CN102275967B - Method for preparing nanometer calcium carbonate by using sintered desulfurated ash residues as raw materials - Google Patents
Method for preparing nanometer calcium carbonate by using sintered desulfurated ash residues as raw materials Download PDFInfo
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- CN102275967B CN102275967B CN2011102094832A CN201110209483A CN102275967B CN 102275967 B CN102275967 B CN 102275967B CN 2011102094832 A CN2011102094832 A CN 2011102094832A CN 201110209483 A CN201110209483 A CN 201110209483A CN 102275967 B CN102275967 B CN 102275967B
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- ash
- calcium carbonate
- lime
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- desulfurated
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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 82
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000002994 raw material Substances 0.000 title claims abstract description 19
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 48
- 238000005245 sintering Methods 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract description 4
- 230000023556 desulfurization Effects 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 16
- 230000003009 desulfurizing effect Effects 0.000 claims description 14
- -1 sorbitol acid anhydride Chemical class 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 7
- 239000000600 sorbitol Substances 0.000 claims description 7
- 239000008187 granular material Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229940070765 laurate Drugs 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 150000005323 carbonate salts Chemical class 0.000 claims description 3
- 239000007822 coupling agent Substances 0.000 claims description 3
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000001587 sorbitan monostearate Substances 0.000 claims description 3
- 229940035048 sorbitan monostearate Drugs 0.000 claims description 3
- 235000011076 sorbitan monostearate Nutrition 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract description 3
- 239000001099 ammonium carbonate Substances 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 238000001514 detection method Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000011265 semifinished product Substances 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 7
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000010440 gypsum Substances 0.000 description 6
- 229910052602 gypsum Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Chemical group CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 2
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011507 gypsum plaster Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N n-hexadecanoic acid Natural products CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y02P20/121—
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a method for preparing nanometer calcium carbonate by using sintered desulfurated ash residues as raw materials. The method comprises the following steps of: adding sulfuric acid with mass concentration of 5-35% into ash residues generated by sintering dry-method desulfuration, soaking for 12h, and washing repeatedly by using clear water; and by using the preprocessed desulfuration ash residue with the whiteness of larger than or equal to 85% as the raw materials, adding a surface dispersant with the mass accounting for 0.1-5.0% of the mass of the ash residues and ammonium bicarbonate 2.05-2.30 times of the surface dispersant in to the raw materials, stirring, grinding for 10-60min in an airtight container at the room temperature, then adding a surface activating agent with the mass accounting for 0.5-5.0% of the mass of the ash residues, raising temperature to 80-120 DEG C, continuously grinding for 20-60 min, washing a calcium carbonate semi-finished product with the grain size of 0.03-1.0 mum obtained after cooling by using clean water in a barrel till no white precipitates are generated in washed liquid under the detection of a BaC12 solution, and drying filtered residues to obtain a nanoscale calcium carbonate product. The preparation method has the advantages of making use of the desulfurated ash residues, solving the problem of the ash yard pollution of the desulfurated ash residues, protecting ecological environment, saving energy, reducing the emission of carbon dioxide and having popularizing and practical values.
Description
Technical field
The present invention relates to a kind ofly take the sintering desulfuration lime-ash as raw material prepares the method for nano-calcium carbonate, belong to the solid waste environmental protection and utilize field.
Background technology
Superfine light calcium carbonate is a kind of Novel super-thin solid material grown up in the later stage eighties in last century, as mineral filler, now has been widely used in the Industrial products such as rubber, plastics, papermaking, coating, printing ink.China has family more than 400 of Production of Light Calcium Carbonate enterprise now according to a preliminary estimate, nearly 3,000,000 tons of yearly capacity, and just with annual tempo more than 15%, increasing progressively.The enterprise of current domestic calcium carbonate superfine powder industrial scale maximum is Guangdong Province Enping Gavin Chemical Industrial Enterprise Co., Ltd., and annual production has reached 350,000 tons.And with fastest developing speed be the grand Science and Technology Co., Ltd. in Shandong, corporate share 2006, after the U.S. successfully goes on the market, has started gross investment and has reached 5,000,000,000 yuan and produce 1000000 tons of nano-calcium carbonate engineerings per year.
