CN107840367A - Ferrochrome fluidizing chlorination method produces the process of anhyd chromic chloride and chrome oxide green - Google Patents
Ferrochrome fluidizing chlorination method produces the process of anhyd chromic chloride and chrome oxide green Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 64
- 229910000604 Ferrochrome Inorganic materials 0.000 title claims abstract description 45
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 41
- 229960000359 chromic chloride Drugs 0.000 title claims abstract description 34
- 238000005660 chlorination reaction Methods 0.000 title claims abstract description 32
- 239000011636 chromium(III) chloride Substances 0.000 title claims abstract description 29
- 235000007831 chromium(III) chloride Nutrition 0.000 title claims abstract description 29
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 title 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 claims abstract description 43
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims abstract description 29
- 239000011651 chromium Substances 0.000 claims abstract description 27
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 26
- 238000009835 boiling Methods 0.000 claims abstract description 21
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 15
- 239000003317 industrial substance Substances 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 31
- 239000012535 impurity Substances 0.000 claims description 30
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 21
- 238000001914 filtration Methods 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 238000011084 recovery Methods 0.000 claims description 16
- 229910052710 silicon Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 10
- 239000001996 bearing alloy Substances 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 claims description 9
- 239000011261 inert gas Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- 229940067573 brown iron oxide Drugs 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- FCMKFNXOHUYWRU-UHFFFAOYSA-N [Cl].[Cr] Chemical compound [Cl].[Cr] FCMKFNXOHUYWRU-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003570 air Substances 0.000 claims description 3
- 229940056319 ferrosoferric oxide Drugs 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 abstract description 16
- 238000005516 engineering process Methods 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 150000001844 chromium Chemical class 0.000 abstract description 3
- 235000021384 green leafy vegetables Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 9
- 230000008901 benefit Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002893 slag Substances 0.000 description 6
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 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
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 230000007096 poisonous effect Effects 0.000 description 3
- 230000009467 reduction Effects 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
- 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
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- RZVXOCDCIIFGGH-UHFFFAOYSA-N chromium gold Chemical compound [Cr].[Au] RZVXOCDCIIFGGH-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/02—Oxides or hydrates thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/04—Chromium halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/10—Halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of ferrochrome fluidizing chlorination method production anhyd chromic chloride and the process of chrome oxide green, it is related to the production method technical field of chromic salts.Ferrochrome and concurrent heating agent are crushed, are added to after being sufficiently mixed in proportion in boiling chloridizing furnace, and is passed through chlorine and carries out chlorination reaction, temperature is maintained at 850 1050 DEG C, anhyd chromic chloride and iron chloride is generated, by controlling the Isolating chlorinated chromium of condenser temperature and iron chloride；Chromium chloride can also pass through 950 1100 DEG C of calcining production chrome oxide greens of high temperature by can be used after refined purification directly as chromium system industrial chemicals.The present invention fundamentally changes former chrominm salt production technology route, shortens technological process, improves product quality, reduce manufacturing cost, overall process does not have Cr6+Generation, thoroughly solve Cr6+Pollution problem, comply fully with national industrial policies, be typical new cleanproduction process, use easy to spread.
Description
Technical field
The present invention relates to the production method technical field of chromic salts, and in particular to ferrochrome fluidizing chlorination method produces anhydrous chlorine
Change the process of chromium and chrome oxide green.
Background technology
At present, anhydrous chromium trichloride preparation method is to lead to chlorine with chrome green to add carbon to react obtained at high operating temperatures, such a
There is long technological process, manufacturing cost height in method, quality is low, has Cr6+The shortcomings of pollution.Chrome green is that chromite is oxidized
Anhydrous sodium dichromate is first made in roasting, leaching, acidifying, crystallization, drying, chromic anhydride then is made with sulfuric acid reaction, chromic anhydride is forged through high temperature again
Burning forms；Or the oxidized roasting of chromite, water logging obtain chromium acid sodium solution, add sulphur reduction and separate out chromium hydroxide precipitation,
Be separated by filtration, wash again, drying, high-temperature calcination and be made；This method technological process is grown, and chromium oxide cost is higher；Particularly Si,
The more difficult removal of the impurity such as Na, S, Fe, poor product quality；Oxidizing roasting, which produces, largely contains Cr6+Poisonous chromium slag, pollute environment,
Control expense is high, and the production technology (out of category) that national authorities do not encourage.And ferrochrome is in electricity by chromite and carbon
In arc stove made from reduction, technical maturity, flow is short, and cost is low, and does not have Cr6+Produce, be i.e. economical and environmentally friendly.Raw material
(evanohm of jigging) can also be obtained by import (equivalent to import energy).
It is to react obtained at high temperature with chlorine with crome metal to also have a kind of anhydrous chromium trichloride preparation method at present, such a method
Equally exist that manufacturing cost is high, quality is low, has the shortcomings that pollution, because the method is all the crome metal produced using aluminothermic process,
And the primary raw material chrome green in aluminothermic process production metal chromium process, all it is to be made using above-mentioned process, so
This method cost is higher.
