CN1321243C - Method for recovering superfine calcium carbonate by clean causticization of green liquor - Google Patents
Method for recovering superfine calcium carbonate by clean causticization of green liquor Download PDFInfo
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- CN1321243C CN1321243C CNB2004100530771A CN200410053077A CN1321243C CN 1321243 C CN1321243 C CN 1321243C CN B2004100530771 A CNB2004100530771 A CN B2004100530771A CN 200410053077 A CN200410053077 A CN 200410053077A CN 1321243 C CN1321243 C CN 1321243C
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- calcium carbonate
- green liquor
- slurry
- superfine powder
- causticization
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 122
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002002 slurry Substances 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 27
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 26
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000009993 causticizing Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims abstract description 15
- 239000012065 filter cake Substances 0.000 claims abstract description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 239000000292 calcium oxide Substances 0.000 claims abstract description 7
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000000843 powder Substances 0.000 claims description 28
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 24
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000007670 refining Methods 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000005997 Calcium carbide Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229930006000 Sucrose Natural products 0.000 claims description 4
- 239000000701 coagulant Substances 0.000 claims description 4
- 230000003750 conditioning effect Effects 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- 241000202567 Fatsia japonica Species 0.000 claims description 3
- 238000010009 beating Methods 0.000 claims description 3
- 229910021538 borax Inorganic materials 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 235000019800 disodium phosphate Nutrition 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical group [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000004328 sodium tetraborate Substances 0.000 claims description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 238000005352 clarification Methods 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 18
- 239000002245 particle Substances 0.000 abstract description 15
- 239000003513 alkali Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 5
- 238000013019 agitation Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000013049 sediment Substances 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 description 43
- 239000004927 clay Substances 0.000 description 10
- 239000000945 filler Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000004537 pulping Methods 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 208000005156 Dehydration Diseases 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Landscapes
- Paper (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a method for recovering superfine calcium carbonate by cleaning and causticizing green liquor. The method mainly comprises the following steps: a. polymeric flocculant is added to green liquor, sediments on the lower layer are removed after the green liquor and the polymeric flocculant are evenly agitated, and clear liquor on the upper layer is retained to be used as refined green liquor for standby; b. quicklime is added to water so as to make calcium hydroxide slurry, and impurities are separated and removed from the calcium hydroxide slurry by a sieve or rotary liquor; c. after the refined green liquor is mixed with the calcium hydroxide slurry, the causticizing reaction is implemented, and a crystal regulating agent is added in the reaction; d. the solid-liquid separation of the causticized slurry is implemented, a filter cake is washed with hot water, and filter liquor is recovered; e. the filter cake is pulped and watered to prepare suspension liquor slurry, and carbon dioxide is introduced so as to obtain superfine calcium carbonate. In the causticizing process, the method is used, the particle sizes are even through the agitation speed rate and the material mixing mode, and thus, the solid-liquid separation effect is enhanced. The recovered superfine calcium carbonate slurry is carbonized secondarily after liquid alkali is filtered, washed and recovered, the product alkalinity is reduced, and the product quality is enhanced.
Description
Technical field:
The black liquor recovery liquid caustic soda that the present invention relates in the papermaking to be produced and the technical field of environmental protection, specifically a kind of green liquor cleaning causticization reclaims the method for calcium carbonate superfine powder.
Background technology:
In the paper mill, when producing, alkaline process system oar produces a large amount of black liquor, serious environment pollution at present.In order to eliminate the pollution of black liquor to environment, each large-scale pulping and paper-making manufacturing enterprise all has black liquor alkali to reclaim, and has eliminated the pollution of black liquor, and the liquid caustic soda of recovery continues on for soda pulping process.The tradition technique for recovering papermaking black liquor alkali is had to a kind of product---and caustic soda (white liquid) produces a large amount of waste residues---white clay simultaneously.In these white claies, both contained the calcium carbonate of causticizing reaction, contain unreacted superfluous lime and raw material (green liquor and lime) again and be entrained to various impurity in the reaction system.This white clay complicated component is a kind of alkaline scrap material of serious environment pollution, and its amount is especially big.Along with the development of paper industry, the especially production-scale expansion of soda pulping process, its pollution is very serious, seriously restricts the sustainable development of national economy.