At present the prospects of light calcium carbonate industry production technique mainly contains: intermittently bubbling carbonizing method, multilevel spray carbonization, high-gravity reactive precipitation etc. continuously.The shortcoming of these techniques is that energy consumption calcium carbonate granule high, that produce is large, the market competitiveness a little less than, the enterprise of true profit is less.
At present, the sulfur removal technology that China's flue gas of sintering machine relates generally to mainly contains dry method, semidrying and wet method.Dry process mainly contains active coke absorption method, the flue gas circulating fluidized bed polycomponent dry method of LJS, ENS dry method, dense-phase tower method, the double-circulating fluid bed T method of GSCA, MEROS in duct sorbent injection dry method, LEC Wingdale row control dry method; Wet processing mainly contains Gypsum Wet, sulphur ammonium wet method, magnesium oxide wet method, two alkali lye wet method, ionic liquid wet method; Semidrying mainly contains NID flue circulation method, SDA rotary spraying technique.Various technique has relative merits, and it is serious that wherein sulphur ammonium wet method not only causes equipment corrosion, and the risk that has ammonia to reveal in operation; And the advantage such as the concrete operation cost of Gypsum Wet is low, but producing a large amount of desulfurization ashs, its secondary resource utilization is urgent need to solve the problem.
The desulfurization ash main chemical compositions of metallurgy industry is CaSO
3and CaSO
4, also contain CaCO
3, Ca (OH)
2, also containing a certain amount of elemental sulfur, this has just determined that desulfurization ash has from the plaster of paris different physicochemical properties is arranged.In the situation that water is arranged, calcium sulfate is a kind of good activity excitant, and complicated chemical reaction will occur the component in desulfurization ash.Owing to containing higher Ca, S in desulfurization ash, desulfurization material is not through washing, and desulfurization ash contains a small amount of Cl
-, and CaCl
2it concerning desulfurization ash, is also a kind of good activity excitant, chemical reaction will occur in lime-ash under this condition, the lime-ash particle surface is lost by aquation, the generating portion hydrated product, as C-S-H gel, Aft, AFm etc., make lime-ash without due pozzolanic activity, its comprehensive utilization is affected.
What is more important, desulfurization ash contains too high calcium sulfite composition, and it is directly used in the brickmaking of building the road, concrete admixture and plaster of Paris becomes impossiblely, has caused the desulfurization ash bulk deposition in countryside, form the ash of numerous serious environment pollution, taken a large amount of good farmlands.According to incompletely statistics, the sintering desulfuration lime-ash that more than 100, whole nation iron and steel enterprise abandons exceedes hundred million tons, how to utilize these desulfurization ashs to become a great problem of China steel enterprise.
Once had enterprise to adopt phosphogypsum to react productive target product ammonium sulfate with ammoniacal liquor, ammonium hydrogencarbonate, byproduct is the macrobead calcium carbonate that economic worth is lower.The calcium carbonate granule that this production technique is produced is large, similar to the difficult problem that current market prepares calcium carbonate by the method for leading to carbonic acid gas.Peace micro industry university " a kind of take gypsum prepare the method for superfine light calcium carbonate as raw material " (200710021709.X) has proposed to take calcium sulfate and has prepared the method for calcium carbonate superfine powder as raw material, Anhui University of Technology " a kind of method of simultaneously producing calcium carbonate superfine powder and volatile salt " (201010532199.4) has proposed to take calcium hydroxide and has prepared the method for calcium carbonate superfine powder as raw material, resemble process, but all avoided, industrial gypsum acid is insoluble, impurity reaches the problem that whiteness is inadequate more, not strong to the actual production directive significance.
