CN100999335A - Method of preparing chromium oxide powder using water heat reducing chromate - Google Patents
Method of preparing chromium oxide powder using water heat reducing chromate Download PDFInfo
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- CN100999335A CN100999335A CN 200610000192 CN200610000192A CN100999335A CN 100999335 A CN100999335 A CN 100999335A CN 200610000192 CN200610000192 CN 200610000192 CN 200610000192 A CN200610000192 A CN 200610000192A CN 100999335 A CN100999335 A CN 100999335A
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- chromate
- chromium oxide
- oxide powder
- surfactant
- reducing agent
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- 238000000034 method Methods 0.000 title claims abstract description 51
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 title claims abstract description 21
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910000423 chromium oxide Inorganic materials 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 5
- 239000011651 chromium Substances 0.000 claims abstract description 66
- 230000009467 reduction Effects 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000002002 slurry Substances 0.000 claims abstract description 4
- 239000002535 acidifier Substances 0.000 claims abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- -1 sodium alkylsulfonate Chemical class 0.000 claims description 5
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 235000019830 sodium polyphosphate Nutrition 0.000 claims description 3
- 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 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 5
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 125000000129 anionic group Chemical group 0.000 claims 1
- 239000003945 anionic surfactant Substances 0.000 claims 1
- 239000002736 nonionic surfactant Substances 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229910052979 sodium sulfide Inorganic materials 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 abstract description 16
- 239000002245 particle Substances 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 16
- 229910052804 chromium Inorganic materials 0.000 abstract description 13
- 230000002829 reductive effect Effects 0.000 abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical class [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000007246 mechanism Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 abstract 2
- 239000013078 crystal Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 230000036571 hydration Effects 0.000 description 13
- 238000006703 hydration reaction Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000013543 active substance Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007790 solid phase Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- JQVALDCWTQRVQE-UHFFFAOYSA-N dilithium;dioxido(dioxo)chromium Chemical compound [Li+].[Li+].[O-][Cr]([O-])(=O)=O JQVALDCWTQRVQE-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010795 gaseous waste Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及一种采用水热还原铬酸盐制备氧化铬粉体的方法，其为以铬酸盐水溶液为原料，CO2气体为酸化剂，通过表面活性剂处理，在水热条件下直接还原得到水合Cr2O3料浆，离心分离并干燥后将水合Cr2O3在不同温度下煅烧制备球形Cr2O3超细粉体，其粒度在亚微米到纳米级范围内调控。本发明采用以表面活性剂调控六价铬盐直接还原得到三价铬晶体的生长过程和控制水合氧化铬煅烧温度双重机制制备粒度可调的球形超细Cr2O3，具有很强的简便性和良好效果，而且该方法工艺流程简单，成本低廉，条件温和，过程中不引入无机杂质，适合于大规模工业生产。The invention relates to a method for preparing chromium oxide powder by using hydrothermal reduction of chromate, which uses chromate aqueous solution as raw material, CO2 gas as acidifying agent, and is directly reduced under hydrothermal conditions through surfactant treatment The hydrated Cr 2 O 3 slurry is obtained, and after centrifugation and drying, the hydrated Cr 2 O 3 is calcined at different temperatures to prepare spherical Cr 2 O 3 ultrafine powders, whose particle size is regulated in the submicron to nanometer range. The invention adopts the double mechanism of controlling the growth process of the trivalent chromium crystal through the direct reduction of the hexavalent chromium salt with the surfactant and controlling the calcination temperature of the hydrated chromium oxide to prepare the spherical ultrafine Cr 2 O 3 with adjustable particle size, which has strong simplicity and good effect, and the method has simple technological process, low cost, mild conditions, no inorganic impurities are introduced in the process, and is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to the functional inorganic materials preparing technical field, specifically relate to a kind of method that adopts water heat reducing chromate to prepare chromium oxide powder.
Background technology
Chromic oxide (Cr
2O
3) be a kind of important inorganic veridian, metallurgical raw material, abrasive substance and catalyzer, be widely used in fields such as fine ceramics, erosion shield, absorbing material, green polishing composition, organic catalysis be synthetic.Present industrial production Cr
2O
3Method mainly contain chromic trioxide pyrolysis method and sexavalence chromic salts reduction method.The chromic trioxide pyrolysis method is to produce chromic trioxide with sodium dichromate 99 through vitriol oil acidifying earlier, then Cr is made in its high-temperature roasting
2O
3, cost is high and seriously polluted; Sexavalence chromic salts reduction method generally is to be reductive agent with sulphur or sulfide, the mineral acid acidifying, and dry method or wet reducing prepare Cr
2O
3, Production Flow Chart is long, and introduces impurity element such as sulphur, is difficult to obtain high-quality product.The more important thing is, with the Cr of above-mentioned traditional method preparation
2O
3Size mostly is micron order and skewness, does not have regular surface topography, is difficult to adapt to the high performance material requirement.
