CN1249176C - Method for purifying and whitening calcium carbonate - Google Patents
Method for purifying and whitening calcium carbonate Download PDFInfo
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- CN1249176C CN1249176C CN 200310109648 CN200310109648A CN1249176C CN 1249176 C CN1249176 C CN 1249176C CN 200310109648 CN200310109648 CN 200310109648 CN 200310109648 A CN200310109648 A CN 200310109648A CN 1249176 C CN1249176 C CN 1249176C
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- Prior art keywords
- lime carbonate
- whitening
- calcium carbonate
- slurry
- purification method
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- 238000000034 method Methods 0.000 title claims abstract description 43
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 41
- 230000002087 whitening effect Effects 0.000 title claims abstract description 29
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 40
- 238000000746 purification Methods 0.000 claims abstract description 28
- 238000012545 processing Methods 0.000 claims abstract description 21
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 14
- -1 kaoline Chemical compound 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010456 wollastonite Substances 0.000 claims abstract description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims abstract description 4
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 78
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 17
- 238000005282 brightening Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 13
- 230000002829 reductive effect Effects 0.000 claims description 13
- 229960004418 trolamine Drugs 0.000 claims description 13
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 11
- 239000003352 sequestering agent Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 8
- 239000000920 calcium hydroxide Substances 0.000 claims description 8
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- 230000029087 digestion Effects 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 235000017550 sodium carbonate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 5
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 5
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 5
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 4
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 4
- PENRVBJTRIYHOA-UHFFFAOYSA-L zinc dithionite Chemical compound [Zn+2].[O-]S(=O)S([O-])=O PENRVBJTRIYHOA-UHFFFAOYSA-L 0.000 claims description 4
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical compound NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 claims description 3
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 claims description 3
- SBGKURINHGJRFN-UHFFFAOYSA-M hydroxymethanesulfinate Chemical compound OCS([O-])=O SBGKURINHGJRFN-UHFFFAOYSA-M 0.000 claims description 3
- 125000005341 metaphosphate group Chemical group 0.000 claims description 3
- 150000003016 phosphoric acids Chemical class 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000058 polyacrylate Polymers 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 2
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical compound OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 239000011575 calcium Substances 0.000 abstract description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 235000010755 mineral Nutrition 0.000 abstract description 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract 8
- 229940088417 precipitated calcium carbonate Drugs 0.000 abstract 2
- 239000000440 bentonite Substances 0.000 abstract 1
- 229910000278 bentonite Inorganic materials 0.000 abstract 1
- 239000002738 chelating agent Substances 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000000873 masking effect Effects 0.000 abstract 1
- 238000010422 painting Methods 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000011143 downstream manufacturing Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000012493 hydrazine sulfate Substances 0.000 description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000009955 starching Methods 0.000 description 2
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
The present invention provides calcium carbonate, particularly a method for purifying and whitening precipitated calcium carbonate. Ca (OH) 2 suspension or CaCO3 clinker slurry is processed by a chemical method so as to remove color base in the clinker slurry; thus, the brightness, the whiteness and the purity of products are increased, and simultaneously, the grade of raw materials and the utilization rate of resource are increased. The purification and whitening method of the calcium carbonate is characterized in that the calcium carbonate suspending slurry is added with 0.01 to 0.5% of one or a plurality of a reducing agent, a masking agent and a chelating agent are added into the calcium carbonate suspending slurry by weight, the slurry concentration is from 8 to 50%, and the calcium carbonate suspending slurry is stirred for 30 to 120 minutes at the temperature from 30 to 90 DEG C; then, the purified and whitened calcium carbonate is obtained after filtration, baking and sieving. The technological condition designed by the present invention can process the precipitated calcium carbonate, and can also purify and whiten the inorganic filling (painting) materials of ground calcium carbonate (GCC), bentonite, kaoline, talcum powder, wollastonite, etc.; the processing effects are favorable; the technological condition of the present invention can be fully used for purifying and whitening inorganic raw mineral materials in the industrial field.
Description
Technical field
The present invention relates to a kind of purification method of whitening of purification method of whitening, especially precipitated chalk of lime carbonate, belong to technical field of inorganic chemical industry.
