CN102720086B - Paper making black liquor recycling zero discharge process adopting rotary membrane treatment - Google Patents
Paper making black liquor recycling zero discharge process adopting rotary membrane treatment Download PDFInfo
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- CN102720086B CN102720086B CN 201210237304 CN201210237304A CN102720086B CN 102720086 B CN102720086 B CN 102720086B CN 201210237304 CN201210237304 CN 201210237304 CN 201210237304 A CN201210237304 A CN 201210237304A CN 102720086 B CN102720086 B CN 102720086B
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Abstract
The invention relates to the technical field of straw pulp raw material production paper making waste water, and particularly discloses a paper making black liquor recycling zero discharge process adopting rotary membrane treatment, which includes the following steps: lignin calcium precipitating, thickening, Fenton strong oxidative system treatment, discharging according to standards and concentrate recycling. After the treatment through the paper making black liquor recycling zero discharge process, the paper making black liquor waste water COD is smaller than 60mg/L, the waste water colority removal rate is equal to and greater than 99%, and the water quality colority index is lower than 10 times. The paper making black liquor recycling zero discharge process has low treatment cost, high treating efficiency and low investment, is stable to operate, can be used in an industrialized way, and facilitates popularization and application.
Description
Technical field
The present invention relates to the straw pulp raw material and produce the paper waste processing technology field, particularly relate to a kind of black liquid of straw pulp paper-making waste water reclaiming processing method.
Background technology
According to statistics, China's papermaking above county level and paper products industry wastewater discharge account for 18.6% of national industrial total release, and COD accounts for 44.0% of national industrial COD total release in the waste discharge.In recent years, through unremitting effort in many ways, though the paper industry water prevention and cure of pollution have obtained certain achievement, the paper industry waste water that accounts for total emission volumn 50% processing up to standard of still being unrealized at present, it is also quite heavy that contaminated wastewater is prevented and treated task.Three strands of waste water are discharged by operation in the paper mill: the one, and pulping cooking waste liquor, i.e. black liquid; The 2nd, separate the washing of paper pulp behind the black liquor, choosing, drift ice, also claim middle section water; The 3rd, the plain boiled water on the paper machine, plain boiled water can be handled the back reuse.In fact middle section water is the incomplete remaining part of black liquid extraction, generally account for total amount 10% in, and contained pollutant accounts for more than 90% of full factory disposal of pollutants total amount in the black liquor, therefore, black liquid is the major part that pollute in the paper mill." polluting namely is the resource that is misplaced ", all contain materials such as cellulose, lignin and hemicellulose in the raw materials such as the stalk of paper grade (stock), cellulose (accounting for 40%) is wherein only taken in papermaking, wherein accounts for 25% lignin and to account for 28% hemicellulose and wood sugar, nitrogen, phosphorus, potassium etc. then discarded with black liquor.Be example with traditional sulfate pulp production, general every production 1t sulfate pulp just has 1t organic matter and 400 kg bases, sulfide to be dissolved in the black liquor, this also is the main component that constitutes paper-making pollution, a large amount of COD are discharged in the water body most of dissolved oxygen in the consume water, cause water quality to worsen because of the dissolved oxygen concentration wretched insufficiency.Processing to black liquid is the key of paper-making industry wastewater treatment.
At present, Chang Yong black liquid treatment technology has Silvola recovery, flocculent precipitation, membrane separation process, acid-precipitation method, aerobic activated sludge process and biotechnology method etc.Wherein Silvola recovery be that present technology is the most ripe, most widely used treating paper-making black liquor in the industry.But Silvola recovery is because investment is big, and general middle or small paper mill is difficult to bear, and it is many to add this measure operation, and operation, complicated operation are difficult to reach environmental emission standard again, and practice result shows and is difficult to apply.
The document that the paper-mill black liquor and development as resource of publishing both at home and abroad that can use is aborning handled is a lot.The for example purifying black liquor in paper making of mentioning among the Chinese patent CN96115935.9 and the method for recycling, this method technology requires high, and operation is many, operation, complicated operation.
Therefore, how effectively black liquid being carried out recycling treatment, make papermaking black liquor wastewater reach emission request, is the technical problem that presses for solution.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can realize the quick separating treatment of black liquid lignin solid-liquid, and the method for will utility wherein carrying out the resource recycling.