Years of researches are carried out in domestic processing to soda pulping process recovery white clay that alkali produces, and mainly contain three kinds of processing methods at present: (1) is flashed back into lime with white clay and recycled.Because the white clay silicon content height that straw pulp black liquor produces when reclaiming alkali is being sintered into the accumulation that causes silicon when lime recycles, form the vicious circle that silicon disturbs, influence normally carrying out of alkali recovery.(2) white clay is through PROCESS FOR TREATMENT such as washing, grindings, and the calcium carbonate impurity content that this method reclaims is many, and whiteness has only about 80, can only be as the papermaking filler of low grade.This pearl filler is big to the wearing and tearing of paper machine simultaneously, and the paper mill is not approved, is difficult to apply yet.(3) the white clay waste residue is transported to cement, factory substitutes the part lime stone as the raw material of producing cement, carries out the regeneration of waste material resource.This method is low in economic efficiency, also can't apply.
Up to the present, China existing large-scale soda pulping process factory for reclaiming the white clay that is produced behind the alkali lye, because of there not being good improvement method, can only enter rivers or landfill.In fact this method with the transfer of white clay pollution, is present makeshift just, causes secondary pollution.Chemical system of domestic He'nan University reclaims black liquid alkali and has carried out darker research, and has applied for patent of invention " improved alkali recovering process from paper-making black liquor " (publication number CN1436894A).Because this patent is in the causticization process, the particle size of the calcium carbonate product that reclaims has been done effective control.And be used for papermaking filler and coating as calcium carbonate product, except requirement, the more important thing is requirement to pattern to particle diameter; Secondly, this technology reduces the basicity of calcium carbonate by the secondary causticization.In fact, because causticizing reaction is a reversible reaction, according to the thermodynamic principles of chemical reaction, can not be by increasing the causticizing reaction time and finally reducing the basicity of product fully, so cause the calcium carbonate product alkalinity of recovery higher with the method for washing.
Along with the development of paper-making industry, the calcium carbonate that filler and surface coating are used proposes different particle diameter and pattern requirement.Carry out carbonization generation calcium carbonate in milk of lime, feeding kiln gas, particle size and pattern how to control product have more research, and reclaim liquid caustic soda and calcium carbonate for green liquor causticizing, but never there is the people that particle size control, particle diameter pattern control aspect are studied; When reclaiming calcium carbonate, how effectively the basicity aspect of control recovery product does not have satisfied result yet simultaneously.
Summary of the invention:
The object of the present invention is to provide a kind of improved green liquor cleaning causticization to reclaim the method for calcium carbonate superfine powder, by particle diameter, pattern and the basicity of control recovery calcium carbonate product, making it former cause discarded " white clay " becomes the industrialization product that has than high added value.
To achieve these goals, technical scheme of the present invention is: a kind of green liquor cleaning causticization reclaims the method for calcium carbonate superfine powder, it is characterized in that: the method that described green liquor cleaning causticization reclaims liquid caustic soda and calcium carbonate superfine powder may further comprise the steps: a, to add percentage by weight in green liquor be the high polymer coagulant of 0.01-0.1%, the back natural subsidence stirs, remove lower floor's precipitum, stay supernatant liquid standby as refining green liquor; B, be that the quick lime of 10-25% adds in 40-60 ℃ the hot water and makes calcium hydroxide slurry, above-mentioned slurry is separated removal of impurities with screen cloth or spinning liquid percentage by weight; C, with the above-mentioned refining green liquor that makes with after calcium hydroxide slurry is mixed by 1: 1~1.05 of theoretical reacting dose, in 30-100 ℃, carry out causticizing reaction, and to add in the calcium carbonate quantity percentage by weight be the crystal structure adjusting agent of 0.2-1.5% in reaction; D, the slurry after the causticization is carried out Separation of Solid and Liquid, filter cake is with 50-70 ℃ of hot wash, and filtrate is reclaimed as liquid caustic soda; E, filter cake making beating is added water be mixed with the suspension slurry that solid content is 15-20%, feed the further carbonization of carbon dioxide again and be neutral, obtain the calcium carbonate superfine powder slurry until slurry.
