CN101020182A - Process of comprehensively utilizing caustic sludge from papermaking industry - Google Patents
Process of comprehensively utilizing caustic sludge from papermaking industry Download PDFInfo
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Abstract
The present invention is process of comprehensively utilizing caustic sludge from papermaking industry. The improved process has increased green liquid purifying treatment procedure, lime material pre-treating procedure, green mud treating procedure, white mud deashing and dealkalizing procedure, and fine white mud treating procedure. The process has no secondary pollution and low running cost, and can produce green mud for desulfurizing in coal burning boiler, superfine white mud calcium carbonate powder product and active calcium carbonate product.
Description
Technical field
The present invention relates to a kind of to the optimization of traditional paper industry alkali recovery process technology with to the solid slag-green mud of generation in producing and the comprehensive development and utilization technology of white clay.
Background technology
The black liquor that paper industry slurrying production process produces is by traditional alkali reclaiming method, can effectively solve its pollution problem, but alkali reclaims the solid slag that production process produces, because there are many incomplete technical problems in traditional treatment process, can't implement well, most of employing is directly discharged green mud, white clay outside the factory or is carried out landfill, has brought pollution problems for the second time.
In present paper industry, alkali reclaims the green mud that produces and can only discharge or landfill, though the processing method of white clay has calcination cycle to utilize method, chemical system to fill out method and the washing system is filled out method, have following deficiency: 1, calcination method mainly is applicable to wood pulp papermaking, but the extensive employing of China is the straw pulp fiber raw material, black liquor silicone content height, and silica removal is subjected to cost, technology limitation, and it is low to make that green liquor clarification difficulty, white clay contain assorted many whiteness, calcination cycle is used and is difficult to realize, and the operating cost height.2, adopt chemical method need dose chemical assistant, cost is not suitable for industrial production than higher.3, WATER-WASHING METHOD is that most of impurity and residual alkali that the white clay of caustic room discharge is removed wherein through several washing, carbonating processing and filtration operation are prepared into the filler that can supply papermaking to use, this method once was applied among a small circle, but along with press to improving constantly that paper product requires, can not satisfy papermaking with the calcium carbonate of this simple process production and add and fill out raw material standard.Because prepared filler particles expansion is poor, quality is loose, and surface strength is low, and fineness and whiteness do not reach requirement.Therefore, in view of above-mentioned several reasons, a lot of papermaking producer directly discharges the causticization white clay outside the factory or carries out landfill, and so both contaminated environment caused the waste of resource again.
Having many experts that alkali is reclaimed the waste residue treatment technology that produces in the industrial production for a long time studies, but total difficult solve satisfactorily green mud, white clay comprehensive utilization and the harmonious technical problem together in alkali recovery process process engineering ground, be difficult to the white mud calcium carbonate filler that will make and copy the paper wet end chemistry organically combine, to reduce the production run cost.How under the prerequisite that does not influence normal alkali recovery process, to obtain to satisfy the calcium carbonate superfine powder product that page is produced; How the waste residue and the green mud of lime mud treatment process are done further comprehensive utilization; How to reduce the process for producing cost that alkali reclaims waste residue most effectively, become people's comprehensive study to utilize alkali to reclaim the blind area of waste residue.
Summary of the invention
Applicant of the present invention is devoted to solve the following problem that runs in the alkali recovery through years of researches:
1, how traditional alkali is reclaimed the application of waste residue (green mud, the white clay) science that production process produces, solve the secondary pollution problem that it brings;
2, how traditional alkali recovery process and waste residue are handled problem effectively harmonious and reduction operating cost;
3, how to solve alkali and reclaim the green mud dehydration problem that production process produces;
4, how to solve the problem of traditional alkali recovery white slime whiteness, neat and well spaced degree, particle surface intensity, purity difference.
The object of the present invention is to provide a kind of new method that reclaims paper industry alkali solid slag,, increased white clay fine processing operation, reach following purpose by traditional burning and causticization process are improved:
1,, in the secondary pollution problem that science solution alkali recovery waste residue brings, guarantees that traditional alkali reclaims the steadily increasing of every economic and technical norms by physical-chemical method;
2, realize that green mud is used for the desulfurization of coal-burning boiler;
3, realize white clay calcium carbonate superfine powder and calcium carbonate activated commercialization;
4, the page of realizing the white mud calcium carbonate after the fine processing adds and fills out, and reduces treatment operating costs.
