CN101723460A - Process for preparing chromium oxide from laterite-nickel ores - Google Patents
Process for preparing chromium oxide from laterite-nickel ores Download PDFInfo
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- CN101723460A CN101723460A CN200910223801A CN200910223801A CN101723460A CN 101723460 A CN101723460 A CN 101723460A CN 200910223801 A CN200910223801 A CN 200910223801A CN 200910223801 A CN200910223801 A CN 200910223801A CN 101723460 A CN101723460 A CN 101723460A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 53
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 29
- 229910000423 chromium oxide Inorganic materials 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 21
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 20
- 239000011651 chromium Substances 0.000 claims abstract description 20
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000012065 filter cake Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000012467 final product Substances 0.000 claims abstract description 3
- 238000005516 engineering process Methods 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002689 soil Substances 0.000 claims description 23
- 230000009467 reduction Effects 0.000 claims description 22
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 13
- 230000002829 reductive effect Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000004411 aluminium Substances 0.000 claims description 8
- 238000007654 immersion Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 230000009466 transformation Effects 0.000 claims description 7
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical group [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 claims description 5
- QLOKJRIVRGCVIM-UHFFFAOYSA-N 1-[(4-methylsulfanylphenyl)methyl]piperazine Chemical compound C1=CC(SC)=CC=C1CN1CCNCC1 QLOKJRIVRGCVIM-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- 239000000047 product Substances 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 10
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000002386 leaching Methods 0.000 abstract 3
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract 1
- 238000011946 reduction process Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 239000010891 toxic waste Substances 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000004927 fusion Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 4
- -1 alkali metal chromate Chemical class 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 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 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910001710 laterite Inorganic materials 0.000 description 2
- 239000011504 laterite Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical compound [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 description 1
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 description 1
- 239000011696 chromium(III) sulphate Substances 0.000 description 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a process for preparing chromium oxide from laterite-nickel ores. The process comprises the steps of carrying out liquid-solid separation and aluminum removal on roast materials obtained by leading the laterite-nickel ores and alkali metal hydroxide to be in molten salt reaction for obtaining alkaline leaching solution which is rich in chromate and the alkali metal hydroxide, taking the alkaline leaching solution as a raw material, taking hydrogen as a reducing agent, leading the alkaline leaching solution and the hydrogen to be in direct hydrothermal reduction reaction under certain temperature and pressure conditions for generating chromium hydroxide slurry, and carrying out the liquid-solid separation on the slurry for obtaining a chromium hydroxide filter cake and filtrate containing a small quantity of hexavalent chromium. A final product of chromium oxide is obtained by drying, high-temperature calcining and washing the chromium hydroxide filter cake; and the filtrate can be returned to the material mixing procedure for realizing the circulating material mixing. The process can effectively recycle and utilize valuable metal chromium in the laterite-nickel ores, thereby not only realizing the pluralism of a laterite-nickel ore product, but also reducing the emissions of toxic wastes, realizing the internal circulation of materials and media, being in line with the requirements on clean production; furthermore, the reduction process has simple flow process and strong industrial operationality.
Description
Technical field
The invention belongs to the Non-ferrous Metallurgy field, be specifically related to a kind of technology for preparing chromic oxide by red soil nickel ore.
Background technology
The technology of carrying nickel, cobalt from red soil nickel ore is subjected to extensive concern day by day, but yet there are no report about the technology of extracting valuable metal chromium and be prepared into relevant chromium products such as chromic oxide from red soil nickel ore, the comprehensive utilization of the laterite further exploitation that awaits.
Chromic salts industry occupies critical positions in national economy, and its main products has sodium dichromate 99, chromic trioxide, potassium bichromate, basic chromium sulfate, chromic oxide etc., is an indispensable industrial chemicals industry in the national economy.Chromic oxide is as a kind of main chromium cpd material, is widely used in that pigment, metallurgy, catalysis are synthetic, industries such as refractory materials and grinding and polishing.
