CN101402500A - Film treatment method for black liquor from papermaking - Google Patents
Film treatment method for black liquor from papermaking Download PDFInfo
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- CN101402500A CN101402500A CNA2008101436417A CN200810143641A CN101402500A CN 101402500 A CN101402500 A CN 101402500A CN A2008101436417 A CNA2008101436417 A CN A2008101436417A CN 200810143641 A CN200810143641 A CN 200810143641A CN 101402500 A CN101402500 A CN 101402500A
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Abstract
The invention provides a method for treating paper-making black liquor by the film technique. The method comprises the following steps:: the paper-making black liquor is filtered by a filter bag to obtain filter residue and filter liquor 1, the filter liquor 1 enters a micro filter film separation device to obtain concentrated solution 1 and filter liquor 2, the filter liquor 2 enters a nano filter film separation device to obtain filter liquor containing alkali and concentrated solution containing lignin and hemicellulose, the filter residue and the concentration solution are evaporated through an evaporator, and the filter liquor containing the alkali is returned for recycling or sent to dissolve alkali ash combusted in a boiler. In the method, the lignin and the hemicellulose in the paper-making black liquor can be concentrated to be 20 percent of solid content and the recovery rate of alkali is more than 90 percent; moreover, the method also has the advantages of no wastewater discharge in the waste liquid reclamation engineering, high economic benefit and good environmental benefit.
Description
Technical field
The present invention relates to the treatment process of black liquid, particularly relate to and adopt the treatment process of membrane separation technique black liquid.
Background technology
The most paper mills of China are raw material with the non-wood-fiber, mainly constitute with Mierocrystalline cellulose, xylogen and hemicellulose (being the poly-pentose class) three big compositions.Mierocrystalline cellulose is the main raw material of papermaking, Mierocrystalline cellulose belongs to the alkali insolubles, in the alkali lye in rotary spherical digester, xylogen and hemicellulose are dissolvable in water and form black liquor in the alkali lye, therefore, wheat straw is in the rotary spherical digester digestion process, xylogen and hemicellulose are dissolved by alkaline solution, formation contains water, residual alkali, Mierocrystalline cellulose, the original slurry of alkali lignin and hemicellulose, original slurry is separated through slurries, be not extracted and separate by alkali lye dissolved Mierocrystalline cellulose (paper pulp), send to laundry, choosing is floated operation and is done further processing, after extracting paper pulp, the waste liquid that contains solid substance is called black liquor because of color is black, mainly contains residual alkali in the black liquor, water and the alkali lignin that is dissolved in the alkali lye, hemicellulose and a spot of inorganic salt and other material.
The black liquor that contains a large amount of xylogen accounts for 47.9% in paper waste COD forms, in forming, colourity accounts for 59.4%, be primary pollution source in the paper waste, hemicellulose then is another primary pollution source in the paper waste, they account for more than 90% of black liquor pollution thing total amount, are the sources of paper waste environmental pollution.
These black liquor adopt traditional technology method or several technology bonded treatment processs such as chemical recovery, flocculation sediment, bio-oxidation, the floating air supporting of medicine at present mostly, but the waste water after these methods are handled does not often reach strict emission control standards.
The treatment process of general pulp black liquor is with black liquor vaporizing, concentrates, then concentrated black liquid is sprayed into the alkali recovery furnace burning, the organic compound combustion in the black liquor produces high-temperature flue gas, and the inorganics in the black liquor burns till melt and dissolved thing, after subsequent disposal such as causticization, alkali is reclaimed repeated use.And the treatment process of this pulp black liquor is used for careless class is the middle-size and small-size papermaking enterprise of main raw material, but be difficult to carry out, its reason mainly is: 1, owing to silicone content in the straw pulp black liquor is very high, substantially exceed the content of pulp black liquor, therefore can cause fouling of evaporator very soon, concentration can not improve, and evaporation capacity descends.It is low to advance furnace black liquid concentration during 2, owing to burning, and viscosity is big, therefore sprays the drop that do not loose, the drying difficulty.3, the straw pulp black liquor calorific value is low, the burning difficulty.4, lime mud treatment difficulty.5, hemicellulose level height hinders the conduction of heat, reduces vaporization efficiency, increases the equipment washing and the residence time.
Chinese patent publication number CN1182149 discloses a kind for the treatment of paper-making black liquor, it is characterized in that black liquor at first adds acid-producing bacteria and carries out the microbial acidification processing in storage pool, secondly after acidifying, add acid carrier in the black liquor, stirred and separate out lignin, water outlet enters two sections processing (middle-stage wastewater processing).Though this invention cost is low, but processing speed is slower, is difficult to the Large Scale and Continuous chemical industry and handles.
