for paper making black liquor |
| CN104478165A (en) * | 2014-12-10 | 2015-04-01 | 中国宣纸股份有限公司 | Treatment method for secondary black liquor |
| CN104478164A (en) * | 2014-12-10 | 2015-04-01 | 中国宣纸股份有限公司 | Treatment system for secondary black liquor |
| CN104478164B (en) * | 2014-12-10 | 2017-01-18 | 中国宣纸股份有限公司 | Treatment system for secondary black liquor |
| CN104944708A (en) * | 2015-06-26 | 2015-09-30 | 浙江凯恩特种材料股份有限公司 | Papermaking pulping black liquor treatment system |
| CN105016571A (en) * | 2015-06-26 | 2015-11-04 | 浙江凯恩特种材料股份有限公司 | Processing method of paper-pulping black liquor |
| CN104944708B (en) * | 2015-06-26 | 2017-03-08 | 浙江凯恩特种材料股份有限公司 | A kind of paper-making pulping black liquor processing system |
| CN109095729A (en) * | 2018-09-30 | 2018-12-28 | 广西大学 | The alkaline defibrination wastewater treatment and circulation utilization method of reverse osmosis membrane apparatus are installed |
| CN109111055A (en) * | 2018-09-30 | 2019-01-01 | 广西大学 | A kind of processing method of chemi-mechanical pulp preparation process wastewater zero discharge |
| CN109205940A (en) * | 2018-09-30 | 2019-01-15 | 广西大学 | A kind of processing of alkalinity defibrination waste water and circulation utilization method |
| CN110092547A (en) * | 2019-05-28 | 2019-08-06 | 宁波三素生物技术研究合伙企业(有限合伙) | Bamboo pulping sewage water treatment method |
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