Use the technology used in the present invention be calcium hydroxide slurry with refining after the green liquor causticizing reaction in, according to the basic principle of crystallography, by adding crystal structure adjusting agent, the nucleation of control crystal and the growth rate of each crystal face are to reach particle diameter and pattern is controlled.In the subtractive process of green liquor, remove the colloid material to greatest extent, reduce the viscosity of system, the rate of settling of accelerated particle; In the causticization process, by the hybrid mode of stir speed (S.S.) and material, the nucleation period of control calcium carbonate separated with growth period, and it is even to reach particle size, avoided the existence of fine particle and influenced the rate of settling, the raising solid-liquid separation effect.Calcium carbonate superfine powder slurry to reclaiming carries out the secondary carbonization after filtration again behind the washing and recycling liquid caustic soda, effectively reduce the basicity of product, improves the quality of products.The calcium carbonate superfine powder of the different-shape that is reclaimed by this technology is suitable for different purposes, example is used for papermaking filler for little calcium carbonate that is agglomerated into colored shape, calcium carbonate for grain of rice shape is used for papermaking paint, and can be used as high-grade filling for rubber plastic for ultra-fine granular calcium carbonate through the stearic acid processing.Have good social benefit and considerable economic.
The specific embodiment:
The invention will be further described below in conjunction with embodiment.
The method that green liquor of the present invention cleaning causticization reclaims liquid caustic soda and calcium carbonate superfine powder may further comprise the steps: a, to add percentage by weight in green liquor be the high polymer coagulant of 0.01-0.1%, the back natural subsidence stirs, remove lower floor's precipitum, the viscosity of reduction system, the rate of settling of accelerated particle stays supernatant liquid standby as refining green liquor; B, be that the quick lime of 10-25% adds in 40-60 ℃ the hot water and makes calcium hydroxide slurry with percentage by weight, above-mentioned slurry screen cloth or spinning liquid are separated removal of impurities, calcium hydroxide slurry behind the quicklime slaking being carried out spinning liquid separate the impurity removal and purification processing, is to enter the causticization system for fear of oxious component; C, by the ratio of the theoretical amount of the reaction of the sodium carbonate in calcium hydroxide and the green liquor be 1.05 mix after, in 30-100 ℃, carry out causticizing reaction, in the causticization process, hybrid mode by stir speed (S.S.) and material, the nucleation period of control calcium carbonate separated with growth period, it is even to reach particle size, avoid the existence of fine particle and influenced the rate of settling, improve solid-liquid separation effect, and adding weight of calcium carbonate percentage is the crystal structure adjusting agent of 0.2-1.5% in reaction, the hybrid mode and the stir speed (S.S.) of control green liquor and calcium hydroxide suspension, the growth rate of regulating each crystal face makes the particle diameter of calcium carbonate and pattern controlled; D, the slurry after the causticization is carried out Separation of Solid and Liquid, filter cake is with 50-70 ℃ of hot wash, and filtrate is reclaimed as liquid caustic soda; E, filter cake making beating is added water be mixed with the suspension slurry that solid content is 15-20%, feed the further carbonization of carbon dioxide again and be neutral, effectively reduce the alkali content in the product, help improving the quality of products, obtain the calcium carbonate superfine powder slurry until slurry.Wherein green liquor be black liquor through calcine sode ash, get with water extraction again, it is a prior art, has here just repeated no more.
In refining calcium hydroxide slurry and the reaction of refining green liquor, the solid content of calcium hydroxide slurry is 25-40%; Add crystal structure adjusting agent in carry out at causticizing reaction preceding 0-40 minute, crystal structure adjusting agent is sodium hydrogen phosphate, sodium sulphate, potassium sulfate, borax and sucrose; The carbon dioxide that adds in the suspension slurry comes from kiln gas or paper plant, and its concentration is 20-35%, and temperature is 10-40 ℃; With the surface conditioning agent that accounts for calcium carbonate superfine powder percentage by weight 1.0~3.5% calcium carbonate superfine powder is carried out surface treatment and make super-fine active calcium carbide, described surface conditioning agent is stearic acid, water-soluble titanate coupling agent AT-15, water-soluble KH-550 silane coupler, and the temperature of processing is 45~90 ℃; The temperature of the final dried of super-fine active calcium carbide is 85~110 ℃.