Summary of the invention
The ash that the object of the present invention is to provide and a kind ofly can effectively utilize the sintering desulfuration lime-ash, solves the sintering desulfuration lime-ash pollute and save the energy, the sintering desulfuration lime-ash of take that reduces CO2 emissions prepares the method for nano-calcium carbonate as raw material.
For achieving the above object, the technical solution used in the present invention is: of the present inventionly a kind ofly take the sintering desulfuration lime-ash and be divided into the pre-treatment of sintering desulfuration lime-ash and the preparation of nano-calcium carbonate as the method that raw material prepares nano-calcium carbonate.
The lime-ash raw material produced with sintering dry desulphurization is put into to container, in this container, add the sulfuric acid that mass concentration is 5～35%, the quality that adds sulfuric acid is 1～3 times of sintering desulfuration lime-ash quality, soaks 12h.Desulfurization ash after soaking is washed 1～3 time with clear water repeatedly, remove residual calcium carbonate granule, calcium hydroxide particle and part iron, manganese and magnesium ion etc. in desulfurization ash, the initial whiteness that guarantees desulfurization ash is more than or equal to 85%, becomes the pretreatment desulfurizing lime-ash.
Get containing the pretreatment desulfurizing lime-ash of mass concentration 1～5% water and put into container, to the surface dispersant that adds pretreatment desulfurizing lime-ash solid masses 0.1～5.0% in container, the bicarbonate of ammonia solid or the soluble carbonate salt that add again 2.05～2.30 times of pretreatment desulfurizing lime-ash solid masses, stir, grind 10～60min 5～35 ℃ of room temperatures in encloses container, add again the calcium carbonate surfactant that quality is pretreatment desulfurizing lime-ash solid masses 0.5～5.0%, be warming up to 80～120 ℃, continue to grind 20～60min, obtaining particle diameter after cooling is the calcium carbonate work in-process of 0.03～1.0 μ m.These calcium carbonate work in-process are used in washing beck to clear water agitator treating 1～3 time, until washing lotion BaCl
2the solution check, without white precipitate, by the dry baking of filter residue, obtains the nanometer grade calcium carbonate product.
Surface dispersant is selected from: anhydrous sorbitol acid anhydride mono-laurate, anhydrous sorbitol acid anhydride monopalmitate, sorbitan monostearate or Sodium dodecylbenzene sulfonate (also can be selected from wherein several, in identical weight ratio).
Surfactant is selected from: stearic acid, titanic acid ester, Aluminate, phosphate coupling agent or silane coupling agent (also can be selected from wherein several, in identical weight ratio).
What adopt that as above technical scheme provides a kind ofly take method that the sintering desulfuration lime-ash prepares nano-calcium carbonate as raw material compared with prior art, and technique effect is:
1. can effectively utilize sintering desulfuration lime-ash (or slag), protect ecotope;
2. save the energy;
3. reduced Carbon emission;
4. economic benefit and social benefit are obvious.
Embodiment
Below in conjunction with embodiment, the specific embodiment of the present invention is described in further detail.
Describedly a kind ofly take the sintering desulfuration lime-ash and comprise the pre-treatment of sintering desulfuration lime-ash and the preparation of nano-calcium carbonate as the method that raw material prepares nano-calcium carbonate.
Described sintering desulfuration lime-ash is the waste residue that sintering dry desulphurization produces, take the sintering desulfuration lime-ash as raw material, this raw material is put into to container, in this container, add the sulfuric acid that mass concentration is 5～35%, the sulfuric acid quality added is 1～3 times of sintering desulfuration lime-ash quality (weight), soaks 12h.Desulfurization ash after soaking, repeatedly with clear water washing 1～3 time, is removed to residual calcium carbonate granule, calcium hydroxide particle and iron, manganese, magnesium ion in desulfurization ash, guarantee that the initial whiteness of desulfurization ash is more than or equal to 85%, become the pretreatment desulfurizing lime-ash.