Background technology
Lime carbonate especially precipitated chalk is widely used in industrial circles such as plastics, rubber, coating, papermaking and food, medicine, electronics as filler or coating pigment use.The whiteness of product is to weigh the important indicator of quality product, and prior art has utilization V-Brite B or zinc dithionite reducing substances that kaolin is bleached processing, with V-Brite B (Na
2S
2O
4) bleaching is for example, this method is many carries out in acidic medium, and often regulating acidity with sulfuric acid (or hydrochloric acid), to cause pH value be sour environment or the acidic reduction atmosphere of 2.5-5, is equipped with V-Brite B to being brightened by the acting in conjunction of drift system.Its principle is by the metallochromy oxide compound (Fe in the drift
2O
3Deng) be reduced the ferrous sulfate (FeSO that generates solubility
4) and remove along with dehydration procedure is filtered.Chinese patent CN85103821A also discloses and added hydrazine hydrate or the V-Brite B that is equivalent to lime carbonate quality (in butt) 0.05-0.5% when the quicklime slaking temperature reaches 60-95 ℃, or be equivalent to the trolamine of lime carbonate quality 0.05-0.5%, directly enter carbonating workshop section, can obtain the product that whiteness is the 88-92 degree through the choosing slurry.
Aforesaid method is used for all bigger limitation of existence are brightened in the purification of lime carbonate, because, lime carbonate belongs to weak acid strong alkali salt class material, if remain on than carrying out reduction reaction under the strong acidic condition by the pH value of strong acid adjusting lime carbonate, the essential property of lime carbonate then can be changed.
Usually the whiteness of the precipitated chalk of producing according to chemical synthesis process (PCC) is about about 90 degree, as bright strict control Wingdale raw material and operations such as calcining, digestion, carbonation and drying, can obtain the calcium carbonate product that whiteness is the 93-95 degree, but cause the complicated and production cost of technology to improve greatly like this.And another to conspicuous contradiction is, lime carbonate downstream manufacturing and processing enterprise is more and more higher to quality (especially whiteness) requirement of calcium carbonate powder, and high-grade Wingdale raw material is fewer and feweri.
Summary of the invention
The object of the present invention is to provide a kind of purification method of whitening of purification method of whitening, especially precipitated chalk of lime carbonate, handle Ca (OH) by chemical process
2Suspension or CaCO
3The grog slurry is removed the coloured group in the slurries, to increase product brightness, improves whiteness and purity, improves raw material grade and resource utilization simultaneously.
Technical scheme of the present invention is achieved in that the purification method of whitening of this inorganic mineral raw material, its feature comprises: under alkaline condition, in calcium carbonate product suspension slip, add the reductive agent be equivalent to its weight 0.01-0.5%, sequestering agent, sequestrant wherein one or more, pulp density 8-50%, temperature 30-90 ℃, stir process 30-120 minute; Filter, oven dry is sieved promptly.
The reductive agent that is suitable for described in the purification method of whitening of described lime carbonate comprises: V-Brite B, thiourea peroxide, zinc dithionite,, hydrazine hydrate, anhydrous hydrazine, unsymmetrical dimethyl hydrazine, hydrazine hydrochloride (hydrazine hydrochloride), hydrazonium sulfate (hydrazine sulfate), oxammonium hydrochloride, oxammonium sulfate, sulphite or hydrosulphite, hydroxymethanesulfinate wherein one or more.
The sequestering agent that is suitable for described in the purification method of whitening of described lime carbonate comprises organic amine compound: trolamine, quadrol, diethylenetriamine, Triethylenetetramine (TETA) wherein one or more.
Ratio when reductive agent and sequestering agent are used described in the purification method of whitening of described lime carbonate is 0.01-1: 0.1-2.
The sequestrant that is suitable for described in the purification method of whitening of described lime carbonate comprise ammonia carboxylic complex compound: EDTA or its sodium salt, three second triamine-pentaacetic acids, nitrilotriacetic acid(NTA), hydroxyethylethylene diamine tri-acetic acid wherein one or more.
Ratio when reductive agent and complexone are used described in the purification method of whitening of described lime carbonate is 1: 1.
The purification method of whitening of described lime carbonate also comprises: in the slip of inorganic mineral raw material, add the dispersion agent be equivalent to inorganic mineral raw material weight 0.05-2%, comprise polyacrylate, phosphoric acid salt, phosphite or metaphosphate wherein one or more.