Along with the progress of science and technology and the development of industry demand, particle diameter is little, narrow distribution range, and have the ultra-fine Cr of special surface pattern
2O
3Powder shows increasing excellent properties.As burningrate catalyst commonly used in the composite solid catalyzer, granularity is more little, and its catalytic efficiency is also high more; Spherical Cr
2O
3Superfine powder is evenly distributed, in senior pigment, top coat, aspect extensive application such as senior abrasive easily owing to its good fluidity.
Now developed the ultra-fine high added value Cr of a series of preparations such as comprising chromium metal oxidation style, chromic salt hydrolytic precipitation method, electrolytic process, phase transfer method
2O
3Novel method, to satisfying different performance Cr
2O
3Vital role has been played in requirement.For example, as " adopt pre-carbonating wet reducing potassiumchromate or Sodium chromate to prepare the method for chromic oxide " at Chinese patent (CN1410356A) in disclosed method, use CO earlier
2Gas acidifying potassiumchromate or chromium acid sodium solution add reductive agent prepared in reaction Cr in the hot pressure reaction still then
2O
3Hydrate, calcining obtains Cr then
2O
3Product, this method use sucrose, glucose, fructose or between them any mixture make reductive agent, reaction back reductive agent product enters filtrate, complicated component is difficult for handling, and needs protection of inert gas in the calcination process, and can only obtain the common Cr of conventional yardstick
2O
3Product.And Chinese patent " preparation method of superfined Cr 2 O 3 " (CN1165782A) in disclosed method, be to adopt emulsification/precipitation/calcining preparation technology, with the H that makes
2The microemulsion 1 of O/ tween 80/primary isoamyl alcohol/NaOH/ hexanaphthene system splashes into the H that makes under agitation condition
2O/ tween 80/primary isoamyl alcohol/Cr (NO
3)
3In the microemulsion 2 of/hexanaphthene system, produce Cr (OH)
3Precipitation is again with Cr (OH)
3Precipitation is calcined, and can obtain the Cr of median size less than 200m
2O
3Particle, but this method need consume a large amount of emulsifying agents, causes environmental pollution, and be feedstock production Cr with the chromic salt
2O
3Cost is higher relatively.A Chinese patent " a kind of spherical chromic oxide superfine powder preparation method of adjustable grain " (CN1454850A) in disclosed method, at first with mineral acid (concentrated nitric acid, the vitriol oil, concentrated hydrochloric acids etc.) acidifying reduction Sodium chromate becomes trivalent chromium solutions, handle through tensio-active agent again, pH regulator, combination precipitation agent precipitation, solid-liquid separation and calcining and other processes obtain spherical chromic oxide superfine powder, though be granularity regulate and control method preferably, but regulate and control precipitation process with tensio-active agent again after restoring trivalent chromium solutions earlier, make flow process complicated, and make souring agent with mineral acid, in system, introduce other impurity, influenced Cr
2O
3Quality.
Summary of the invention
The objective of the invention is to overcome existing Cr
2O
3The low defective of cost height, complex process, contaminate environment and product quality in the production, thus provide that a kind of technical process is simple, the direct reducing chromate of employing hydro-thermal of low production cost, non-pollutant discharge and suitable large-scale commercial production prepares the method for chromic oxide superfine powder.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of method that adopts water heat reducing chromate to prepare chromium oxide powder, it comprises following step:
1) compound concentration is the chromic salt M of 10～40wt%
2CrO
4The aqueous solution;
Described chromic salt M
2CrO
4In M be K, Na or Li;
2) chromate aqueous solution, reductive agent and tensio-active agent are placed reactor together, with reactor airtight after, feed CO
2Gas is as souring agent;
Described reductive agent is ferrous sulfate, sodium sulphite, oxalic acid, sucrose, hydrazine hydrate, methyl alcohol, formaldehyde, formic acid or ethanol, preferred oxalic acid, sucrose, methyl alcohol, formaldehyde, formic acid, ethanol, more preferably methyl alcohol, formaldehyde, formic acid; The consumption of described reductive agent (by stoichiometric ratio) is 100～140mol% of chromic salt in the mixed solution;
Described tensio-active agent is negatively charged ion or nonionogenic tenside, as sodium laurylsulfonate, sodium polyphosphate, alkyl sodium sulfonate, polyoxyethylene glycol, polyacrylamide, sorbitan fatty acid ester etc.;
The consumption of described tensio-active agent is the 0.1～2wt ‰ of chromate aqueous solution;
Feed CO
2The initial partial pressure of gas is 0.5～1MPa;
3) mixing solutions under agitation is warming up to 140～190 ℃ of reactions 2～4 hours, obtains hydration Cr
2O
3Slip;
4) centrifugation slip obtains hydration Cr
2O
3, drying is 8～10 hours under 100～120 ℃;
5) with dried hydration Cr
2O
3In retort furnace, calcined 2 hours in 500～1000 ℃;
6) material after will calcining after washing, centrifugation, is dried to constant weight, and the chromium oxide powder that obtains is the spheroidal particle of favorable dispersity, and its particle size range is at 40～1000nm.