In force, add sodium polyacrylate polymer flocculant or water soluble starch in green liquor, addition is 0.01~0.1% of an amount of liquid, and the back natural subsidence that stirs is removed lower floor's precipitum, and supernatant liquid is standby for refining green liquor; Quick lime is added in 40~60 ℃ the hot water, static 15~20 minutes, stirred again 15 minutes, thick calcium hydroxide slurry is further separated residue through the secondary cyclone hydraulic separators must make with extra care calcium hydroxide slurry.With this calcium hydroxide slurry natural subsidence, supernatant liquor is used for digesting once more, and lower floor's precipitum is that the calcium hydroxide slurry of high solids is standby; Calcium hydroxide slurry is mixed stirring with the green liquor made from extra care, and be warming up to 50~100 ℃ of reactions, when the conversion ratio of causticizing reaction adds crystal structure adjusting agent sodium hydrogen phosphate, sodium sulphate, potassium sulfate, borax and sucrose etc. 0%~30% the time, addition is 0.2%~1.5% of a calcium carbonate quantity, regulates the particle diameter and the pattern of calcium carbonate.
Reaction equation is: Ca (OH) 2+Na2CO3=CaCO3 ↓+2NaOH
Then the slurry after the causticization is carried out centrifugal dehydration treatment after natural subsidence, the filter cake hot wash.Supernatant liquor, the liquid caustic soda of filtrate for reclaiming can be used for paper industry.Cleaning solution is used for the leaching of sode ash, promptly produces green liquor; Filter cake is added water, and to be mixed with solid content be 15%~20% suspension slurry, under agitation feed the further carbonization of kiln gas (pH is 7) to terminal, this calcium carbonate superfine powder slurry promptly directly is sent to paper plant and makes the calcium carbonate superfine powder coating for paper as papermaking filler or after dewatering; The calcium carbonate superfine powder slurry is heated to 45~95 ℃, adds the processing that coats of 0.5~3.5% covering by the weight of calcium carbonate, coating the processing time is 0.5~3.5 hour.Used covering is one or both in stearic acid, water-soluble titanate coupling agent AT-15 and the water-soluble KH-550 silane coupler etc., its preparation method is 5~20% the aqueous solution for covering being mixed with concentration, regulate pH value of aqueous solution 8~13 in 50~80 ℃ of temperature ranges, dissolving is emulsifiable in the water stand-by.Can be used as the functional stuffing of high-grade rubber, plastics and vehicle paint base by the super-fine active calcium carbide of this method processing.
Embodiment 1
Adding solid content in a certain amount of green liquor is the aqueous solution of 3.0% Sodium Polyacrylate flocculant, and addition is 0.01% of a green liquor amount, mixes the back and filters in static 30 minutes, and clear liquid is used for causticizing reaction.
Quick lime joined in 50 ℃ the hot water, static 15 minutes, stirred again 15 minutes, the calcium hydroxide coarse particles, coarse particles is crossed 200 eye mesh screens, removes residue, after the slurry natural subsidence, extracts supernatant liquor, the calcium hydroxide pulpous state thing of lower floor's high solids.Ratio by the theoretical amount of the reaction of the sodium carbonate in calcium hydroxide and the green liquor is 1.05, be mixed in the causticizing reaction still, under agitation be warming up to 90 ℃, react 0.5% crystal structure adjusting agent sodium citrate aqueous solution of adding calcium carbonate theoretical amount after 10 minutes and continued isothermal reaction 1 hour.After question response is intact, filter causticization liquid, reclaim liquid caustic soda with the hot wash filter cake.Filter cake is pulled an oar after adding clear water, is mixed with that to contain be 15% slurry admittedly, feeds kiln gas at normal temperatures again and carries out the secondary carbonization, is reaction end about the pH of suspension value reduces to 7.This product is fusiform microaggregate, and whiteness is greater than 92, and the pH value is 8.2, and settling volume is 3.1, is suitable for as papermaking filler.
Embodiment 2
After green liquor and calcium hydroxide slurry made with extra care, to be warmed up to 70 ℃ after the mixing of two liquid, isothermal reaction 15 minutes, the aqueous solution that adds 1.0% Boratex of calcium carbonate theoretical amount again continues reaction 1 hour, with embodiment 1 filtered and recycled alkali lye, pull an oar after filter cake added clear water, be made into solid content and be 18% slurry, feed kiln gas at normal temperatures again and carry out the secondary carbonization, about the pH value of suspension reduces to 7, be reaction end.This product is a sheet, and average grain diameter is 0.50 micron, and whiteness is greater than 92.This slurries filtration is got the filter cake of high solids, after dispersion treatment, be applicable to and do papermaking paint.