The processing of brightening for lime carbonate raw material (calcium hydroxide) described in the purification method of whitening of described lime carbonate can be in calcium oxide digestion near fully the time, utilize the digestion heat release to handle during greater than 80 ℃, or handle when behind the choosing slurry, making calcium hydroxide charge pulp temperature greater than 80 ℃ by intensification again in temperature.
Brightening processing and can under strong alkaline condition, carry out for lime carbonate charge pulp (calcium hydroxide).
The purification method of whitening of described lime carbonate of yellow soda ash or sodium hydroxide or the mixture of the two add 0.5-5% in to(for) described lime carbonate grog slurry, in 100-150 ℃, lime carbonate grog slurry is carried out the molten processing of alkali, the coloured group beyond the stripping calcium-magnesium removing ion.
The inorganic mineral raw material that aforesaid method brightens be can use in the purification method of whitening that elongation technology scheme of the present invention is described lime carbonate and precipitated chalk, water-ground limestone, wilkinite, kaolin, talcum powder, wollastonite comprised.
Method provided by the present invention is to pass through Ca (OH) in the different workshop sections that lime carbonate is produced
2, CaCO
3Grog slurry etc. carry out once or above purification of secondary and obtain to have the purity height, calcium carbonate product that whiteness is good.The calcium carbonate product whiteness can improve 2-6 percentage point according to the difference of number of processes on original whiteness basis, can reach 93-95 respectively, between the 94-97.5.This lime carbonate with high-purity, high white performance has important application in industry such as papermaking, plastics, light-colour rubber.
The processing condition of the present invention's design, except lime carbonate, inorganic filling out (face) such as water-ground limestone (GCC), wilkinite, kaolin, talcum powder, wollastonite are expected to purify to brighten, also obtained better effects, may extend into fully purifies to the inorganic mineral raw produce of these industrial circles brightens.
Embodiment
Below in conjunction with processing example explanation the specific embodiment of the present invention at variant production and processing condition.
Embodiment 1: the lime carbonate grog slurry 1000ml that takes off dense 11 degree Beaume of tower, calcium carbonate content is 141g/l, slip is warming up to 68 ℃, temperature equates during with following tower, stir and to add EDTA0.14g and V-Brite B 0.14g (all by lime carbonate quality 0.1%) down successively, the insulated and stirred reaction finished in 45 minutes.Treated 1000ml lime carbonate grog slurry is divided into two, half direct filtration, dries, sieve, second half refilters, dries, sieves after washing, meanwhile, without the magma that brightens processing also after filtration, dry, sieve.
Detected result: former pulp brightness 90.38, direct filtration whiteness 93.23, washing back whiteness 93.88.The amplitude of brightening is respectively 2.85 and 3.5 degree.
The foregoing description provided a kind of by a kind of ammonia carboxylic complexing stablizer to CaCO
3Fe in the grog slurry
+ 3Ion carries out complexing, adds a kind of reducing substances then, with Fe
+ 3Be reduced to Fe
+ 2Ion, along with centrifuge dehydration workshop section with Fe soluble in water
+ 2The method that ion filter is removed; Preferred complexone comprises ethylenediamine tetraacetic acid (EDTA) (EDTA) and sodium salt thereof, three second triamine-pentaacetic acids (DTPA), nitrilotriacetic acid(NTA) (NTA), hydroxyethylethylene diamine tri-acetic acid (HEDTA) etc.Preferred reducing substances comprises V-Brite B, zinc dithionite, thiourea peroxide (formamidine sulfinic acid), hydrazine hydrate, anhydrous hydrazine, unsymmetrical dimethyl hydrazine, hydrazine hydrochloride (hydrazine hydrochloride), hydrazonium sulfate (hydrazine sulfate), oxammonium hydrochloride, oxammonium sulfate, sulfurous acid (hydrogen) salt, hydroxymethanesulfinate etc.Preferred other material also has thiocyanate-, sulphosalicylic acid etc.
Treatment condition: pH value 7-10, best pH value environment is 7-9; 50-90 ℃ of lime carbonate grog slurry temperature, optimum range 60-85 ℃; Lime carbonate grog slurry concentration 8-50%, most economical rational concentration 10-30%; The consumption of complexone is the 0.03-0.2% with respect to the lime carbonate quality, and the consumption of reducing substances is the 0.03-0.2% with respect to the lime carbonate quality.