For achieving the above object, technical scheme provided by the invention is:
A kind of method that reclaims paper industry alkali solid slag, this method is carrying out having increased following technology on the improved basis to traditional burning and causticization process:
(1) technological improvement of green liquor production and purification processes thereof
Green liquor in the tradition alkali recovery process is to be dissolved in hot water or the rare white liquid by the fused mass that combustion furnace flows out to produce.Owing to do not fire charcoal, ion salt and other various colloidal impurities from containing part in the alkali stove fused mass, making has the existence of green mud in the green liquor.The green mud that above-mentioned impurity forms is light and soft, and is black, though the method that traditional alkali recovery process is taked to precipitate is handled, is difficult to reach the degree of separating fully, must influence whiteness and purity that causticization produces.
The present invention is by analysis and research to the green liquor physicochemical characteristics, what discovery added inorganic alkaline flocculant and high polymer coagulant composition in the fusion groove that green liquor generates is the flocculation sediment auxiliary agent of response type with respect to the green liquor medium, will help the clarification of green liquor and the processed of green mud.Green liquor purification processes process, concrete steps are:
Alkali stove fused mass is prepared in the green liquor in dissolving tank, the flocculation sediment auxiliary agent of forming by inorganic alkaline flocculant and high polymer coagulant that adds 2%-5% fused mass amount, fully the stirring back changes green liquor in the defecator over to the green liquor delivery pump and clarifies, and obtains clarifying green liquor.
Above-mentioned flocculation sediment auxiliary agent generally selects for use lime slurry and instant starch to mix with 4: 1 ratios, response type that in said process, adds and the sodium carbonate in the green liquor generation lime deposit that reacts, because the precipitation of calcium carbonate surface area per unit volume is long-pending big, high adsorption capacity, ion and colloidal impurity in its absorption green liquor, again because the existence of macromolecule starch, be gathered at the lime deposit granule and do not fire charcoal in the oarse-grained process and will be wrapped up in in the aggregation and precipitate rapidly.
Be and be chosen in the reason that adds the flocculation sediment auxiliary agent of response type in the burning fusion groove: the fusion groove is the place that the sodium carbonate fusion thing is dissolved into sodium carbonate liquor (green liquor) under the alkali stove high temperature, can guarantee flocculation temperature from adding flocculant here, improve the activation energy of molecule, increase the frequency of molecular collision, the green mud particle of generation is increased, help improving clarifying effect, make it to satisfy the requirement of vacuum filter filtration simultaneously, for vacuum filtration and the mass dryness fraction that improves filtration back green mud create conditions to particle diameter; Mixed effect after flocculant is added strengthens, help with green liquor in the contacting of impurity, purification efficiency is improved.In dissolving tank, add simultaneously, can reduce steam consumption, thereby reduce production costs, because alkali stove sodium carbonate fusion thing temperature height is dissolved in the water and can produces high-temperature area; Adding also can make the concentration of green liquor suitably improve in the dissolving stove, is increased to 140-160g/l by 110-120g/l, can reduce pump output like this, reduces operation energy consumption, improves the quality of alkali lye and the utilization rate of rare white liquid, helps the raising of alkali recovery.
(2) preprocessing process of lime raw material
Alkali reclaims traditional technology and uses green liquor directly to digest lime, its objective is for the concentration of alkali lye and the granularity of white clay, guaranteeing that causticization normal operation of producing and the quality that reclaims alkali meet the demand of pulping process, but the impurity in the lime can bring in the causticization system, influences the purity of white clay.Lime raw material of the present invention is selected high calcium lime for use and is carried out classification processings of sieving through 6-10 order mesh sieve, with the thin ash after sieving, prepares the flocculation sediment auxiliary agent; Smart ash with after sieving is used for the causticization process; After the smart ash that green liquor digestion classification is handled, carry slag by traditional digestion slag extracting machine and handle, and with the processing of sieving of 200-300 purpose screen cloth, lime-ash that sieves and rubble lime-ash merge to and are for further processing in the green mud and fully utilize.
(3) processing procedure of green mud
The green mud that the tradition alkali recovery process produces be mixedly wash with white clay, directly discharging or landfill after the processed.The present invention is mixed with the lime-ash of digestion separation of emulsions with green mud, dewater through lime mud folter, adjust vacuum to 500-600mmHg, make the mass dryness fraction of green mud slag reach 50-55%, this moment, the main component of green mud slag was a calcium carbonate, some carbon powder, it mixes and is used as desulfurizing agent in the coal-burning boiler, makes it obtain comprehensive utilization.
