CN102120587A - Method for preparing high-purity sodium-based smectite, white carbon black and size-controllable nano silicon dioxide from cristobalite-rich calcium-based bentonite ore - Google Patents
Method for preparing high-purity sodium-based smectite, white carbon black and size-controllable nano silicon dioxide from cristobalite-rich calcium-based bentonite ore Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910000278 bentonite Inorganic materials 0.000 title claims abstract description 31
- 239000000440 bentonite Substances 0.000 title claims abstract description 31
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 29
- 239000011734 sodium Substances 0.000 title claims abstract description 28
- 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 title claims abstract description 26
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 26
- 239000006229 carbon black Substances 0.000 title claims abstract description 17
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 17
- 239000011575 calcium Substances 0.000 title claims abstract description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 14
- 239000005543 nano-size silicon particle Substances 0.000 title claims abstract description 11
- 229910021647 smectite Inorganic materials 0.000 title description 8
- 238000000746 purification Methods 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 238000003672 processing method Methods 0.000 claims abstract description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 43
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 40
- 238000001556 precipitation Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000007634 remodeling Methods 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 13
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 230000001360 synchronised effect Effects 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- -1 polyoxyethylene Polymers 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 230000003340 mental effect Effects 0.000 abstract 1
- 239000002585 base Substances 0.000 description 24
- 229940092782 bentonite Drugs 0.000 description 22
- 229910052500 inorganic mineral Inorganic materials 0.000 description 22
- 239000011707 mineral Substances 0.000 description 22
- 235000010755 mineral Nutrition 0.000 description 22
- ONCZQWJXONKSMM-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4].[Si+4].[Si+4].[Si+4] ONCZQWJXONKSMM-UHFFFAOYSA-N 0.000 description 12
- 229940080314 sodium bentonite Drugs 0.000 description 12
- 229910000280 sodium bentonite Inorganic materials 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- 238000005341 cation exchange Methods 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 7
- 229960001866 silicon dioxide Drugs 0.000 description 7
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010433 feldspar Substances 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229910001919 chlorite Inorganic materials 0.000 description 2
- 229910052619 chlorite group Inorganic materials 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 239000002734 clay mineral Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021532 Calcite Inorganic materials 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 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
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910001649 dickite Inorganic materials 0.000 description 1
- LRCFXGAMWKDGLA-UHFFFAOYSA-N dioxosilane;hydrate Chemical compound O.O=[Si]=O LRCFXGAMWKDGLA-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000021321 essential mineral Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019580 granularity Nutrition 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052677 heulandite Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000011022 opal Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052655 plagioclase feldspar Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052679 scolecite Inorganic materials 0.000 description 1
- 229960004029 silicic acid Drugs 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004856 soil analysis Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention belongs to the deep processing technology of non-mental bentonite ore. The method mainly consists of following processes: modification purification, alkaline exaction separation, high-purity sodium-based bentonite preparation, high-purity white carbon black preparation, size-controllable nano silicon dioxide preparation and the like based on cristobalite-rich natural calcium-based bentonite as a staring point; and finally, the purity of the obtained sodium-based bentonite is larger than 96%, the purities of the white carbon black and nano silicon dioxide are larger than 99%, the size of the nano silicon dioxide is controlled to 52nm and 68nm, and the properties of four products are excellent. The invention provides the deep processing method of the cristobalite-rich calcium-based bentonite, the method has the advantages of high resource utilization and small environment pollution, and is economic and practicable, thereby providing a technical basis for energy consumption-low cost-low and added value-high development and utilization of cristobalite-rich bentonite ore resources.
Description
Technical field
The invention belongs to nonmetal bentonite ore object depth processing technology.Being applicable to mainly that the natural calcium base bentonite that will be rich in cristobalite is purified respectively after remodeling, removal of impurities, alkaline process separate is the nano silicon of the high-purity na-montmorillonite of high-quality, high-purity white carbon black and controllable size.