The reductibility of carrying out in lime carbonate grog slurry brightens Fe
+ 3Reaction be reversible, it can be reoxidized or make because of pH value is too high the product color reversion by airborne oxygen.This problem is comprising the industrial application meaning of two aspects, and one must avoid being oxidized to high volence metal ion once again and making and brighten inefficacy through the reductive low valence metal ion brightening workshop section as far as possible; The two adds calcium oxide, calcium hydroxide or sodium hydroxide etc. in can the backwater after brightening makes backwater obtain handling, to avoid environmental pollution.And the calcium oxide that waste water treatment is used, calcium hydroxide can be by directly obtaining in the waste residue of production workshop section.
Embodiment 2: taking off tower concentration is the lime carbonate grog slurry 1000ml of 19 degree Beaume, record calcium phosphate content and still be 141g/l, slip is warming up to 72 ℃, stir and add Sodium hexametaphosphate 99 0.14g down successively, EDTA0.14g and V-Brite B 0.14g (by the lime carbonate quality 0.1%), insulated and stirred reaction finished in 45 minutes.Other treating method is all with embodiment 1.
Detected result: former pulp brightness 92.4, direct filtration whiteness 95.2, washing back whiteness 95.7.The amplitude of brightening is respectively 2.80 degree and 3.3 degree.
The processing of in embodiment 2, the lime carbonate grog being starched, if it is too high, dispersed bad to relate to grog slurry viscosity, needing to add a kind of ion dispersion agent is disperseed, this dispersion agent is preferably polyacrylate, phosphoric acid salt, phosphite or metaphosphate, Sodium hexametaphosphate 99 more precisely, consumption is the 0.05-2% of lime carbonate quality.
Embodiment 3:Ca (OH)
2Suspension starching concentration 9 degree Beaume, last tower side amount 35m
343 ℃ of last tower temperature, 69 ℃ of lime carbonate grog slurry temperature after carbonation reaction finishes, lime carbonate grog slurry behind the following tower is 16 degree Beaume, and the about 5000kg of the theoretical contents on dry basis of lime carbonate adds Sodium hexametaphosphate 99 10kg (0.2%) under stirring successively, EDTA5kg (0.1%), V-Brite B 5kg (0.1%), stirring reaction 45 minutes carries out treatment and finishing sections such as centrifuge dehydration.
Detected result: former pulp brightness 91.2, centrifugal filter cake oven dry back whiteness 94.3, dressing sieve finished product whiteness 94.2 degree.The amplitude of brightening is respectively 3.10 degree and 3.0 degree.
Embodiment 4:Ca (OH)
2Suspension starching concentration 18 degree Beaume, last tower side amount 22m
346 ℃ of last tower temperature, 65 ℃ of lime carbonate grog slurry temperature after carbonation reaction finishes, lime carbonate grog slurry behind the following tower is 14 degree Beaume, the about 5000kg of the theoretical contents on dry basis of lime carbonate adds EDTA5kg (0.1%), V-Brite B 5kg (0.1%) under stirring successively, stirring reaction 45 minutes carries out treatment and finishing sections such as centrifuge dehydration.
Detected result: former pulp brightness 91.55, centrifugal filter cake oven dry back whiteness 94.5, dressing sieve finished product whiteness 94.7 degree, the amplitude of brightening is respectively 2.95 degree and 3.15 degree.
Embodiment 5: taking off tower concentration is the lime carbonate grog slurry 1000ml of 19 degree Beaume, record the lime carbonate solid content and still be 142g/l, slip is warming up to 70 ℃, and the thiourea peroxide with 0.05% (formamidine sulfinic acid) replaces V-Brite B, and treating method is with embodiment 2.
It is bright to detect knot: former pulp brightness 92.3, direct filtration whiteness 93.02, washing back whiteness 95.4.The amplitude of brightening is respectively 0.72 degree and 3.1 degree.
If list is used thiourea peroxide, brighten slip drying whiteness without any increase, be former pulp brightness substantially; If be used with thiourea peroxide and EDTA, without washing, whiteness does not have bigger improvement yet, then is improved largely through washing back whiteness.
Embodiment 6: taking off tower concentration is the lime carbonate grog slurry 1000ml of 14 degree Beaume, records the lime carbonate solid content and still is 142g/l, and slip is warming up to 70 ℃, and the oxammonium hydrochloride with 0.1% replaces V-Brite B, and treating method is with embodiment 2.