The technology of industrial production chromic oxide mainly contains sulphur reduction roasting method, thermolysis chromic trioxide method, high temperature gas-solid hydrogen reduction etc.The sulphur reduction roasting method mainly is that potassium bichromate or sodium dichromate 99 directly are reduced into chromic oxide by sulphur under heating condition, in order to improve finished color and to improve the chromium yield, needs to add a small amount of ammonium chloride and starch.This method is the traditional technology of producing pigment-level chromic oxide, but owing to the higher industrial scale that causes of cost reduces gradually.Thermolysis chromic trioxide method is the main production of China's chromic oxide, adopts chromic anhydride to be heated and directly is decomposed into chromic oxide.This method is a little that technology is simple, and the finished product pigment performance is better; But shortcoming is also clearly: raw materials cost and energy consumption height, and industrial scale is less, and product contains a small amount of sexavalent chrome and causes environmental pollution serious.High temperature gas-solid hydrogen reduction prepares the chromium product early research, it is raw material with dichromate or alkali metal chromate that Bayer A.G has delivered patent report in succession, with hydrogen is reductive agent, is 900 ℃～1600 ℃ technologies that prepare low sulfur content chromic oxide by the gas-solid successive reaction at reduction temperature.This technology generates alkali metal hydroxide with an alkali metal salt and hydrogen reaction, is converted into an alkali metal salt by with introducing salify gas (halogen gas) salt-forming reaction taking place.But there is significant disadvantages in this technology: the hydrogen reduction temperature is higher, causes the energy consumption height, to device security and the higher requirement of handling proposition; In addition, this technology also need be introduced salify gas, is converted into the cheap byproduct an alkali metal salt of value with being worth higher alkali metal oxyhydroxide, thereby in a disguised form increases cost.Because the existence of these shortcomings causes high temperature gas-solid hydrogen reduction to prepare the chromium cpd product and is difficult to realize the industry amplification.Other industrial manufacture processes of chromic oxide also have sulphur wet reducing method, sodium sulphite wet reducing method etc., but it is low generally slightly to have content at chromic oxide, shortcoming such as impurity is many, environmental pollution is serious.
Along with the development and the growth of chromic salts industry, at the above-mentioned limitation of chromic oxide traditional processing technology, many investigators have carried out relevant research work.
U.S. Pat 4,957, materials such as 562 interpolation sulfonic acid and polyacrylic acid prepare pigment-level chromic oxide and have low water absorbable.U.S. Pat 6,174,360B1 adds elements formation diamond-rhombohedral iron ore structures such as aluminium, antimony in product sosoloid has high near-infrared reflection.But above-mentioned technology also is in conceptual phase at present, and short-term can't realize industrialization.
The open CN101475217 of Chinese invention patent is low at high temperature gas-solid hydrogen reduction method raw material availability, cost is high, device security and handling requirement height, waste residue have been invented with the chromic salt shortcomings such as the pollution of environment are big is raw material, and hydrogen is the technology that the low temperature gas-solid hydrogen reduction of reductive agent prepares chromic oxide.This technology has the raw material availability height, and flow process is simple, pollutes little advantage.But this technological reaction condition is gentle not enough, the gas-solid reaction less stable.
In sum, though a lot of about the technical study of chromic oxide product, shortcomings such as these technology ubiquity cost height, complex process, severe reaction conditions, environmental pollution; In addition, also do not paid close attention to, so developing a kind of clearer production technology that fully utilizes valuable metal chromium in the red soil nickel ore and prepare the chromic oxide product has crucial realistic meaning by the people about the technology of from red soil nickel ore, extracting chromium and comprehensive utilization.