Chinese patent publication number CN1994941 discloses a kind of technological process for the treatment of papermaking method, it is characterized in that with clear water paper waste being diluted to solid content in settling tank is 7g/L-15g/L, the COD value is 5g/L-12g/L, the ash powder content is 0.2%-0.51%, after relative density is the pretreated water of 0.20-0.41, the liming of the 0.02-0.06% unslaked lime of the pretreated water weight of in settling tank, evenly splashing again, the precipitation water that precipitates after 12-48 hour enters biochemical treatment tank, regulate the pH value of water to 6-8.5 with urea and calcium superphosphate, deposited 90 days, cultivate the dissolved oxygen amount of the little lively plant raising water in the water, water quality reaches the environment protection emission requirement.This method had both needed to add a lot of medicaments, needed to spend long time again, was not suitable for suitability for industrialized production.
Chinese patent publication number CN1431158 discloses a kind of paper waste treatment process, it mainly adopts waste water after filtering to enter preliminary sedimentation tank, remove suspended substance, mud discharging is to tempering tank, and waste water enters the aeration tank again, medium sediment pool returned sluge groove, adopt volume pump that drift ice is made an addition to medium sediment pool returned sluge groove continuously, through medium sediment pool, final deposition pool, draw back sludge thickener by reclaiming sludge pump again, upper clear liquid gets final product qualified discharge.This method floor space is big, and elapsed time is long, and day output is big inadequately, need improve.
Although what aforesaid method had comes into operation, but from producing, do not have higher production efficiency, its shortcoming mainly shows: 1. the interpolation of precipitation agent makes macrobead precipitations such as suspended substance in the black liquor and colloid, and the method for adding precipitation agent can increase the input of resource; 2. preliminary sedimentation tank, medium sediment pool, selecting for use of final deposition pool adopt various settling bowls to come the sedimentation pollutants in waste water, and floor space is big, and under the situation that land used is in short supply, this method should not adopt at present; 3. the employing of biological method selects for use biological method to handle black liquor, and the culturing sludge time is long, not anti-high punching press water, and length consuming time is unfavorable for the Large Scale and Continuous equalization.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method with membrane technique processing black liquid, and is low to overcome combustion method processing black liquor efficient, pollutes to weigh, and takes up an area of greatly; Biological process is handled the slow-footed shortcoming of black liquor.
The present invention includes following steps:
Film treatment method for black liquor from papermaking, to contain alkali, the black liquid of lignin and hemicellulose is through the filter bag pre-treatment, the filter residue that obtains enters vaporizer, and filtrate to enter with pressure be the microfiltration membrane separating device that drives, macromolecular particle is held back, again the concentrated solution after the microfiltration process is entered vaporizer, and filtrate enters nanofiltration membrane treatment equipment and separates and concentrate, acquisition contains alkali filtrate and xylogen and hemicellulose concentrated solution, after lignin and hemicellulose tunicle are held back and are concentrated to solid content 20%, deliver to evaporator evaporation again, the clean sode ash that contains after alkali filtrate (alkali concn is identical with the waste liquid alkali concn) goes to dissolve boiler combustion.
The molecular weight cut-off of the microfiltration membrane that the present invention relates to is 50000-100000, and the molecular weight cut-off scope of nanofiltration membrane is 150-1000;
The microfiltration process service temperature is 5-55 ℃, and pressure is 1-5Kg/cm
2, preferred temperature is 35-45 ℃, pressure is 2-5Kg/cm
2Following operation.
The nanofiltration process service temperature is 15-45 ℃, and pressure is 15-40Kg/cm
2, preferred temperature is 35-45 ℃, pressure is 15-35Kg/cm
2Following operation.
The alkali that the present invention relates to is sodium hydroxide.
The microfiltration membrane that the present invention relates to and the material of nanofiltration membrane are the organic or inorganic material, and the assembly of film is a kind of in board-like film, tubular membrane, rolled film and the hollow-fibre membrane.
In nanofiltration process, when the volume total amount of nanofiltration filtrate reaches the 80%-90% of micro-filtration filtrate total amount, add the saturating wash water of micro-filtration filtrate total amount 30%-40%.