Detected result: former pulp brightness 91.9, direct filtration whiteness 93.5, washing back whiteness 94.1.The amplitude of brightening is respectively 1.6 degree and 2.2 degree.
Embodiment 7: taking off tower concentration is the lime carbonate grog slurry 1000ml of 14 degree Beaume, records the lime carbonate solid content and still is 142g/l, and slip is warming up to 70 ℃, and the hydrazine hydrate solution with 0.1% replaces V-Brite B, and treating method is with embodiment 2.
Detected result: former pulp brightness 91.9, direct filtration whiteness 93.2, washing back whiteness 93.9.The amplitude of brightening is respectively 1.3 degree and 2.0 degree.
Embodiment 8: getting concentration is 9 degree Beaume Ca (OH)
2Suspension 1000ml, the about 142g/l of the theoretical contents on dry basis of lime carbonate, 45 ℃ add triethanolamine solution 1.5ml down, and stirring reaction after 30 minutes is divided into two this suspension, half direct filtration, dry, sieve, second half refilters, dries, sieves after washing.
Detected result: primary pulp brightness 88.38, direct filtration whiteness 90.02, washing back whiteness 91.0.The amplitude of brightening is respectively 1.64,2.62 degree.
The foregoing description provides the service condition by sequestering agent, is preferably trolamine, quadrol, diethylenetriamine, Triethylenetetramine (TETA) etc., and trolamine, quadrol, diethylenetriamine, Triethylenetetramine (TETA) etc. can be used in Ca (OH) separately
2In the suspension, perhaps these organic amines are used with any one reducing substances of the present invention respectively, the most preferred Ca (OH) that is used for
2The pure reductive agent that brightens processing of suspension dike is a thiourea peroxide.The consumption of these organic amines and thiourea peroxide is respectively with respect to the 0.05-1% of lime carbonate quality and 0.005-0.5%.
Must be when trolamine etc. use separately to Ca (OH) under 30-100 ℃
2The Fe of suspension
2O
3, Al
2O
3Shelter processing, pH value is about the 12.5-13.2 scope, suspension concentration 8-50%, the consumption of trolamine is the 0.02-2% with respect to the calcium hydroxide quality, treatment time is 30-120 minute, dispose and then the moisture in this suspension is sloughed moisture by enrichment left-falling stroke water or centrifuge dehydration operation, add fresh water again, send into the carburizing reagent still and carry out carbonation reaction to suitable concn.
Embodiment 9:Ca (OH)
2Suspension temperature is 80 ℃, and adding and adding the theoretical contents on dry basis of lime carbonate behind the triethanolamine solution 1.5ml again is 0.1% EDTA, and operation is with embodiment 8.
Detected result: primary pulp brightness 88.38, direct filtration whiteness 90.24, washing back whiteness 92.85.The amplitude of brightening is respectively 1.86,4.37 degree.
Embodiment 10: getting concentration is 9 degree Beaume Ca (OH)
2Suspension 0.05m
3, the about 7500g of the theoretical contents on dry basis of lime carbonate, Ca (OH)
2Suspension temperature is chosen in 45 ℃, stir and add trolamine 35ml down, react and filter this suspension with filter bag after 30 minutes, convert water again to original content, send into small-sized simulated experiment tower and together carry out carbonation reaction with former tower slurry, reaction finishes, and again by Sodium hexametaphosphate 99: EDTA: V-Brite B respectively is that 0.1% usage ratio adds successively in former tower slurry and the experiment slurry and respectively two kinds of grogs slurries brightened processing, records comparing result after the omnidistance reaction end:
Embodiment 11: with embodiment 8, still use primary slurry, difference is Ca (OH)
2Suspension temperature is 80 ℃, and adding and adding the theoretical contents on dry basis of lime carbonate behind the triethanolamine solution 1.5ml again is 0.025% thiourea peroxide stirring reaction 30 minutes.
Detected result: primary pulp brightness 88.38, direct filtration whiteness 90.15, washing back whiteness 94.03.The amplitude of brightening is respectively 1.75,5.65 degree.
Experimental technique is identical, just trolamine is changed to quadrol, diethylenetriamine and Triethylenetetramine (TETA) respectively, and all between 94.0-94.5, the amplitude of brightening is about the 5.5-6.0 degree to washing back whiteness.