Summary of the invention
At above shortcomings in the prior art, main purpose of the present invention be overcome that red soil nickel ore is made a low multiple use, chromic oxide product preparation process complexity, severe reaction conditions, pollution are big, device security and drawbacks such as manipulation request is higher, cost height, make sexavalent chrome extract technology and the combination of hydro-thermal hydrogen reduction technology in the red soil nickel ore, the process for cleanly preparing that the comprehensive utilization of valuable metal chromium is arranged in a kind of red soil nickel ore is provided.
First technical scheme of the present invention is: a kind of technology that is prepared chromic oxide by red soil nickel ore.It is characterized in that this technology may further comprise the steps:
(1) with red soil nickel ore and alkali metal hydroxide through mixing, roasting, liquid-solidly separate, remove aluminium after, the alkali immersion liquid of being rich in chromic salt, alkali metal hydroxide that obtains is placed in the autoclave, after the reactor sealing, feed a certain amount of hydrogen as reductive agent, open reactor and stir and be warming up to certain temperature, keep certain hour, carry out the hydro-thermal H-H reaction, obtain the chromium hydroxide slurry;
(2) slurry that step (1) is obtained obtains the chromium hydroxide filter cake and contains a small amount of chromic alkaline filtrate after liquid-solid separation;
(3) chromium hydroxide that step (2) is obtained is at high temperature calcined after drying, reduces to room temperature after the calcining;
(4) material after step (3) calcining is obtained final product chromic oxide after washing, separation, drying.
Second technical scheme of the present invention is: according to the described technology of first technical scheme, it is characterized in that: after the described hydro-thermal hydrogen reduction of step (1), the transformation efficiency of chromium reaches more than 90%.
The 3rd technical scheme of the present invention is: according to the described technology of first technical scheme, it is characterized in that: after the described calcining of step (3), the purity of chromic oxide reaches more than 98%.
The 4th technical scheme of the present invention is: according to the described technology of first technical scheme, it is characterized in that: the described alkali metal hydroxide of step (1) is sodium hydroxide or potassium hydroxide, and concentration is 100～200g/L; Described chromic salt is Sodium chromate or potassiumchromate, and concentration is 40～300g/L; The initial partial pressure of described feeding hydrogen is 0.5～2.5MPa; The temperature of described hydro-thermal hydrogen reduction is 170 ℃～250 ℃, and the reaction times is 1～3 hour.
The 5th technical scheme of the present invention is: according to the described technology of first technical scheme, it is characterized in that: 500 ℃～1100 ℃ of the described material calcining temperature of step (3), calcination time 0.5～4 hour.
The 6th technical scheme of the present invention is: according to the described technology of first technical scheme, it is characterized in that: the described material washing of step (4) condition is: the solid-liquid mass ratio is 1: 1～1: 8, washing times 3～5 times, the washing time was controlled at 20～50 minutes at every turn.Drying conditions is: drying is 1～2 hour under 100 ℃～120 ℃.
The 7th technical scheme of the present invention is: according to the described technology of any one technical scheme in six technical schemes of first technical scheme to the, it is characterized in that: step (2) is described to contain a small amount of chromic alkaline filtrate after manipulation of regeneration, returns step (1) and recycles.
According to the present invention, a kind of technology that adopts chromic salt in the immersion liquid of hydro-thermal hydrogen reduction laterite alkali and prepare chromic oxide has been proposed, this technology has following superiority compared with the prior art:
(1) sexavalent chrome and the further prepared chromic oxide product that adopts the hydro-thermal hydrogen reduction that can effectively utilize red soil nickel ore generation fused salt reaction back to leach, thereby the industrial utilization that improves red soil nickel ore is worth, strengthen the red soil nickel ore product diversification, increase economic benefit, for the comprehensive utilization of red soil nickel ore provides an effective way.
(2) can effectively realize the comprehensive utilization of poisonous elemental chromium in the red soil nickel ore, thereby reduce pollution, meet the requirement of cleaner production environment.