It is the microfiltration membrane and the nanofiltration membrane treatment black liquid of motivating force that the present invention adopts with pressure, does not need to add any medicament, can reach the resources conservation purpose; The film device floor space is little; it is big that day is handled the black liquor amount; and processing speed is fast; can drop in the large-scale serialization production process; and treatment effect is far above chemical method and combustion method; can be good at making alkali lye to separate, and be used respectively, so not only made full use of resource but also protected environment with lignin and hemicellulose.The present invention can make the lignin and the hemicellulose that separate in the black liquor be concentrated to 20% of solid content, and alkali recovery is higher than 90%;
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1:
With 100m
3NaOH concentration is 1.94g/L, and COD is 126800mg/L, and colourity is that 18000 black liquor carries out prefiltration by filter bag, then at 45 ℃ of temperature, pressure 2Kg/cm
2Condition under through membrane flux be the rolling microfiltration membrane system of 100LMH, filtrate is again at 35 ℃ of temperature, pressure 25Kg/cm
2Condition under be the rolled film nanofiltration system of 6.6LMH through membrane flux, reach 85m when seeing through liquid measure
3The time, begin to add wash water 30m
3, finally concentrate volume 10m
3The filtrate alkali content is 11.62g/L, and COD is 31500mg/L, and colourity is 2000.
Embodiment 2:
With 100m
3NaOH concentration is 1.71g/L, and COD is 94600mg/L, and colourity is that 20000 black liquor carries out prefiltration by filter bag, then at 40 ℃ of temperature, pressure 2.5Kg/cm
2Condition under through membrane flux be the tube type filter membrance system of 150LMH, filtrate is again at 40 ℃ of temperature, pressure 17Kg/cm
2Condition under be the rolled film nanofiltration system of 4.2LMH through membrane flux, reach 90m when seeing through liquid measure
3The time, begin to add wash water 30m
3, finally concentrate volume 10m
3The filtrate alkali content is 8.37g/L, and COD is 28150mg/L, and colourity is 2500.
Embodiment 3:
With 100m
3NaOH concentration is 1.84g/L, and COD is 106800mg/L, and colourity is that 16000 black liquor carries out prefiltration by filter bag, then at 45 ℃ of temperature, pressure 3Kg/cm
2Condition under through membrane flux be the tube type filter membrance system of 100LMH, filtrate is again at 40 ℃ of temperature, pressure 35Kg/cm
2Condition under be the tubular membrane nanofiltration system of 8.6LMH through membrane flux, reach 90m when seeing through liquid measure
3The time, begin to add wash water 30m
3, finally concentrate volume 8m
3The filtrate alkali content is 10.62g/L, and COD is 30000mg/L, and colourity is 2800.
Claims (10)
1. method of handling black liquid with membrane technique, it is characterized in that, at first adopt filter bag that black liquid is carried out pre-filtering, filter residue enters vaporizer, and will enter with pressure through pre-filtered filtrate is the microfiltration membrane tripping device of motivating force, concentrated solution 1 enters vaporizer, is the nanofiltration membrane separation device of motivating force and will the filtrate after microfiltration membrane is separated enter with pressure, obtains to contain alkali filtrate and xylogen and hemicellulose concentrated solution 2.
Described microfiltration process service temperature is 5-55 ℃, and pressure is 1-5Kg/cm
2
Described nanofiltration process service temperature is 15-45 ℃, and pressure is 15-40Kg/cm
2
2. method according to claim 1 is characterized in that, will filter back gained filter residue and concentrated solution 1 and concentrated solution 2 and deliver to evaporator evaporation.
3. method according to claim 1 is characterized in that, the alkali filtrate that contains that finally obtains is returned recycle.
4. according to claim 1 and 2 described methods, it is characterized in that, the sode ash after alkali filtrate is used to dissolve evaporator evaporation of containing that finally obtains.
5. method according to claim 1 is characterized in that, the material of described pressure-driven separatory membrane is the organic or inorganic material.
6. method according to claim 1 is characterized in that, said microfiltration membrane is a kind of in board-like film, tubular membrane, rolled film or the hollow-fibre membrane.
7. method according to claim 1 is characterized in that, said nanofiltration membrane is a kind of in board-like film, tubular membrane, rolled film or the hollow-fibre membrane.