Get water content (wt) 1～5% pretreated desulfurization ash and put into container, to the surface dispersant that adds pretreatment desulfurizing lime-ash solid masses 0.1～5.0% in container, the effect of dispersion agent is that the calcium carbonate granule generated is not reunited, even particle size distribution.The bicarbonate of ammonia solid or the soluble carbonate salt that add again 2.05～2.30 times of pretreatment desulfurizing lime-ash solid masses, stir, grind 10～60min 5～35 ℃ of room temperatures in encloses container, add again the calcium carbonate surfactant that quality is pretreatment desulfurizing lime-ash solid masses 0.5～5.0%, be warming up to 80～120 ℃, continue to grind 20～60min, obtaining particle diameter after cooling is the calcium carbonate work in-process of 0.03-1.0 μ m, clear water agitator treating 1～3 time in washing beck for the calcium carbonate work in-process that are 0.03～1.0 μ m (micron) by this particle diameter, until filtrate is used BaCl
2the solution check, without white precipitate, is dried (the best is oven drying at low temperature) by filter residue, obtains nanometer (nm) level calcium carbonate product.
When above-mentioned reaction is carried out, separate out the ammonium sulphite crystal closing in the tail gas introducing condenser of overflowing in close container, or can obtain ammonium sulfate product through the strong oxide treatment of air pressurized.
Surface dispersant is selected from: anhydrous sorbitol acid anhydride mono-laurate, anhydrous sorbitol acid anhydride list palmitic acid lipid, sorbitan monostearate or Sodium dodecylbenzene sulfonate.
Surfactant is selected from: stearic acid, titanic acid ester, Aluminate, phosphate coupling agent or silane coupling agent.
Embodiment 1: take the sintering desulfuration ash ground-slag 1000g of Hubei steel enterprise, the sulfuric acid (H with 5%
2sO
4) 2000ml soaks 12h, adds water and stirs, and gets the slip washing on upper strata 80% at every turn, filter, repeat 3 times, filter residue, add Sodium dodecylbenzene sulfonate 1g, processing industry ammonium hydrogencarbonate solid 600g, grind after 60min with the little mill of experiment after stirring that to add the water washing filter 23 inferior, washs to filtrate and use BaCl
2the solution check is without white precipitate, and drying, obtain nano level light calcium carbonate, and product cut size is 0.10 μ m approximately, and collection filtrate adds dilute sulphuric acid adjusting PH and obtains ammonium sulphite for evaporate to dryness after neutral.
Embodiment 2: take the sintering desulfuration ash ground-slag 1000g of Hunan valin group steel enterprise, the sulfuric acid (H with 5%
2sO
4) 3000ml soaks 12h, adding water stirs, get the slip washing on upper strata 80% at every turn, filter, repeat 3 times, then add 200g industry calcium oxide to filter residue, and add 1g anhydrous sorbitol acid anhydride mono laurate fat and 600g industrial carbonic acid hydrogen ammonia solid, add 20% ammoniacal liquor 50ml by above-mentioned material stirring evenly after, grind again 20min with after the little mill grinding of experiment 30min, adding the 5g silane coupling agent.Add water washing filter 23 time, wash to filtrate and use BaCl
2the solution check is without white precipitate, and drying, obtain superfine light calcium carbonate, and product cut size is 0.03 μ m approximately.In above-mentioned reaction, the tail gas that reaction is produced with after the way oxidation of pressure oxidation again evaporate to dryness obtain ammonium sulfate product.
Embodiment 3: take dried sintering desulfuration lime-ash 100g and industrial hydrogen calcium oxide 100g that Hunan valin group steel enterprise produces, adding water 300ml and Sodium dodecylbenzene sulfonate 1.0g stirs, add again sodium bicarbonate solid 210g, after stirring 90min, filter, collect filtrate and add dilute sulphuric acid and regulate PH for after neutral and add in the situation of forced oxidation, evaporate to dryness reclaims S-WAT.Filtrate water repetitive scrubbing to filtrate is used BaCl
2, solution is checked without white precipitate, and drying, obtain superfine light calcium carbonate, granularity 1 μ m.