Method provided by the invention is to be raw material with the chromate aqueous solution, CO
2Gas is souring agent, handles by tensio-active agent, and directly reduction obtains hydration Cr under hydrothermal condition
2O
3Slip, after centrifugation and the drying with hydration Cr
2O
3The spherical Cr of calcining preparation under differing temps
2O
3Superfine powder, its granularity is regulated and control in the nano level scope in submicron.With compare by trivalent chromium solutions precipitation process regulation and control product particle diameter in the existing method, the invention has the advantages that:
1) adopt the hydrothermal reduction legal system to be equipped with superfine powder Cr
2O
3, made full use of the advantage that liquid phase method prepares the inorganic materials mild condition, is convenient to process control, directly obtain in the trivalent chromium crystalline process of growth at reduction of hexavalent chromium salt, by selecting suitable tensio-active agent and consumption thereof, and control hydration Cr
2O
3Calcining temperature, thereby regulated and control the product size-grade distribution, obtain the Cr of favorable dispersity
2O
3Spheroidal particle, its particle size range is at 40～1000nm.
2) present method technical process is simple, and low production cost is realized zero emission by the material internal recycle.In whole water-heat process, temperature is up to 190 ℃, and system pressure is less than 2MPa.To be not equipped with high temperature resistant, resistance to pressure is less demanding.
3) the present invention adopts CO
2Gas is souring agent, can effectively utilize on the one hand wide material sources, cheap industrial gaseous waste CO
2, having avoided on the other hand in existing most of method of reducing with the mineral acid is souring agent, introduces unnecessary impurity.
4) the present invention has used the organic micromolecule compound (as formaldehyde, methyl alcohol, formic acid, ethanol, oxalic acid etc.) with strong reducing power to make reductive agent, and composition is simple, does not introduce other elements except that C, H, O in system.With formaldehyde is example, and its process can be represented with following reaction:
CrO
4 2-+CH
2O_Cr(OH)
3↓+HCOO
-
CrO
4 2-+HCOO
-_Cr(OH)
3↓+CO
3 2-
HCO in the liquid phase that reaction obtains
3-, CO
3 2-Crystallization becomes by product, and the sexavalent chrome of carrying secretly in minute quantity organism and the filter cake returns the main body reduction reaction, thereby realizes the efficient utilization and the zero emission of material.Adopt larger molecular organicses such as sulphur, sulfide or sucrose to make reductive agent with respect to existing method, reaction back solid product impurity is few, and liquid phase component is simple and easy to separate and utilizes.
5) mild condition of the present invention is not introduced inorganic impurity in reaction process, be suitable for large-scale commercial production.
6) the present invention adopts with the direct reduction of tensio-active agent regulation and control sexavalence chromic salts and obtains trivalent chromium crystalline process of growth and the adjustable spherical super fine Cr of control hydrated chromium oxide calcining temperature double mechanism prepared sizes
2O
3, have very strong simplicity and good result.
Embodiment
Embodiment 1
With 200gK
2CrO
4Be dissolved in 800gH
2Among the O, obtain the K that concentration is 20wt%
2CrO
4The aqueous solution, other gets 85ml37wt% formaldehyde solution, and the consumption of formaldehyde (by stoichiometric ratio) is the 140mol% of potassiumchromate in the mixed solution, with aforementioned K
2CrO
4Solution places the hot pressure reaction still together, adds sodium laurylsulfonate 0.8g again, mixes, and the airtight back of reactor is fed CO
2Gas 0.8MPa is with 600rmin
-1Speed stirs down and is warming up to 160 ℃, reacts to stop after 3 hours heating, and waits to be cooled to drive still below 50 ℃ and get material, with the above-mentioned hydration Cr that obtains
2O
3Slip centrifugation under 8000rpm, solid phase was placed in the retort furnace down at 100 ℃ in dry 10 hours, calcined 2 hours down for 500 ℃, and three after drying of the washing centrifugation of the product after the calcining are promptly obtained Cr
2O
3Product, by analysis, chromic reduction transformation efficiency is 99.8%, Cr
2O
3Particle is spherical in shape, basic hard aggregation-free, and its granularity is at 40～80nm.