8. method according to claim 1 is characterized in that, described microfiltration process service temperature is 35-45 ℃, and pressure is 2-5Kg/cm
2
9. method according to claim 1 is characterized in that, described nanofiltration process service temperature is 35-45 ℃, and pressure is 15-35Kg/cm
2
10. method according to claim 1 is characterized in that, in nanofiltration process, when the volume total amount of nanofiltration filtrate reaches the 80%-90% of micro-filtration filtrate total amount, adds the saturating wash water of micro-filtration filtrate total amount 30%-40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101436417A CN101402500A (en) | 2008-11-18 | 2008-11-18 | Film treatment method for black liquor from papermaking |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101436417A CN101402500A (en) | 2008-11-18 | 2008-11-18 | Film treatment method for black liquor from papermaking |
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| Publication Number | Publication Date |
|---|---|
| CN101402500A true CN101402500A (en) | 2009-04-08 |
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|---|---|---|---|
| CNA2008101436417A Pending CN101402500A (en) | 2008-11-18 | 2008-11-18 | Film treatment method for black liquor from papermaking |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812813A (en) * | 2010-04-07 | 2010-08-25 | 中南大学 | Method and device for treating paper-making black liquid acid-precipitation waste liquid film |
| CN101948192A (en) * | 2010-08-31 | 2011-01-19 | 长沙绿芯科技有限公司 | Membrane technology-based papermaking black liquor high-efficiency comprehensive treatment method |
| CN102390903A (en) * | 2011-09-30 | 2012-03-28 | 蒲茂军 | Papermaking black liquid membrane treating method |
| 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 |
| CN103215838A (en) * | 2013-03-11 | 2013-07-24 | 中国地质大学（武汉） | Process of wood pulp papermaking black liquor resourceful treatment |
| CN103657419A (en) * | 2013-12-06 | 2014-03-26 | 南京工业大学 | Process for recovering alkali by double-membrane separation method in chemical fiber production |
| CN104556555A (en) * | 2014-12-04 | 2015-04-29 | 通道神华林化有限公司 | Zero pollution discharge system for treating papermaking black liquor and treatment method thereof |
| CN105714590A (en) * | 2016-04-15 | 2016-06-29 | 广西科学院 | Method for separating lignin and hemicellulose from papermaking black liquor and recycling alkali liquor |
| CN107055924A (en) * | 2017-05-24 | 2017-08-18 | 广西碧清源环保科技有限公司 | Ceramic membranous system and its handling process for Sewage |
| CN108423902A (en) * | 2018-02-27 | 2018-08-21 | 西王药业有限公司 | A kind of circulation utilization method of chromatographic isolation wash water |
| CN111018213A (en) * | 2018-10-10 | 2020-04-17 | 上海凯鑫分离技术股份有限公司 | Non-wood plant papermaking black liquor recycling treatment system and treatment process |
| CN111961428A (en) * | 2020-07-07 | 2020-11-20 | 广西大学 | Preparation method of lignin modified phenolic resin adhesive |
-
2008
- 2008-11-18 CN CNA2008101436417A patent/CN101402500A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812813A (en) * | 2010-04-07 | 2010-08-25 | 中南大学 | Method and device for treating paper-making black liquid acid-precipitation waste liquid film |
| CN101948192A (en) * | 2010-08-31 | 2011-01-19 | 长沙绿芯科技有限公司 | Membrane technology-based papermaking black liquor high-efficiency comprehensive treatment method |
| CN102390903A (en) * | 2011-09-30 | 2012-03-28 | 蒲茂军 | Papermaking black liquid membrane treating method |
| CN103215838B (en) * | 2013-03-11 | 2016-02-03 | 中国地质大学（武汉） | A kind of technique to the process of wood pulp papermaking black liquor and development as resource |
| CN103215838A (en) * | 2013-03-11 | 2013-07-24 | 中国地质大学（武汉） | Process of wood pulp papermaking black liquor resourceful treatment |
| 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 |
| CN103657419A (en) * | 2013-12-06 | 2014-03-26 | 南京工业大学 | Process for recovering alkali by double-membrane separation method in chemical fiber production |
| CN104556555A (en) * | 2014-12-04 | 2015-04-29 | 通道神华林化有限公司 | Zero pollution discharge system for treating papermaking black liquor and treatment method thereof |
| CN104556555B (en) * | 2014-12-04 | 2016-06-29 | 通道神华林化有限公司 | A kind of no pollution exhaust system for processing black liquid and processing method thereof |
| CN105714590A (en) * | 2016-04-15 | 2016-06-29 | 广西科学院 | Method for separating lignin and hemicellulose from papermaking black liquor and recycling alkali liquor |
| CN107055924A (en) * | 2017-05-24 | 2017-08-18 | 广西碧清源环保科技有限公司 | Ceramic membranous system and its handling process for Sewage |
| CN108423902A (en) * | 2018-02-27 | 2018-08-21 | 西王药业有限公司 | A kind of circulation utilization method of chromatographic isolation wash water |
| CN111018213A (en) * | 2018-10-10 | 2020-04-17 | 上海凯鑫分离技术股份有限公司 | Non-wood plant papermaking black liquor recycling treatment system and treatment process |
| CN111961428A (en) * | 2020-07-07 | 2020-11-20 | 广西大学 | Preparation method of lignin modified phenolic resin adhesive |
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Open date: 20090408 |