Method of the present invention is suitable for the various chemical gypsums such as power plant desulfurization gypsum, phosphogypsum, fluorgypsum, citric acid gypsum equally.
Claims (2)
1. take the sintering desulfuration lime-ash and prepare the method for nano-calcium carbonate as raw material for one kind, it is characterized in that: the lime-ash raw material produced with sintering dry desulphurization is put into to container, add the sulfuric acid that mass concentration is 5～35% in this container, the quality that adds sulfuric acid is 1～3 times of desulfurization ash quality, soak 12h, desulfurization ash after soaking is washed 1～3 time with clear water repeatedly, remove residual calcium carbonate granule, calcium hydroxide particle and iron, manganese and magnesium ion in desulfurization ash, the initial whiteness of desulfurization ash is more than or equal to 85%, becomes the pretreatment desulfurizing lime-ash;
Get containing the pretreatment desulfurizing lime-ash of mass concentration 1～5% water and put into container, to the surface dispersant that adds pretreatment desulfurizing lime-ash solid masses 0.1～5.0% in container, the bicarbonate of ammonia solid or the soluble carbonate salt that add again 2.05～2.30 times of pretreatment desulfurizing lime-ash solid masses, stir, grind 10～60min 5～35 ℃ of room temperatures in encloses container, add again the calcium carbonate surfactant that quality is pretreatment desulfurizing lime-ash solid masses 0.5～5.0%, be warming up to 80～120 ℃, continue to grind 20～60min, obtaining particle diameter after cooling is the calcium carbonate work in-process of 0.03～1.0 μ m, these calcium carbonate work in-process are used in washing beck to clear water agitator treating 1～3 time, until washing lotion BaCl
2the solution check, without white precipitate, is dried filter residue, obtains the nanometer grade calcium carbonate product, described
Surface dispersant is selected from: anhydrous sorbitol acid anhydride mono-laurate, anhydrous sorbitol acid anhydride monopalmitate, sorbitan monostearate or Sodium dodecylbenzene sulfonate;
Surfactant is selected from: stearic acid, titanic acid ester, Aluminate, phosphate coupling agent or silane coupling agent.
2. according to claim 1ly a kind ofly take the sintering desulfuration lime-ash and prepare the method for nano-calcium carbonate as raw material, it is characterized in that: if pretreated sintering desulfuration clinker water content (wt) is greater than 15%, the industrial calcium oxide or the calcium hydroxide that add sintering desulfuration lime-ash solid masses 10～20%, participate in the preparation section of nano-calcium carbonate together.
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| CN101045544A (en) * | 2007-04-26 | 2007-10-03 | 安徽工业大学 | Method for preparing superthin light calcium carbonate using plaster as raw material |
| CN101538060A (en) * | 2009-05-05 | 2009-09-23 | 贵州西洋肥业有限公司 | Method for producing light calcium carbonate and coproducing hydrogen sulfide by using crude calcium sulfide |
| CN101830494A (en) * | 2010-05-11 | 2010-09-15 | 安徽工业大学 | Method for preparing active calcium carbonate by taking gypsum as raw material |
| CN102112637A (en) * | 2008-05-30 | 2011-06-29 | 阿尔托大学基金会 | Method of producing calcium carbonate from waste and byproducts |
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| CN101045544A (en) * | 2007-04-26 | 2007-10-03 | 安徽工业大学 | Method for preparing superthin light calcium carbonate using plaster as raw material |
| CN102112637A (en) * | 2008-05-30 | 2011-06-29 | 阿尔托大学基金会 | Method of producing calcium carbonate from waste and byproducts |
| CN101538060A (en) * | 2009-05-05 | 2009-09-23 | 贵州西洋肥业有限公司 | Method for producing light calcium carbonate and coproducing hydrogen sulfide by using crude calcium sulfide |
| CN101830494A (en) * | 2010-05-11 | 2010-09-15 | 安徽工业大学 | Method for preparing active calcium carbonate by taking gypsum as raw material |
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