Background technology
Wilkinite is to be a kind of clay mineral of main component with the montmorillonite, claims polynite again.International clay research association (AIPEA) is defined as wilkinite " be the rock of main ingredient with the smectite type mineral, be that smectite type mineral reaches the clay or the tonstein that can utilize content ".
Bentonitic essential mineral composition is a smectite type mineral, and content from 40% to 90% does not wait; Next contains other clay mineral, comprise kaolinite, dickite, halloysite, chlorite, malthacite, convex-concave rod stone etc., and siliceous mineral (quartz, cristobalite, tridymite, opal etc.), feldspar (potassium felspar sand, plagioclase etc.), zeolite (clinoptilolite, mordenite, heulandite, scolecite etc.), carbonate (calcite, aragonite, rhombspar etc.), vitriol non-clay class mineral such as (gypsum, barites etc.).
The montmorillonite crystal is formed by two-layer silicon-oxy tetrahedron therebetween layer of aluminum (magnesium) oxygen (hydrogen-oxygen) is octahedra, belong to 2: 1 type lamellar aluminosilicates, there is a spot of silicon to be replaced in the tetrahedron by aluminium, there is a spot of aluminium to be replaced in the octahedron by magnesium, make to produce permanent negative charge between crystal layer, thereby between crystal layer, adsorb a large amount of tradable positively charged ions.Difference according to the cation type that adsorbs between montmorillonite layer can be divided into wilkinite calcium-base bentonite, sodium bentonite, hydrogen (aluminium) base bentonite, magnesium base bentonite etc.China's wilkinite mineral products aboundresources, widely distributed, total reserves is at the forefront in the world, but 90% be calcium-base bentonite, natural sodium bentonite is seldom.The kind of known exchangeable cation and exchange capacity (CEC) have much relations: high-valence cationic (Ca
2+, Mg
2+Deng) hydration shell is thin, expansion multiple is low, and CEC is little; And low price positively charged ion (Na
+, K
+Deng) the aquation thickness, the expansion multiple height, CEC is big.Sodium ion has stronger hydration than calcium ion, therefore sodium bentonite has more superior physical and chemical performance than calcium-base bentonite, and is big as water-intake rate, expansion multiple is high, cation exchange capacity is big, oilness is good, Heat stability is good and have stronger plasticity-and cementability etc.
The sodium modification of calcium-base bentonite all is the emphasis of wilkinite deep processing research and industrialization as the effective way that improves wilkinite using value and economic worth all the time.Since wilkinite in becoming the ore deposit process under multiple factor interaction some other mineral of association as quartz, feldspar, hydromica, illite, chlorite, limonite, carbonic acid landwaste etc., its existence can have a strong impact on bentonitic various performance, therefore must purify to bentonite ore in actual applications.The The Purification of Swelled-ground removal of impurities is most important for the viscosity, adsorptivity, expansion multiple, the cation exchange capacity that improve polynite, so The Purification of Swelled-ground and remodeling are considered to the most important thing of wilkinite deep processing research.
At present, the The Purification of Swelled-ground modified method mainly contains two kinds of dry method and wet methods.Dry method is mainly used in the purification of smectite content greater than 80% raw ore, and it is according to the hardness of impure mineral in the natural montmorillonite and all big than the montmorillonite characteristics of density, by centrifugal settling step by step impurity is separated, thereby obtains refining soil.This method technical process is easy, and treatment capacity is big, but quality product is wayward.Wet method is applicable to the purification of smectite content at 30%～80% middle low-grade bentonite.This method mainly utilizes montmorillonite to have good hydrophilicity and the montmorillonite structure cell is tiny and can be in water medium abundant dispersive principle, impure mineral is separated with montmorillonite.