(3) it is simple that the hydro-thermal hydrogen reduction prepares the chromic oxide technical process, and the reaction conditions gentleness can realize operate continuously, is applicable to large-scale industrial production.
(4) adopt hydrogen as reductive agent, avoid introducing the influence that other elements bring environment and chromic oxide product quality.
(5) internal recycling of whole technology realization response material and reaction medium had both been saved cost, realized the zero release of waste again, can not produce to contain chromium saltcake chromium slag etc. in the existing industrial manufacture process, was a kind of process for cleanly preparing of decontamination from the source.
Embodiment
Embodiment 1.
Get red soil nickel ore and sodium hydroxide through the alkali fusion reaction, liquid-solidly separate, obtain after removing aluminium contain Sodium chromate 40g/L, sodium hydroxide 100g/L alkali immersion liquid 1000ml places autoclave, reactor sealing back feeds hydrogen as reductive agent, and initial partial pressure is 1.0MPa.The unlatching reactor stirs, rotating speed is 250r/min, after temperature rises to 200 ℃, the cooling of reaction 3h postcooling, reduce to pressure release below 60 ℃ to temperature in the kettle and get material, obtain the chromium hydroxide slurry, slip obtains chromium hydroxide filter cake and the filtrate that contains drop hexavalent chromium through liquid-solid separation, and the reduction transformation efficiency that the filtrate sampling analysis gets chromium is 90.9%.Filter cake places retort furnace after drying, calcines 2h under 900 ℃ of conditions, and the calcining materials that obtains obtains the spherical chromium oxide powder of the finished product through washing, liquid-solid separation, after being dried to constant weight, and the purity of chromic oxide is 99% by analysis.
Embodiment 2.
Get red soil nickel ore and sodium hydroxide through the alkali fusion reaction, liquid-solidly separate, obtain after removing aluminium contain Sodium chromate 160g/L, sodium hydroxide 150g/L alkali immersion liquid 1000ml places autoclave, reactor sealing back feeds hydrogen as reductive agent, and initial partial pressure is 1.5MPa.The unlatching reactor stirs, rotating speed is 500r/min, after temperature rises to 220 ℃, the cooling of reaction 4h postcooling, reduce to pressure release below 60 ℃ to temperature in the kettle and get material, obtain the chromium hydroxide slurry, slip obtains chromium hydroxide filter cake and the filtrate that contains drop hexavalent chromium through liquid-solid separation, and the reduction transformation efficiency that the filtrate sampling analysis gets chromium is 93.5%.Filter cake places retort furnace after drying, calcines 2.5h under 850 ℃ of conditions, and the calcining materials that obtains obtains the spherical chromium oxide powder of the finished product through washing, liquid-solid separation, after being dried to constant weight, and the purity of chromic oxide is 98.2% by analysis.
Embodiment 3.
Get red soil nickel ore and sodium hydroxide through the alkali fusion reaction, liquid-solidly separate, obtain after removing aluminium contain Sodium chromate 300g/L, sodium hydroxide 200g/L alkali immersion liquid 1000ml places autoclave, reactor sealing back feeds hydrogen as reductive agent, and initial partial pressure is 0.5MPa.The unlatching reactor stirs, rotating speed is 300r/min, after temperature rises to 180 ℃, the cooling of reaction 2.5h postcooling, reduce to pressure release below 60 ℃ to temperature in the kettle and get material, obtain the chromium hydroxide slurry, slip obtains chromium hydroxide filter cake and the filtrate that contains drop hexavalent chromium through liquid-solid separation, and the reduction transformation efficiency that the filtrate sampling analysis gets chromium is 90%.Filter cake places retort furnace after drying, calcines 1.5h under 1000 ℃ of conditions, and the calcining materials that obtains obtains the spherical chromium oxide powder of the finished product through washing, liquid-solid separation, after being dried to constant weight, and the purity of chromic oxide is 99.1% by analysis.
Embodiment 4.