Embodiment 2
With 200gK
2CrO
4Be dissolved in 800gH
2Among the O, obtain the K that concentration is 20wt%
2CrO
4The aqueous solution, other gets 85ml37wt% formaldehyde solution, and the consumption of formaldehyde (by stoichiometric ratio) is the 140mol% of potassiumchromate in the mixed solution, with aforementioned K
2CrO
4Solution places the hot pressure reaction still together, adds sodium laurylsulfonate 0.8g again, mixes, and airtight back feeds CO
2Gas 0.8MPa is with 600rmin
-1Speed stirs down and is warming up to 160 ℃, reacts to stop after 3 hours heating, and waits to be cooled to drive still below 50 ℃ and get material, with the above-mentioned hydration Cr that obtains
2O
3Slip centrifugation under 8000rpm, solid phase was placed in the retort furnace down at 100 ℃ in dry 10 hours, calcined 2 hours down for 700 ℃, and three after drying of the washing centrifugation of the product after the calcining are promptly obtained Cr
2O
3Product, by analysis, chromic reduction transformation efficiency is 99.8%, Cr
2O
3Particle is spherical in shape, basic hard aggregation-free, and its granularity is at 100～200nm.
Embodiment 3
With 200gK
2CrO
4Be dissolved in 800gH
2Among the O, obtain the K that concentration is 20wt%
2CrO
4The aqueous solution, other gets 85ml37wt% formaldehyde solution, and the consumption of formaldehyde (by stoichiometric ratio) is the 140mol% of potassiumchromate in the mixed solution, with aforementioned K
2CrO
4Solution places the hot pressure reaction still together, adds sodium laurylsulfonate 0.8g again, mixes, and airtight back feeds CO
2Gas 0.8MPa is with 600rmin
-1Speed stirs down and is warming up to 160 ℃, reacts to stop after 3 hours heating, and waits to be cooled to drive still below 50 ℃ and get material, with the above-mentioned hydration Cr that obtains
2O
3Slip centrifugation under 8000rpm, solid phase was placed in the retort furnace down at 120 ℃ in dry 8 hours, calcined 2 hours down for 1000 ℃, and three after drying of the washing centrifugation of the product after the calcining are promptly obtained Cr
2O
3Product, by analysis, chromic reduction transformation efficiency is 99.8%, Cr
2O
3The basic hard aggregation-free of particle, its granularity is at 150～260nm.
Embodiment 4
With 400gNa
2CrO
4Be dissolved in 600gH
2Among the O, obtain the Na that concentration is 40wt%
2CrO
4The aqueous solution, other gets methyl alcohol 50ml, and the consumption of methyl alcohol (by stoichiometric ratio) is the 100mol% of Sodium chromate in the mixed solution, with aforementioned Na
2CrO
4Solution places the hot pressure reaction still together, adds sodium polyphosphate 0.1g again, mixes, and airtight back feeds CO
2Gas 1.0MPa is with 600rmin
-1Speed stirs down and is warming up to 190 ℃, reacts to stop after 4 hours heating, and is cooled to drive still below 50 ℃ and get material, with the above-mentioned hydration Cr that obtains
2O
3Slip is centrifugal under 8000rpm, and solid phase was placed in the retort furnace down at 100 ℃ in dry 10 hours, calcines 2 hours down for 800 ℃, and the product after the calcining is promptly obtained Cr through three after drying of washing centrifugation
2O
3Product, by analysis, chromic reduction transformation efficiency is 99.5%, Cr
2O
3Particle is spherical in shape, basic hard aggregation-free, and its granularity is about 80～120nm.
Embodiment 5
With 100gK
2CrO
4Be dissolved in 900gH
2Among the O, compound concentration is the K of 10wt%
2CrO
4The aqueous solution, other gets 85wt% formic acid solution 30ml, and the consumption of formic acid (by stoichiometric ratio) is the 130mol% of potassiumchromate in the mixed solution, with aforementioned K
2CrO
4Solution places the hot pressure reaction still together, adds polyglycol surfactants 1.0ml again, mixes, and airtight back feeds CO
2Gas 0.5MPa is with 700rmin
-1Speed stirs down and is warming up to 150 ℃, reacts to stop after 3 hours heating, and is cooled to drive still below 50 ℃ and get material, with the above-mentioned hydration Cr that obtains
2O
3Slip centrifugation under 8000rpm, solid phase was placed in the retort furnace down at 120 ℃ in dry 8 hours, calcined 2 hours down for 900 ℃, and the product after the calcining is promptly obtained Cr through three after drying of washing centrifugation
2O
3Product, by analysis, chromic reduction transformation efficiency is 99.6%, and particles dispersed is good, and its median size is about 350nm.