Although it is the wet purification effect stability, be widely used, very undesirable for the refining effect of the very approaching impure mineral of structure, density and granularities such as some cristobalites that exist in the montmorillonite, quartz and montmorillonite.Since these mineral normally with the montmorillonite symbiosis, be embedded in, it is impossible that traditional wet purification only depends on centrifugal settling that cristobalite is separated.Consider that simultaneously impurity such as cristobalite tiny in the montmorillonite, quartz have very strong carinogenicity, and can badly influence the physical and chemical performance of montmorillonite, so the removal of impure mineral such as cristobalite is the gordian technique difficult point of restriction wilkinite deep processing in the wilkinite.
(Jiang Guilan such as Jiang Guilan, Zhang Peiping, wilkinite processing and application, Chemical Industry Press, 2005.2) the purification experimental result of a small amount of cristobalite in Liu house, Jilin Province wilkinite is thought, the use alkali extraction method can be removed a small amount of cristobalite in the wilkinite, and purification material phase analysis as a result shows that smectite content can reach more than 95%.
(Marc Pansu, Jacques Gautheyrou, Handbook of SoilAnalysis such as Marc Pansu, Springer, 2006) and Daniela Sauer (Daniela Sauer, Biogeochemistry, 2006,80,89) find that also alkaline matter is (as NaOH, Na
2CO
3) to a small amount of SiO contained in the polynite
2Removal effect is in various degree arranged.
Chinese invention patent CN101016157A uses the basic solution of 0.5-3N to contain the montmorillonite of cristobalite 100-140 ℃ of hydrothermal treatment consists, can effectively remove cristobalite through steps such as washing, centrifugal, oven dry, obtain smectite content greater than 95% purifying montmorillonite.A spot of cristobalite has good effect in the wilkinite although above method is for removing, but for the higher polynite raw ore of cristobalite content, alkali treatment method is produced high energy consumption (pyroreaction and a large amount of aftertreatments), expensive (use of big content of starting materials), the heavily contaminated problems such as (dischargings of a large amount of strong basicity waste liquids) that montmorillonite brings and is still seriously restricted its suitability for industrialized production.
Not high at ubiquitous resource utilization in China's SOLID MINERAL RESOURCES development and use, the wasting of resources and environmental pollution are serious, secondary resource is recycled problems such as degree is low, by the Ministry of Science and Technology, the National Development and Reform Commission, Ministry of Land and Resources, " the SOLID MINERAL RESOURCES technical policy main points " that four ministries and commissions of National Energy Board dispatch a joint document (No. (2009) 176, state Ke Fa society) explicitly call for basis and perspective utilisation technologies such as development non-metallic minerals high efficiency separation and material purification techniques, therefore how to realize being rich in the economy of cristobalite wilkinite mineral products resource, efficiently, sustainable use is the key of this type of wilkinite mineral products resource deep processing.
Summary of the invention
The invention provides a kind of resource utilization height, little, the economically viable cristobalite calcium-base bentonite deep processing method that is rich in of environmental pollution.The present invention is a starting point with the natural calcium base bentonite that is rich in cristobalite, mainly is made up of the operations such as nano silicon preparation of remodeling purification, alkaline extraction, the preparation of high pure sodium base bentonite, high-purity white carbon black and controllable size, mainly may further comprise the steps:
(1) prepares sodium-based montmorillonite by wet method remodeling purification synchronous process, make purification operations run through whole flow process, through disperse, steps such as heating remodeling, centrifugal removal of impurities remove the impure mineral of easily removing, utilize simultaneously the better wetting ability of sodium-based montmorillonite with easier in water medium the dispersive characteristics create conditions for next step alkaline extraction separates cristobalite;