(4) white clay ash disposal, dealkalize process
In order to improve the conversion ratio of sodium salt, the consumption raising 5%-8% with its causticization lime causes producing in the white clay a certain amount of Ca (OH) in traditional alkali recovery process
2Excessive ash, these excessive ashes that are retained in white clay are partially recycled by being able to behind white clay and the green mud mixture.White clay will reclaim and refinement treatment, and it is incompatible that traditional PROCESS FOR TREATMENT reclaims the method for excessive ash.The technical method that the present invention adopts is to set up except that ash process in the causticization production process, promptly in the causticization production process white clay being taken out the back from white liquid defecator reacts with the green liquor of purifying in soot blower, the principle of utilizing chemical reaction equilibrium to shift makes the Ca (OH) that is kept in the white clay
2Excessive ash all is converted into calcium carbonate, and with purifying white mud calcium carbonate quality, reaction density is 20-30%, reaction temperature 90 ℃-105 ℃ (comprising 105 ℃), reaction time 90-120 minute.
The white clay of handling by ash disposal is after vacuum filter carries out Separation of Solid and Liquid, owing to contain a certain amount of alkali, though this part alkali can be removed effectively by the method for washing in the traditional handicraft, water consumption increases on the one hand, can cause the discharging of water; Repeatedly wash the whiteness that can influence white clay on the other hand, the production process reflection: whenever add water washing once, whiteness will descend about 0.5 degree.The technical solution used in the present invention is to add CaCl in the white clay sink
2Solution also fully stirs, and stops to add CaCl when the solution pH value reaches PH9.5-PH10.5
2Solution.
(5) white clay fine processing process
In white clay fine processing process, the wet method sand milling technology that the present invention adopts, the granularity and the neat and well spaced degree of white clay are handled to the quality requirement that satisfies the calcium carbonate superfine powder product, specific embodiment is with the white clay of causticization through purification processes, after the processing of sieving, send in the activated bath, feed steam and be warming up to 70 ℃-75 ℃, add 1-3% activator after treatment by the activating process requirement, in activated bath, carry out wet-process activation and handle after 35-45 minute, wash with being pumped into vacuum filter again, wash the back and in transferring dense groove, regulate concentration, through material loading pumping sand mill milled processed, regulate pH value to PH9.5-10.5, the calcium carbonate emulsion of gained is directly used in page and adds and fill out.The particle size of calcium carbonate can be next controlled by the rotating speed adjustment to sand mill in the calcium carbonate emulsion, and rotating speed is fast more, and throughput is few more, and sand grains is more littler than the calcium carbonate particle diameter of more little gained.The calcium carbonate product that the present invention produces is directly used in page with the form of emulsion and adds and fill out, integrated cost is far superior to make finished product, but page adds that to fill out technology must be neutral, alkalescence or false neutral papermaking, adopts to add with the talcum powder proportioning and fills out the effect optimum, and its ratio is at 60-85%.
Owing to adopted above technical scheme, thereby made the present invention have following effect:
1, the present invention has not only solved traditional alkali and reclaims and produce that the white clay whiteness that produces is low, the problem of purity difference, and by means of powder wet grinding technology, solved the problem that the neat and well spaced degree of white clay is poor, surface strength is low, the fineness index is not high, make the white mud calcium carbonate quality reach the quality standard of ultra-fine precipitates calcium carbonate, the real waste residue utilization of realizing, turn waste into wealth, obtain favorable economic benefit.
2, the present invention makes the dehydration of green mud and it is mixed to be used as desulfurizing agent in the coal-burning boiler and to be achieved in the processing that solves the white clay waste residue simultaneously, and all waste residues that production process produces all obtain comprehensive utilization.
3, the method that combines by physical-chemical of the present invention has well solved the contradictory problems that obtains white clay high quality filler fine particle calcium carbonate that is implemented in of alkali recovery process.Because produce qualified alkali, to guarantee to produce and normally carry out, the particle mean size of the white clay that causticization produces must be more than 780 orders, otherwise clarification system is difficult to clarification, filter can't be realized vacuum filtration, and the quality of alkali lye and explained hereafter can't be guaranteed; And must below 2000 orders, exist the contradictory problems of alkali lye recovery and white clay recovering process process as its particle mean size of white clay fine particle calcium carbonate that filler uses.Present technique solves by the fine processing technology of setting up white clay, the method of wet grinding simultaneously, can adjust the filler granularity neatly, to satisfy the needs of different user, make the purity and the neat and well spaced degree of winnofil of generation better, by adjusting process for refining even can producing active and nano level calcium carbonate product.Make the comprehensive utilization benefit maximization of white clay.