Comparative Examples 1
With 100gK
2CrO
4Be dissolved in 900gH
2Among the O, compound concentration is the K of 10wt%
2CrO
4The aqueous solution, other gets 30ml 85% formic acid solution, with aforementioned K
2CrO
4Solution places the hot pressure reaction still together, mixes, and airtight back feeds CO
2Gas 0.5MPa is with 700rmin
-1Speed stirs down and is warming up to 150 ℃, reacts to stop after 3 hours heating, and waits to be cooled to drive still below 50 ℃ and get material, with the above-mentioned hydration Cr that obtains
2O
3Slurry filtration separates, and filter cake was placed in the retort furnace down at 120 ℃ in dry 8 hours, calcines 2 hours down for 900 ℃, and the product after the calcining is promptly obtained Cr through three after drying of washing centrifugation
2O
3Product, by analysis, chromic reduction transformation efficiency is 99.7%, Cr
2O
3Particle shape in the form of sheets, its granularity distributes at 0.8～2 μ m.Compare with embodiment 5, do not use tensio-active agent in the Comparative Examples 1, thereby the granularity of the powder of the chromic oxide that obtains is bigger, and skewness.
Embodiment 6
With 300gLi
2CrO
4Be dissolved in 700gH
2Among the O, obtain the Li that concentration is 30wt%
2CrO
4The aqueous solution, other gets 110ml 37wt% formaldehyde solution, and the consumption of formaldehyde (by stoichiometric ratio) is the 120mol% of lithium chromate in the mixed solution, with aforementioned Li
2CrO
4Solution places the hot pressure reaction still together, adds polyacrylamide 2g again, mixes, and the airtight back of reactor is fed CO
2Gas 0.6MPa is with 600rmin
-1Speed stirs down and is warming up to 140 ℃, reacts to stop after 2 hours heating, and waits to be cooled to drive still below 50 ℃ and get material, with the above-mentioned hydration Cr that obtains
2O
3Slip centrifugation under 8000rpm, solid phase was placed in the retort furnace down at 110 ℃ in dry 9 hours, calcined 2 hours down for 800 ℃, and three after drying of the washing centrifugation of the product after the calcining are promptly obtained Cr
2O
3Product, by analysis, chromic reduction transformation efficiency is 99.8%, Cr
2O
3Particle is spherical in shape, basic hard aggregation-free, and its granularity is at 40～100nm.
Claims (5)
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| CN101168085A (en) * | 2007-11-30 | 2008-04-30 | 河南工业大学 | Chromium slag reduction and detoxification process |
| CN103241774A (en) * | 2012-02-03 | 2013-08-14 | 裴振昭 | Spray chrome oxide preparation method |
| CN103265078A (en) * | 2013-04-12 | 2013-08-28 | 湖北振华化学股份有限公司 | A method for preparing colored hydrated chromium oxide by normal pressure reduction method |
| CN103570069A (en) * | 2013-10-31 | 2014-02-12 | 中国科学院过程工程研究所 | Method for decontaminating potassium sub-molten salt soluble crystal liquid and preparing chromic oxide |
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| CN104109767A (en) * | 2014-07-18 | 2014-10-22 | 中信锦州金属股份有限公司 | Production method of chromium sesquioxide |
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| CN101168085A (en) * | 2007-11-30 | 2008-04-30 | 河南工业大学 | Chromium slag reduction and detoxification process |
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| CN104487388A (en) * | 2012-07-06 | 2015-04-01 | 朗盛德国有限责任公司 | Method for reducing hexavalent chromium in oxidic solids |
| CN104487388B (en) * | 2012-07-06 | 2017-04-12 | 朗盛德国有限责任公司 | Method for reducing hexavalent chromium in oxidic solids |
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| CN103570069B (en) * | 2013-10-31 | 2016-04-06 | 中国科学院过程工程研究所 | The molten brilliant liquid removal of impurities of a kind of potassium system sub-molten salt and prepare the method for chromic oxide |
| CN103570069A (en) * | 2013-10-31 | 2014-02-12 | 中国科学院过程工程研究所 | Method for decontaminating potassium sub-molten salt soluble crystal liquid and preparing chromic oxide |
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