Get red soil nickel ore and potassium hydroxide through the alkali fusion reaction, liquid-solidly separate, obtain after removing aluminium contain potassiumchromate 40g/L, potassium hydroxide 200g/L alkali immersion liquid 1000ml places autoclave, reactor sealing back feeds hydrogen as reductive agent, and initial partial pressure is 2.0MPa.The unlatching reactor stirs, rotating speed is 450r/min, after temperature rises to 200 ℃, the cooling of reaction 3h postcooling, reduce to pressure release below 60 ℃ to temperature in the kettle and get material, obtain the chromium hydroxide slurry, slip obtains chromium hydroxide filter cake and the filtrate that contains drop hexavalent chromium through liquid-solid separation, and the reduction transformation efficiency that the filtrate sampling analysis gets chromium is 95.6%.Filter cake places retort furnace after drying, calcines 2h under 900 ℃ of conditions, and the calcining materials that obtains obtains the spherical chromium oxide powder of the finished product through washing, liquid-solid separation, after being dried to constant weight, and the purity of chromic oxide is 99.5% by analysis.
Embodiment 5.
Get red soil nickel ore and potassium hydroxide through the alkali fusion reaction, liquid-solidly separate, obtain after removing aluminium contain potassiumchromate 200g/L, potassium hydroxide 150g/L alkali immersion liquid 1000ml places autoclave, reactor sealing back feeds hydrogen as reductive agent, and initial partial pressure is 2.5MPa.The unlatching reactor stirs, rotating speed is 300r/min, after temperature rises to 170 ℃, the cooling of reaction 4h postcooling, reduce to pressure release below 60 ℃ to temperature in the kettle and get material, obtain the chromium hydroxide slurry, slip obtains chromium hydroxide filter cake and the filtrate that contains drop hexavalent chromium through liquid-solid separation, and the reduction transformation efficiency that the filtrate sampling analysis gets chromium is 91.7%.Filter cake places retort furnace after drying, calcines 2h under 1000 ℃ of conditions, and the calcining materials that obtains obtains the spherical chromium oxide powder of the finished product through washing, liquid-solid separation, after being dried to constant weight, and the purity of chromic oxide is 99% by analysis.
Claims (7)
1. technology for preparing chromic oxide by red soil nickel ore.It is characterized in that this technology may further comprise the steps:
(1) with red soil nickel ore and alkali metal hydroxide through mixing, roasting, liquid-solidly separate, remove aluminium after, the alkali immersion liquid of being rich in chromic salt, alkali metal hydroxide that obtains is placed in the autoclave, after the reactor sealing, feed a certain amount of hydrogen as reductive agent, open reactor and stir and be warming up to certain temperature, keep certain hour, carry out the hydro-thermal H-H reaction, obtain the chromium hydroxide slurry;
(2) slurry that step (1) is obtained obtains the chromium hydroxide filter cake and contains a small amount of chromic alkaline filtrate after liquid-solid separation;
(3) chromium hydroxide that step (2) is obtained is at high temperature calcined after drying, reduces to room temperature after the calcining;
(4) material after step (3) calcining is obtained final product chromic oxide after washing, separation, drying.
2. technology according to claim 1 is characterized in that: after the described hydro-thermal hydrogen reduction of step (1), the transformation efficiency of chromium reaches more than 90%.
3. technology according to claim 1 is characterized in that: after the described calcining of step (3), the purity of chromic oxide reaches more than 98%.
4. technology according to claim 1 is characterized in that: the described alkali metal hydroxide of step (1) is sodium hydroxide or potassium hydroxide, and concentration is 100～200g/L; Described chromic salt is Sodium chromate or potassiumchromate, and concentration is 40～300g/L; The initial partial pressure of described feeding hydrogen is 0.5～2.5MPa; The temperature of described hydro-thermal hydrogen reduction is 170 ℃～250 ℃, and the reaction times is 1～3 hour.