Description of drawings
Fig. 1 is the process chart of caustic sludge from papermaking industry.
The specific embodiment one
Further specify technical process of the present invention below in conjunction with Figure of description:
The present invention improves traditional burning and causticization process process, and except that improving step, all the other steps are implemented by current techique, and improvement may further comprise the steps:
(1) green liquor purification processes process, when alkali stove fused mass is prepared green liquor in the fusion groove, add 2% fused mass amount by lime slurry and instant starch with 4: 1 mixed flocculation sediment auxiliary agents of forming, fully the stirring back changes green liquor in the defecator over to the green liquor delivery pump and clarifies, and obtains clarifying green liquor.
(2) preprocessing process of lime raw material is selected high calcium lime for use, and lime is carried out the classification processing of sieving with 6 purpose mesh sieves, with the thin ash after sieving, and preparation flocculation sediment auxiliary agent; Smart ash with after sieving is mixed with emulsion and is used for the causticization process, after the green liquor digestion emulsion, carries slag and handles, and sieves with 200 order mesh sieves, obtains lime-ash.
(3) processing procedure of green mud, concrete steps are:
The lime-ash of digestion separation of emulsions in the green mud that produces in the step 1 preparation green liquor process and the step 2 is mixed, dewater through lime mud folter, adjust vacuum to 500mmHg, the mass dryness fraction of green mud slag is reached more than 50%, the green mud slag is mixed be used as desulfurizing agent in the coal-burning boiler.
(4) white clay ash disposal, dealkalize process, concrete steps are:
In the causticization production process, white clay taken out from white liquid defecator the back in soot blower with step 1 in the green liquor of purifying react, reaction density is 20%, 90 ℃-105 ℃ of reaction temperatures, reaction 90 minutes, the reaction back adds CaCl in the white clay sink
2Solution regulator solution pH value fully stirs to PH9.5.
(5) white clay fine processing process, with the white clay of causticization,, send in the activated bath through the processing of sieving through purification processes, feed steam and be warming up to 70 ℃, activator after adding 1% is handled carries out wet-process activation and handles after 35 minutes in activated bath, wash with being pumped into vacuum filter again, wash the back and in transferring dense groove, regulate concentration, after material loading pumping sand mill milled processed, regulate pH value to PH9.5, be directly used in page and add the product of filling out.
The specific embodiment two
Implement by the specific embodiment one, just in step (1), change the addition of flocculation sediment auxiliary agent into 3% fused mass amount; Change the mesh sieve in the step (2) processing of sieving of into 7 orders, carry slag and sieve with 250 order mesh sieves in handling; Vacuum in the step (3) is adjusted to 550mmHg carry out the dehydration of vacuum washery slag; Change the reaction condition in the step (4) into reaction density 25%, 95 ℃ of reaction temperatures, 100 minutes reaction time and react, after the reaction pH value is adjusted to PH10, fully stir; Be warming up to 72 ℃ with feeding steam in the step (5), add 2% activator after handling, carry out wet-process activation in the activated bath and handle washing after 40 minutes, regulate concentration and also after milled processed, regulate pH value and adjust to PH10, form calcium carbonate emulsion.
The specific embodiment three
Implement by the specific embodiment one, just in step (1), change the addition of flocculation sediment auxiliary agent into 4% fused mass amount; Change the mesh sieve in the step (2) processing of sieving of into 9 orders, carry slag and sieve with 250 order mesh sieves in handling; Vacuum in the step (3) is adjusted to 550mmHg carry out the dehydration of vacuum washery slag; Change the reaction condition in the step (4) into reaction density 25%, 100 ℃ of reaction temperatures, 110 minutes reaction time and react, after the reaction pH value is adjusted to PH10, fully stir; Be warming up to 74 ℃ with feeding steam in the step (5), add 2% activator after handling, carry out wet-process activation in the activated bath and handle washing after 40 minutes, regulate concentration and also after milled processed, regulate pH value and adjust to PH10, form calcium carbonate emulsion.