(2) dilute alkaline soln of use 0.2-0.5mol/L carries out the alkaline extraction separation to the sodium-based montmorillonite of above-mentioned gained, temperature of reaction is controlled at 50-100 ℃, reaction times 0.5-6 hour, after the reaction after filtration, washing (to pH＜9), oven dry make the high pure sodium base montmorillonite, and collect filtrate in order to further handling;
(3) filtrate that Shou Jis through precipitation, filter to take off and obtain high-purity mother liquor after assorted, add precipitation agent in the mother liquor and react, temperature of reaction is controlled at 20-90 ℃, reaction times 0.5-4 hour, obtain unformed white carbon black precipitation, after filtration, obtain high-purity white carbon black after the oven dry;
(4) filtrate that Shou Jis through precipitation, filter to take off and obtain high-purity mother liquor after assorted, when the adding precipitation agent reacts in mother liquor, the growth that adds certain amount of surfactant control silicon dioxide granule, temperature of reaction is controlled at 20-90 ℃, reaction times 0.5-4 hour, obtain nano silicon, after filtration, the oven dry after obtain high-purity nm silicon-dioxide;
Advantage of the present invention:
(1) the present invention at first utilizes wet method remodeling purification synchronous process that the large granular impurity of easily removing in the wilkinite is removed, simultaneously also utilize the good dispersiveness of sodium bentonite to make its abundant swelling, make the cristobalite impurity of inlaying and wrapping up fully come out, created favourable condition for next step alkaline extraction separates cristobalite;
(2) the present invention uses dilute alkaline soln that cristobalite impurity is extracted, the cristobalite of solid phase is converted into sodium silicate liquid to be separated, gentle reaction conditions (lower concentration, low temperature) makes the original structure of polynite and performance can not be subjected to the corrosion of alkali and changes, thereby guaranteed the high purity and the premium properties of the sodium-based montmorillonite that obtains;
(3) the present invention uses carbonate to be precipitation agent, realized the rapid precipitation of white carbon black, liquid phase after white carbon black filters simultaneously is a sodium carbonate solution, can directly prepare the remodeling agent of sodium-based montmorillonite, thereby realize raw-material effective recycle as raw ore of calcium base bentonite wet method remodeling in the first step;
(4) the present invention adds certain amount of surfactant when using carbonate as precipitation agent, realizes the control growing of silicon dioxide granule easily;
(5) process economics of the present invention is feasible, resource utilization is high, desired raw material cheaply is easy to get, and has realized being rich in the development and use of the less energy-consumption of cristobalite wilkinite mineral products resource, low cost, high added value.
Description of drawings
Fig. 1 process flow sheet of the present invention
The X-ray diffracting spectrum of Fig. 2 embodiment 1 raw ore of calcium base bentonite
The X-ray diffracting spectrum of the sodium bentonite after Fig. 3 embodiment 1 remodeling, the removal of impurities
The X-ray diffracting spectrum of Fig. 4 embodiment 1 high pure sodium base montmorillonite
The X-ray diffracting spectrum of Fig. 5 embodiment 1 high-purity white carbon black
The X-ray diffracting spectrum of Fig. 6 embodiment 2 high pure sodium base montmorillonites
The X-ray diffracting spectrum of Fig. 7 embodiment 3 high pure sodium base montmorillonites
Embodiment
The invention will be further described below in conjunction with embodiment:
Embodiment 1
Raw ore of calcium base bentonite consists of montmorillonite 61.4%; Cristobalite 28.9%; Quartzy 5.3%; Feldspar 4.4% (X-ray diffracting spectrum is seen Fig. 2), cation exchange capacity (CEC) is 78.3mmol/100g, inhaling blue amount (MB) is 33.6g/100g.The measuring method of cation exchange capacity and the blue amount of suction according to " wilkinite " (GB/T20973-2007).
Raw ore of calcium base bentonite is modified as sodium bentonite through pulverizing, slurrying, remodeling, step such as centrifugal when removing the impure mineral of easily removing.Sodium bentonite after remodeling, the removal of impurities consists of: montmorillonite 65.1%; Cristobalite 33.0%; Quartzy 1.9% (X-ray diffracting spectrum is seen Fig. 3), cation exchange capacity (CEC) is 94.2mmol/100g, inhaling blue amount (MB) is 40.6g/100g.