Embodiment 12: yellow soda ash or sodium hydroxide or the mixture of the two at above-mentioned lime carbonate grog slurry adding 0.5-5%, in 100-150 ℃, lime carbonate grog slurry is carried out the molten processing of alkali, and make soluble mineral impurity such as SiO
2, Fe
2O
3, Fe
2+, Al
3+Generate inclined to one side sodium ferrite, sodium metaaluminate, water glass and Na[Al (OH) etc. component
4] or the like and so on water-soluble cpds leach, with insoluble Ca
2+, Mg
2+Component is separated, and brightens purpose thereby reach to purify.
Test is adopted uncovered form or with Stainless steel pressure cooking-vessel lime carbonate grog slurry was boiled under 100-150 ℃ 1 hour, and again this grog pulp-water being washed till pH value is 7-8, and whiteness has improved the 2-4 degree.
Any reductive agent of enumerating in complexone and the technical scheme in the above embodiment of the present invention is used the whiteness that all can make lime carbonate must be to bigger improvement, carries out two sections and brightens processing if be used in combination, and the whiteness of gained will be higher.Embodiments of the invention do not constitute any restriction to claim of the present invention just in order more properly to describe realization approach of the present invention.
Embodiment 13: get the water-ground limestone sample 300g after levigate, place the 1000ml beaker, add water to the 1000ml scale, be warming up to 70 ℃ under stirring, add each 0.3g of EDTA and V-Brite B successively, handle and after 45 minutes this slip is washed, filters, dries, sieved.
Detected result: water-ground limestone sample whiteness 93.1, brighten the whiteness 95.7 after the processing, amplification 2.6.
In addition, get paper making and cloth coating with water-ground limestone (the lime carbonate solid content is 70%) through the slip 1000ml behind the first road ball mill grinding, it is 64 ℃ that this slip goes out the machine natural temperature, in this slip, add EDTA and each 0.7g of V-Brite B then successively, handle and after 45 minutes this slip is washed, filters, dries, sieved.
Detected result: whiteness 93.3 after the raw sample drying, brighten the whiteness 96.8 after the processing, amplification 3.5.
Embodiment 14: get 4 each 500g of commercially available kaolin breeze sample, add suitable quantity of water and stir, in the ratio of the theoretical contents on dry basis 200g/l of kaolin, place the beaker of 4 1000ml respectively, add yellow soda ash Na
2CO
3Regulating the slip pH value is 9.5, be heated to 80 ℃, add each 2.0ml of trolamine, quadrol, diethylenetriamine and Triethylenetetramine (TETA) then respectively in 4 beakers, respectively add 0.15% thiourea peroxide again, stirring reaction was washed this slip, filter, dry, sieve after 30 minutes.
Detected result:
Embodiment 15: get wilkinite sample ore 500g, soak after 3 hours and smash slurry, and with the big and heavy particle of 325 mesh sieve filterings, carry out brute force with strong mixer again and mix.Allocating this pulp density then is 20%, measures this ore pulp to beaker scale 1000ml, uses yellow soda ash Na
2CO
3Regulating the slip pH value is 9.0, is heated to 80 ℃, and each adds with respect to the EDTA of contents on dry basis 0.8% and 0.5% thiourea peroxide again, and stirring reaction was washed this slip, filter, dry, sieve after 30 minutes.
Detected result: whiteness 39.1 after the raw pulp drying, brighten the whiteness 86.7 after the processing, amplification 47.6.
Claims (10)
1, the purification method of whitening of lime carbonate, under alkaline condition, in the suspension slip of lime carbonate grog or raw material, add the reductive agent be equivalent to weight of calcium carbonate 0.01-0.5%, sequestering agent, sequestrant wherein one or more, its feature comprises: add polyacrylate, phosphoric acid salt, phosphite or metaphosphate one or more dispersion agents wherein be equivalent to its weight 0.05-2% in the slip of lime carbonate, lime carbonate pulp density 8-50%, temperature 30-90 ℃, stir process 30-120 minute; Be the 7-8 after-filtration through being washed to the pH value, oven dry is sieved promptly.