The specific embodiment four
Implement by the specific embodiment one, just in step (1), change the addition of flocculation sediment auxiliary agent into 5% fused mass amount; Change the mesh sieve in the step (2) processing of sieving of into 10 orders, carry slag and sieve with 300 order mesh sieves in handling; Vacuum in the step (3) is adjusted to 600mmHg carry out the dehydration of vacuum washery slag; Change the reaction condition in the step (4) into reaction density 30%, 105 ℃ of reaction temperatures, 120 minutes reaction time and react, after the reaction pH value is adjusted to PH10.5, fully stir; Be warming up to 75 ℃ with feeding steam in the step (5), add 3% activator after handling, carry out wet-process activation in the activated bath and handle washing after 40 minutes, regulate concentration and also after milled processed, regulate pH value and adjust to PH10.5, form calcium carbonate emulsion.
The present invention implements according to above-mentioned four specific embodiment, all can produce a desired effect, thereby realize the purpose that caustic sludge from papermaking industry fully utilizes.
Claims (2)
1, a kind of method of caustic sludge from papermaking industry is characterized in that traditional burning and causticization process are improved, and it may further comprise the steps:
(1) green liquor purification processes process, concrete steps are:
When alkali stove fused mass is prepared green liquor in the fusion groove, the flocculation sediment auxiliary agent of forming by inorganic alkaline flocculant and high polymer coagulant that adds 2%-5% fused mass amount, fully the stirring back changes green liquor in the defecator over to the green liquor delivery pump and clarifies, and obtains clarifying green liquor;
(2) preprocessing process of lime raw material, concrete steps are:
Select high calcium lime for use, lime is carried out the classification processing of sieving with 6-10 order mesh sieve, with the thin ash after sieving, preparation flocculation sediment auxiliary agent; Smart ash with after sieving is used for the causticization production process by traditional causticization process;
(3) processing procedure of green mud, concrete steps are:
The lime-ash that separates after the green liquor digestion emulsion in the green mud that produces in the step 1 preparation green liquor process and the step 2 is mixed, dewater through lime mud folter, adjust vacuum to 500-600mmHg, make the mass dryness fraction of green mud slag reach 50-55%, the green mud slag is mixed be used as desulfurizing agent in the coal-burning boiler;
(4) white clay ash disposal, dealkalize process, concrete steps are:
In the causticization production process, white clay taken out from white liquid defecator the back in soot blower with step 1 in the green liquor of purifying react, reaction density is 20-30%, reaction temperature 90-105 ℃, reaction time 90-120 minute, and the reaction back adds CaCl in the white clay sink
2Solution regulator solution pH value fully stirs to PH9.5-10.5;
(5) white clay fine processing process, concrete steps are:
With the white clay of causticization through purification processes, through the processing of sieving, send in the activated bath, feed steam and be warming up to 70-75 ℃, the activator after handling by activating process requirement adding 1-3%, carrying out wet-process activation in activated bath handled after 35-45 minute, wash with being pumped into vacuum filter again, wash the back and in transferring dense groove, regulate concentration, after material loading pumping sand mill milled processed, regulate pH value to PH9.5-10.5, be directly used in page and add the product of filling out.
2, a kind of method that reclaims paper industry alkali solid slag according to claim 1 is characterized in that: the flocculation sediment auxiliary agent described in the step 1 by lime slurry and instant starch with 4: 1 mixed mixtures.
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| CN101391794B (en) * | 2008-10-24 | 2010-06-09 | 魏湘 | Novel method for preparing light calcium carbonate by recovering solid white slime through alkaline pulping |
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| CN1225586C (en) * | 2002-02-09 | 2005-11-02 | 艾栋 | Improved alkali recovering process from paper-making black liquor |
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| CN102094346A (en) * | 2010-12-02 | 2011-06-15 | 陕西科技大学 | Acid method silica removal process for green liquor in alkali recovery section of papermaking |
| CN103180506A (en) * | 2011-09-19 | 2013-06-26 | 北京沃特玛德环境技术股份有限公司 | Method for comprehensively utilizing solid waste during soda recovery in papermaking industry |
| CN102423608A (en) * | 2011-10-28 | 2012-04-25 | 长沙理工大学 | Desulfurizer prepared by causticized white mud and method thereof for flue gas desulphurization |
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| CN112014427B (en) * | 2020-09-09 | 2024-03-12 | 惠州海关综合技术中心(惠州国际旅行卫生保健中心、惠州海关口岸门诊部) | Vacuum type Kenan test device with solid-liquid dual-measurement function |
| CN116375072A (en) * | 2023-04-11 | 2023-07-04 | 重庆碳福森环保科技有限公司 | Method for producing modified calcium carbonate by aid method |
| CN116375072B (en) * | 2023-04-11 | 2024-02-27 | 重庆碳福森环保科技有限公司 | Method for producing modified calcium carbonate by aid method |
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