The scheme of technical solution problem of the present invention is:
The paper-mill black liquor and development as resource technique of zero discharge that the present invention adopts rotary-type film to handle comprises following processing step:
(1) adding concentration in the black liquid is the calcium chloride solution of 10%-90%, begins simultaneously to stir, and the pH value is adjusted to 6-8, separates out lignin calcium;
(2) add the spent acid of iron content in (1) again, the pH value is adjusted to 4-6;
(3) waste water in (2) is carried out thickening through rotary-type film device I;
(4) rotary-type film device water outlet enters the strong oxidative system of Fenton and further handles the back qualified discharge;
(5) paste after film device concentrates fully mixes with discharge water again, lignin calcium after film device concentrates fully mixes with discharge water again, entering rotary-type film device II then concentrates, wash to colourity and be lower than till 50 times, last concentrate can be as the special-purpose flocculant of carborundum wastewater treatment, and cleaning solution to the strong oxidative system of Fenton is handled.
The paper-mill black liquor and development as resource technique of zero discharge that the present invention adopts rotary-type film to handle, described waste water comprises that with straw, wheat straw, reed or bamboo be the black liquor that produces in the raw material papermaking digesting process.
The paper-mill black liquor and development as resource technique of zero discharge that the present invention adopts rotary-type film to handle describedly adds acid to adjust pH used acid in the 4-6 technology is to contain the sulfur waste acid of iron ion or abraum salt acid.
The paper-mill black liquor and development as resource technique of zero discharge that the present invention adopts rotary-type film to handle, it is 0.001-0.02 μ m rotating circular disk Flat Membrane that described rotary-type film device adopts the aperture.
The present invention compares with traditional process, adopts rotary-type round dull and stereotyped UF film group to solve the blockage problem of film fully, the advantage of its rotary-type round dull and stereotyped UF film:
1. can backwash, surface washing and air are scrubbed;
2. interlock, diaphragm damage and can change by monolithic;
3. face and filter liquide relative velocity are low, can not cause face to cut (mill) and decrease;
4. PVDF material UF film has and is not stained with glutinous characteristic, cleans easily;
5. unlike hollow fiber membrane and the easy fracture of wire of rolled film, not easy cleaning;
6. the space is big between diaphragm, and the water inlet flow process is short, and crushing is little, can stand the high floating outstanding former water of particle (SS), can not block film;
7. film group design is changed easily, and shell needn't be changed.
The present invention has: equipment investment is few, operating cost is low, stable effluent quality, satisfy the advantage that through engineering approaches required, was convenient to large-scale promotion application.
The specific embodiment
The invention will be further described below in conjunction with embodiment, but the protection domain that the present invention requires is not limited to the scope of embodiment statement.
Example 1: handling wheat straw is the papermaking black liquor wastewater COD=24000-30000mg/L of raw material
Adopt 20% calcium chloride solution, adding acid solution is steel tube factory's spent acid, and it is 0.02 μ m Kynoar (PVDF) that milipore filter adopts the aperture.Concrete operations: (1) is added to 20% calcium chloride solution in the black liquid, adjust pH value to 6, reaction time 30min, the steel tube factory's spent acid that adds iron content then, adjust pH value to 4, reaction time 30min, the CODCr clearance reaches 90%, the SS clearance is about 85%, chroma removal rate reaches 95%, the lignin calcium rate of recovery is about 80%, the lignin calcium of flocculation being separated out with the rotating circular disk Flat Membrane carries out Separation of Solid and Liquid then, the supernatant that obtains enters the strong oxidative system of Fenton and further handles, water outlet COD after the strong oxidation processes of Fenton reduces below 60 mg/L, reach " city miscellaneous water water standard " (GBT18920-2002) middle road-cleaning, the fire-fighting requirement is fully cleaned the lignin calcium that separates with part qualified discharge water, and the solubility small organic molecule that contains in the lignin calcium is removed through the Fenton oxidation processes.The big molecule lignin calcium of not allowing is manufactured into the special-purpose flocculant of carborundum wastewater treatment and uses.
Move more than the two weeks the stable emission request that reaches continuously.
Example 2: handling straw is the papermaking black liquor wastewater COD=15000-20000mg/L of raw material
Adopt 20% calcium chloride solution, adding acid solution is steel tube factory's spent acid, and it is 0.02 μ m Kynoar (PVDF) that milipore filter adopts the aperture.Concrete operations: (1) is added to 20% calcium chloride solution in the black liquid, adjust pH value to 7, reaction time 30min, the steel tube factory's spent acid that adds iron content then, adjust pH value to 6, reaction time 30min, the CODCr clearance reaches 90%, the SS clearance is about 85%, chroma removal rate reaches 95%, the lignin calcium rate of recovery is about 80%, the lignin calcium of flocculation being separated out with the rotating circular disk Flat Membrane carries out Separation of Solid and Liquid then, the supernatant that obtains enters the strong oxidative system of Fenton and further handles, and the water outlet COD after the strong oxidation processes of Fenton reduces below 48 mg/L, reaches " city miscellaneous water water standard " (GBT18920-2002) middle road-cleaning, the fire protection criteria requirement.With part qualified discharge water the lignin calcium that separates is fully cleaned again, and the solubility small organic molecule that contains in the lignin calcium is removed through the Fenton oxidation processes.The big molecule lignin calcium of not allowing is manufactured into the special-purpose flocculant of carborundum wastewater treatment and uses.