2, the purification method of whitening of lime carbonate according to claim 1 is characterized in that described suitable reductive agent comprises: V-Brite B, thiourea peroxide, zinc dithionite, hydrazine hydrate, anhydrous hydrazine, unsymmetrical dimethyl hydrazine, hydrazine hydrochloride, hydrazonium sulfate, oxammonium hydrochloride, oxammonium sulfate, sulphite or hydrosulphite, hydroxymethanesulfinate wherein one or more.
3, the purification method of whitening of lime carbonate according to claim 1 is characterized in that described suitable sequestering agent comprises organic amine compound: trolamine, quadrol, diethylenetriamine, Triethylenetetramine (TETA) wherein one or more.
4,, it is characterized in that the ratio when described reductive agent and sequestering agent are used is 0.01-1: 0.1-2 according to the purification method of whitening of claim 1 or 2 or 3 described lime carbonate.
5, the purification method of whitening of lime carbonate according to claim 1, it is characterized in that described suitable sequestrant comprise ammonia carboxylic complex compound: EDTA or its sodium salt, three second triamine-pentaacetic acids, nitrilotriacetic acid(NTA), hydroxyethylethylene diamine tri-acetic acid wherein one or more.
6, the purification method of whitening of lime carbonate according to claim 5 is characterized in that the ratio when described reductive agent and complexone are used is 1: 1.
7, the purification method of whitening of lime carbonate according to claim 1, it is characterized in that: the dispersion agent that adds in the slip of lime carbonate is a Sodium hexametaphosphate 99.
8, the purification method of whitening of lime carbonate according to claim 1, it is characterized in that the described processing of brightening for lime carbonate raw material (calcium hydroxide) can be in calcium oxide digestion near fully the time, utilize the digestion heat release to handle during greater than 80 ℃, or handle when behind the choosing slurry, making calcium hydroxide charge pulp temperature greater than 80 ℃ by intensification again in temperature.
9, the purification method of whitening of lime carbonate according to claim 1, its feature also is to add at described lime carbonate grog slurry yellow soda ash or sodium hydroxide or the mixture of the two of 0.5-5%, in 100-150 ℃, lime carbonate grog slurry is carried out the molten processing of alkali, the coloured group beyond the stripping calcium-magnesium removing ion.
10, the purification method of whitening of the described lime carbonate of claim 1 is used for the purposes that brightens processing of light calcium carbonate, water-ground limestone, wilkinite, kaolin, talcum powder, wollastonite.
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| CN101987480A (en) * | 2009-07-31 | 2011-03-23 | 施永义 | Preparation method of non-pickling raw kaolin ore |
| CN102653411B (en) * | 2012-05-16 | 2015-01-21 | 山东山大华特科技股份有限公司 | Process for preparing light-weight calcium carbonate by recycling white mud by alkali |
| CN103897434B (en) * | 2014-04-19 | 2016-03-30 | 芮城新泰纳米材料有限公司 | The preparation method that plastic master batch is Nano calcium carbonate dedicated |
| CN104909398A (en) * | 2014-07-04 | 2015-09-16 | 池州市富华粉体科技有限公司 | Preparation method for high purity calcium carbonate |
| CN105256652A (en) * | 2015-09-18 | 2016-01-20 | 金华盛纸业（苏州工业园区）有限公司 | Method for improving whiteness of papermaking filler |
| CN107522217A (en) * | 2017-09-30 | 2017-12-29 | 广西华洋矿源材料有限公司 | A kind of production method of conventional lightweight calcium carbonate |
| CN108047766B (en) * | 2017-12-19 | 2020-12-08 | 安徽省宣城市华纳新材料科技有限公司 | Method for surface modification of nano calcium carbonate |
| CN109911911A (en) * | 2019-04-11 | 2019-06-21 | 杨天睿 | A kind of method of whitening and talcum of impure talcum mud |
| CN113461023A (en) * | 2021-07-27 | 2021-10-01 | 上饶市广丰区方正非矿开发有限公司 | Calcining and purifying method of Guangfeng black talc |
| CN114195161B (en) * | 2021-12-16 | 2024-01-23 | 中国有色桂林矿产地质研究院有限公司 | Method for improving whiteness of talcum slurry slag |
| CN114685141A (en) * | 2022-05-05 | 2022-07-01 | 董坤 | Iron-removing whitening method for ceramic raw material |
| CN115057462B (en) * | 2022-05-27 | 2023-11-24 | 河北立信新材料科技有限公司 | Method for preparing Gao Baigao pure light calcium carbonate |
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