Embodiment 3
After green liquor and calcium hydroxide slurry made with extra care, add the aqueous solution of 1.0% sucrose of calcium carbonate theoretical amount after two liquid are mixed again, be warmed up to 50~70 ℃, isothermal reaction 1 hour.With embodiment 1 filtered and recycled alkali lye, pull an oar after filter cake added clear water, be made into solid content and be 14% slurry, feed kiln gas at normal temperatures again and carry out the secondary carbonization, about reducing to 7, the pH value of suspension is reaction end.2.5% stearic acid covering of calcium carbonate quantity is dissolved in 90 ℃ the hot water, the pH value that adds the alkali regulator solution carries out emulsification treatment to covering about 13.Covering is joined in the calcium carbonate slurry that is warmed up to 80 ℃ then, the constant temperature coating reaction is 1 hour in the time of 80 ℃, with slurry filtered while hot, drying, final baking temperature is not more than 100 ℃ and gets the super-fine active calcium carbide product, the average grain diameter of this product is 0.15 micron, and whiteness is greater than 92, and activation grade is big by 99%, oil factor is 28~35g/100gCaCO3, and does not have agglomeration.Can be used as the functional stuffing that high-grade rubber, plastics are used.
Claims (8)
1. a green liquor cleans the method that causticization reclaims calcium carbonate superfine powder, it is characterized in that, may further comprise the steps: a, to add percentage by weight in green liquor be the high polymer coagulant of 0.01-0.1%, the back natural subsidence stirs, remove lower floor's precipitum, stay clarification night work in upper strata standby for refining green liquor; B, be that the quick lime of 20-25% adds in 40-60 ℃ the hot water and makes calcium hydroxide slurry, above-mentioned slurry is separated removal of impurities with screen cloth or spinning liquid percentage by weight; C, by the ratio of the theoretical amount of the reaction of the sodium carbonate in calcium hydroxide and the green liquor be 1.05 mixes after, in 30-100 ℃, carry out causticizing reaction, and adding weight of calcium carbonate percentage is the crystal structure adjusting agent of 0.2-1.5% in reaction; D, the slurry after the causticization is carried out Separation of Solid and Liquid, filter cake is with 50-70 ℃ of hot wash, and filtrate is reclaimed as liquid caustic soda; E, filter cake making beating is added water be mixed with the suspension slurry that solid content is 15-20%, feed the further carbonization of carbon dioxide again and be neutral, obtain the calcium carbonate superfine powder slurry until slurry.
2, a kind of green liquor cleaning causticization according to claim 1 reclaims the method for calcium carbonate superfine powder, it is characterized in that, in the coating process of calcium carbonate superfine powder slurry, add and account for calcium carbonate superfine powder percentage by weight 0.5~3.5% covering, coating the processing time is 0.5~3.5 hour, make super-fine active calcium carbide, used covering is stearic acid and water-soluble KH-550 silane coupler.
3, a kind of green liquor cleaning causticization according to claim 1 reclaims the method for calcium carbonate superfine powder, it is characterized in that in refining calcium hydroxide slurry and the reaction of refining green liquor, the solid content of calcium hydroxide slurry is 25-40%.
4, a kind of green liquor cleaning causticization according to claim 1 reclaims the method for calcium carbonate superfine powder, it is characterized in that, add crystal structure adjusting agent in carry out at causticizing reaction preceding 0-40 minute, crystal structure adjusting agent is sodium hydrogen phosphate, sodium sulphate, potassium sulfate, borax and sucrose.
5, a kind of green liquor cleaning causticization according to claim 1 reclaims the method for calcium carbonate superfine powder, it is characterized in that the carbon dioxide that adds in the suspension slurry comes from kiln gas or paper plant, and its concentration is 20-35%, and temperature is 10-40 ℃.
6, a kind of green liquor cleaning causticization according to claim 1 reclaims the method for calcium carbonate superfine powder, it is characterized in that, with the surface conditioning agent that accounts for calcium carbonate superfine powder percentage by weight 1.0~3.5% calcium carbonate superfine powder is carried out surface treatment and make super-fine active calcium carbide, described surface conditioning agent is stearic acid and water-soluble KH-550 silane coupler, and the temperature of processing is 45~90 ℃.
7, a kind of green liquor cleaning causticization according to claim 1 reclaims the method for calcium carbonate superfine powder, it is characterized in that high polymer coagulant is Sodium Polyacrylate or water soluble starch.
8, a kind of green liquor cleaning causticization according to claim 1 reclaims the method for calcium carbonate superfine powder, it is characterized in that the final dried temperature of super-fine active calcium carbide is 85~110 ℃.
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