The aqueous sodium hydroxide solution that adds 0.5mol/L in the sodium bentonite slurries after remodeling, the removal of impurities, add-on is 1/4 of a wilkinite quality, sodium-based montmorillonite to above-mentioned gained carries out the alkaline extraction separation, temperature of reaction is controlled at 90 ℃, 5 hours reaction times, after the reaction after filtration, washing (to pH＜9), the high pure sodium base montmorillonite that makes of oven dry consist of: montmorillonite 97.3%; Quartzy 2.7% (X-ray diffracting spectrum is seen Fig. 4), cation exchange capacity (CEC) is 131.5mmol/100g, inhaling blue amount (MB) is 56.8g/100g.And collect filtrate in order to further handling.
The filtrate of collecting through sedimentation, filter to take off and obtain high-purity mother liquor after assorted, adding the precipitation agent sodium bicarbonate reacts, the precipitation agent add-on is 0.6mol/L, temperature of reaction is controlled at 70 ℃, in 2 hours reaction times, obtains unformed white carbon black precipitation, after filtration, obtain high-purity white carbon black after the oven dry, the high-purity white carbon black purity that makes＞99.9% (X-ray diffracting spectrum is seen Fig. 5), the DBP oil-absorption(number) is 2.35ml/g, average particle size is 340nm.Is the DBP oil-absorption(number) measured according to " rubber ingredients precipitated hydrated silica dibutyl phthalate absorption? " (HG/T3072-2008), particle diameter is measured by Zetasizer Nano size distribution instrument.
Embodiment 2
Raw ore of calcium base bentonite composition and other corresponding detection method are identical with embodiment 1.
Raw ore of calcium base bentonite is removed the impure mineral of easily removing and is modified as sodium bentonite simultaneously through pulverizing, slurrying, remodeling, step such as centrifugal.The aqueous sodium hydroxide solution that adds 0.3mol/L in the sodium bentonite slurries after remodeling, the removal of impurities, add-on is 1/3 of a wilkinite quality, sodium-based montmorillonite to above-mentioned gained carries out the alkaline extraction separation, temperature of reaction is controlled at 70 ℃, 6 hours reaction times, after the reaction after filtration, washing (to pH＜9), the sodium-based montmorillonite that makes of oven dry consist of: montmorillonite 96.7%; Quartzy 3.3% (X-ray diffracting spectrum is seen Fig. 6), cation exchange capacity (CEC) is 129.8mmol/100g, inhaling blue amount (MB) is 55.9g/100g.And collect filtrate in order to further handling.
The filtrate of collecting through sedimentation, filter to take off and obtain high-purity mother liquor after assorted, adding precipitation agent bicarbonate of ammonia reacts, the precipitation agent add-on is 0.8mol/L, also add simultaneously surfactant polyethylene (PEG), add-on is 0.35mg/ml, temperature of reaction is controlled at 80 ℃, 1.5 hours reaction times, obtain armorphous nano silicon-dioxide, after filtration, obtain high-purity nm silicon-dioxide after the oven dry, nano silicon purity＞99.9% that makes, DBP oil-absorption(number) are 3.11ml/g, and average particle size is 52nm.
Embodiment 3
Raw ore of calcium base bentonite composition and other corresponding detection method are identical with embodiment 1.
Raw ore of calcium base bentonite is removed the impure mineral of easily removing and is modified as sodium bentonite simultaneously through pulverizing, slurrying, remodeling, step such as centrifugal.The aqueous sodium hydroxide solution that adds 0.25mol/L in the sodium bentonite slurries after remodeling, the removal of impurities, add-on is 1/3 of a wilkinite quality, sodium-based montmorillonite to above-mentioned gained carries out the alkaline extraction separation, temperature of reaction is controlled at 80 ℃, 5 hours reaction times, after the reaction after filtration, oven dry, the sodium-based montmorillonite that makes of washing (to pH＜9) consist of: montmorillonite 96.9%; Quartzy 3.1% (X-ray diffracting spectrum is seen Fig. 7), cation exchange capacity (CEC) is 129.9mmol/100g, inhaling blue amount (MB) is 56.4g/100g.And collect filtrate in order to further handling.