Move more than the two weeks the stable emission request that reaches continuously.
Claims (3)
1. paper-mill black liquor and development as resource technique of zero discharge that adopts rotary-type film to handle is characterized in that comprising following processing step:
(1) adding concentration in the black liquid is the calcium chloride solution of 10%-90%, begins simultaneously to stir, and the pH value is adjusted to 6-8, separates out lignin calcium;
(2) add the spent acid of iron content in (1) again, the pH value is adjusted to 4-6;
(3) waste water in (2) is carried out thickening through rotary-type film device I;
(4) rotary-type film device water outlet enters the strong oxidative system of Fenton and further handles the back qualified discharge;
(5) the lignin calcium after film device concentrates fully mixes with discharge water again, entering rotary-type film device II then concentrates, wash to colourity and be lower than till 50 times, last concentrate can be as the special-purpose flocculant of carborundum wastewater treatment, and cleaning solution to the strong oxidative system of Fenton is handled;
It is 0.001-0.02 μ m rotating circular disk Flat Membrane that described rotary-type film device adopts the aperture.
2. the paper-mill black liquor and development as resource technique of zero discharge handled of the rotary-type film of employing as claimed in claim 1, it is characterized in that: described black liquid comprises that with straw, wheat straw, reed or bamboo be the black liquor that produces in the raw material papermaking digesting process.
3. the paper-mill black liquor and development as resource technique of zero discharge handled of the rotary-type film of employing as claimed in claim 1 is characterized in that: describedly add acid to adjust pH used acid in the 4-6 technology be to contain the sulfur waste acid of iron ion or abraum salt acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 201210237304 CN102720086B (en) | 2012-07-11 | 2012-07-11 | Paper making black liquor recycling zero discharge process adopting rotary membrane treatment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210237304 CN102720086B (en) | 2012-07-11 | 2012-07-11 | Paper making black liquor recycling zero discharge process adopting rotary membrane treatment |
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| CN102720086A CN102720086A (en) | 2012-10-10 |
| CN102720086B true CN102720086B (en) | 2013-08-14 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6428705B1 (en) * | 1996-11-26 | 2002-08-06 | Microbar Incorporated | Process and apparatus for high flow and low pressure impurity removal |
| CN1397684A (en) * | 2001-07-13 | 2003-02-19 | 阮键华 | Method for treating and comprehensively utilizing black liquor of alkaline pulping and paper making |
| CN101511739A (en) * | 2006-09-13 | 2009-08-19 | 纳尔科公司 | A method of improving membrane bioreactor performance |
| CN102295376A (en) * | 2010-06-24 | 2011-12-28 | 湖北盛华再生能源开发有限公司 | Recycling treatment method for lignin production wastewater |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62106892A (en) * | 1985-11-05 | 1987-05-18 | Ibiden Eng Kk | Method for primary treatment of waste liquid from process for manufacturing electronic circuit substrate |
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2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6428705B1 (en) * | 1996-11-26 | 2002-08-06 | Microbar Incorporated | Process and apparatus for high flow and low pressure impurity removal |
| CN1397684A (en) * | 2001-07-13 | 2003-02-19 | 阮键华 | Method for treating and comprehensively utilizing black liquor of alkaline pulping and paper making |
| CN101511739A (en) * | 2006-09-13 | 2009-08-19 | 纳尔科公司 | A method of improving membrane bioreactor performance |
| CN102295376A (en) * | 2010-06-24 | 2011-12-28 | 湖北盛华再生能源开发有限公司 | Recycling treatment method for lignin production wastewater |
Non-Patent Citations (3)
| Title |
|---|
| JP昭62-106892A 1987.05.18 |
| 制浆黑液的处理与利用技术;程泽胜;《湖北造纸》;20111231(第4期);38-40 * |
| 程泽胜.制浆黑液的处理与利用技术.《湖北造纸》.2011,(第4期),38-40. |
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