5. technology according to claim 1 is characterized in that: 500 ℃～1100 ℃ of the described material calcining temperature of step (3), calcination time 0.5～4 hour.
6. technology according to claim 1 is characterized in that: the described material washing of step (4) condition is: the solid-liquid mass ratio is 1: 1～1: 8, washing times 3～5 times, and the washing time was controlled at 20～50 minutes at every turn.Drying conditions is: drying is 1～2 hour under 100 ℃～120 ℃.
7. according to any described technology in the claim 1 to 6, it is characterized in that: step (2) is described to contain a small amount of chromic alkaline filtrate after manipulation of regeneration, returns step (1) and recycles.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102238013A CN101723460B (en) | 2009-11-23 | 2009-11-23 | Process for preparing chromium oxide from laterite-nickel ores |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102238013A CN101723460B (en) | 2009-11-23 | 2009-11-23 | Process for preparing chromium oxide from laterite-nickel ores |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101723460A true CN101723460A (en) | 2010-06-09 |
| CN101723460B CN101723460B (en) | 2010-12-08 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010005A (en) * | 2010-11-02 | 2011-04-13 | 天津派森科技有限责任公司 | Method for preparing chromic oxide |
| CN105016387A (en) * | 2015-07-20 | 2015-11-04 | 中国科学院过程工程研究所 | Chromium salt mud treatment method |
| CN106006736A (en) * | 2016-05-16 | 2016-10-12 | 武汉理工大学 | Method of using hydrogen for preparing vanadium trioxide from vanadium-containing solution |
| CN107523840A (en) * | 2017-09-07 | 2017-12-29 | 中国科学院青海盐湖研究所 | The method that chrome oxide green is prepared using ferrochrome |
| CN111621641A (en) * | 2020-06-03 | 2020-09-04 | 中国恩菲工程技术有限公司 | Method for removing hexavalent chromium in process of preparing nickel cobalt hydroxide from laterite-nickel ore |
| CN114436332A (en) * | 2022-01-30 | 2022-05-06 | 青海省博鸿化工科技股份有限公司 | Hydroxyl chromic oxide with bottom-center orthogonal structure and preparation method of chromic oxide |
| CN115029729A (en) * | 2022-07-11 | 2022-09-09 | 江南大学 | Chromium oxide/metal oxide composite material and preparation method and application thereof |
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2009
- 2009-11-23 CN CN2009102238013A patent/CN101723460B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010005A (en) * | 2010-11-02 | 2011-04-13 | 天津派森科技有限责任公司 | Method for preparing chromic oxide |
| CN105016387A (en) * | 2015-07-20 | 2015-11-04 | 中国科学院过程工程研究所 | Chromium salt mud treatment method |
| CN106006736A (en) * | 2016-05-16 | 2016-10-12 | 武汉理工大学 | Method of using hydrogen for preparing vanadium trioxide from vanadium-containing solution |
| CN107523840A (en) * | 2017-09-07 | 2017-12-29 | 中国科学院青海盐湖研究所 | The method that chrome oxide green is prepared using ferrochrome |
| CN111621641A (en) * | 2020-06-03 | 2020-09-04 | 中国恩菲工程技术有限公司 | Method for removing hexavalent chromium in process of preparing nickel cobalt hydroxide from laterite-nickel ore |
| CN114436332A (en) * | 2022-01-30 | 2022-05-06 | 青海省博鸿化工科技股份有限公司 | Hydroxyl chromic oxide with bottom-center orthogonal structure and preparation method of chromic oxide |
| CN115029729A (en) * | 2022-07-11 | 2022-09-09 | 江南大学 | Chromium oxide/metal oxide composite material and preparation method and application thereof |
| CN115029729B (en) * | 2022-07-11 | 2023-08-08 | 江南大学 | Chromium oxide/metal oxide composite material and preparation method and application thereof |
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| CN101723460B (en) | 2010-12-08 |
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