The filtrate of collecting through sedimentation, filter to take off and obtain high-purity mother liquor after assorted, adding the precipitation agent sodium bicarbonate reacts, the precipitation agent add-on is 0.7mol/L, also add simultaneously tensio-active agent cetyl trimethylammonium bromide (CTAB), add-on is 0.25mg/ml, temperature of reaction is controlled at 60 ℃, 2.5 hours reaction times, obtain armorphous nano silicon-dioxide, after filtration, obtain high-purity nm silicon-dioxide after the oven dry, nano silicon purity＞99.9% that makes, DBP oil-absorption(number) are 3.01ml/g, and average particle size is 68nm.
Claims (9)
1. one kind is rich in cristobalite calcium-base bentonite deep processing method, it is characterized in that the natural calcium base bentonite that will be rich in cristobalite is purified respectively to be the nano silicon of high-quality high pure sodium base montmorillonite, high-purity white carbon black and controllable size after remodeling, removal of impurities, alkaline process separate.Step comprises that mainly (1) wet method remodeling purification synchronous process prepares sodium-based montmorillonite; (2) utilize dilute alkaline soln that sodium-based montmorillonite is carried out alkaline extraction and separate, isolating solid after filtration, make high pure sodium base montmorillonite product after the washing, oven dry; (3) filtrate that Shou Jis through sedimentation, filter and to take off assorted back and add precipitation agent and react, after the reaction after filtration, obtain high-purity white carbon black product after drying; (4) in (3), add when precipitation agent reacts, add the growth of certain amount of surfactant control silicon dioxide granule, after filtration, obtain the high-purity nm silica product of controllable size after the oven dry.
2. method according to claim 1, the sodium-based montmorillonite that it is characterized in that using dilute alkaline soln that wet method remodeling purification synchronous process is prepared gained carries out alkaline extraction to be separated, and isolating solid is after filtration, make high pure sodium base montmorillonite product after the washing, oven dry.
3. method according to claim 2 is characterized in that using the diluted alkaline type to be a kind of or its mixture in sodium bicarbonate, yellow soda ash, the sodium hydroxide; The diluted alkaline add-on is the 1/8-1/2 of wilkinite quality, is preferably 1/6-1/2; Diluted alkaline concentration is 0.2-0.5mol/L, is preferably 0.3-0.4mol/L.
4. method according to claim 2 is characterized in that alkaline extraction separating reaction temperature is controlled at 50-100 ℃, is preferably 60-90 ℃; Reaction times 0.5-6 hour, be preferably 2-5 hour.
5. method according to claim 1, it is characterized in that the filtrate of collecting behind the dilute alkaline soln extraction separation through sedimentation, filter and take off assorted back and add precipitation agent and carry out precipitin reaction, after the reaction after filtration, obtain high-purity white carbon black product after drying.
6. method according to claim 5 is characterized in that the precipitation agent type is a kind of or its mixture in sodium bicarbonate, the bicarbonate of ammonia; The precipitation agent add-on is 0.2-1.0mol/L, is preferably 0.4-0.9mol/L.
7. method according to claim 5 is characterized in that precipitation reaction temperature is controlled at 20-90 ℃, is preferably 40-80 ℃; Reaction times 0.5-4 hour, be preferably 1-3 hour.
8. method according to claim 1, it is characterized in that the filtrate of collecting behind the dilute alkaline soln extraction separation through sedimentation, filter and take off assorted back and add precipitation agent and sink when reacting, the growth that adds certain amount of surfactant control silicon dioxide granule, after filtration, obtain the high-purity nm silica product after the oven dry.
9. method according to claim 8 is characterized in that surfactant types is a kind of or its mixture in Sodium dodecylbenzene sulfonate, cetyl trimethylammonium bromide, the polyoxyethylene glycol; The tensio-active agent add-on is 0.01-1.00mg/ml, is preferably 0.1-0.5mg/ml.
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