Industrialized production chrome oxide green generally uses " having calcium roasting " and " calcium-free roasting " two kinds of techniques, " having calcium roasting " i.e.
The same alkali of chromite (soda ash, sodium hydroxide) and calcic filler (dolomite, lime stone etc.) carry out high temperature oxidation roasting, trivalent chromium
Cr3+It is oxidized to Cr VI Cr6+, soluble sodium chromate is generated, through leaching, being acidified, crystallizing, dries sodium dichromate first processed, then same sulphur
Acid reaction chromic anhydride, chromic anhydride produce chrome oxide green through high-temperature calcination again；Or water logging obtains chromium acid sodium solution, sulphur reduction is added
Chromium hydroxide precipitation is separated out, then is separated by filtration, washes, drying, high-temperature calcination production chrome oxide green.This method technological process is grown,
Cost of goods manufactured is high；The more difficult removal of the impurity such as Si, S, Na, Fe, poor product quality；Oxidizing roasting, which produces, largely contains Cr6+'s
Poisonous chromium slag, pollutes environment, and control expense is high.And " calcium-free roasting " only makees filler with the return slag of not calcic, the production quantity of slag is compared with " having calcium
Roasting " reduces by 70%, Cr in slag6+Content reduce by 90%, problem of environmental pollution is not still solved, but the method
The conversion ratio of oxidizing roasting process chromium is relatively low, and subsequent technique is identical with " having calcium roasting ", therefore equally exists technological process
Long, cost of goods manufactured is high, of poor quality, it is hexavalent chromium polluted serious the shortcomings of.
Current Chinese Chrome Salt Industry is continued up using old technique decades ago, though there are local improvement and innovation,
It is that overall craft route does not change, has had larger chromic salts enterprise of more families to stop production or even close down in recent years, its is main
Reason is that production manufacturing cost is high, poisonous chromium slag (Cr6+) administer difficult and control expense height.Chrome Salt Industry wants health
Development, is badly in need of the development and application of new cleanproduction process.Based on this, a kind of life of ferrochrome (chrome-bearing alloy) fluidizing chlorination method is designed
The process for producing anhyd chromic chloride and chrome oxide green is particularly necessary.
The content of the invention
In view of the shortcomings of the prior art, the present invention seeks to be to provide a kind of ferrochrome (chrome-bearing alloy) boiling chlorine
Change method produces the process of anhyd chromic chloride and chrome oxide green, fundamentally changes former chrominm salt production technology route, significantly
Shorten the technological process of production, improve product quality, reduce manufacturing cost, overall process does not have Cr6+Pollution production
It is raw, thoroughly solve Cr6+Pollution problem, comply fully with national industrial policies, be typical new cleanproduction process, be easy to push away
It is wide to use.
To achieve these goals, the present invention is to realize by the following technical solutions：Ferrochrome (chrome-bearing alloy) seethes with excitement
Chloridising produces the process of anhyd chromic chloride and chrome oxide green, and its processing step is：By ferrochrome (chrome-bearing alloy) and concurrent heating
Agent (iron oxide and ferroso-ferric oxide) crushes, and is added to after being sufficiently mixed in proportion in boiling chloridizing furnace；Or ferrochrome (is contained into chromium
Alloy) crush after be added in boiling chloridizing furnace while add appropriate concurrent heating agent, oxygen or air, and be passed through chlorine progress chlorination
Reaction, temperature are maintained at 850-1050 DEG C, anhyd chromic chloride and iron chloride are generated, by controlling the Isolating chlorinated chromium of condenser temperature
And iron chloride, main reaction formula are：2Cr+3Cl2=2CrCl3；Chromium chloride is by can be former directly as chromium system chemical industry after refined purification
Material uses, and can also pass through (950-1100 DEG C) calcining production chrome oxide green of high temperature；Can also be by adding watery hydrochloric acid except de-iron etc.
Be dissolved in the impurity of acid, catalyst added after filtering and is allowed to solid and is dissolved in water to become liquid, then be removed by filtration the indissolubles such as silicon acid or
The impurity of alkali, then with ammoniacal liquor and generation chromium hydroxide precipitation, then through (950-1100 DEG C) of high temperature calcining production chrome oxide green；
Iron chloride can further produce poly-ferric chloride purifying agent, the ceramic material (colour glaze) containing chromium, iron pigment, spherical oxidation
The products such as iron；Described ferrochrome is using chrome-bearing alloy etc..
Preferably, described ferrochrome uses high, medium and low, chromic carbide iron, it is corresponding according to how much supplyings of phosphorus content
The concurrent heating agent brown iron oxide of ratio, brown iron oxide release a large amount of heat energy with carbon and chlorine hybrid reaction, protect fluidizing chlorination furnace temperature
Hold at 850-1050 DEG C, reaction equation is：2FeO+C+3Cl2=2FeCl3+CO2 2Fe2O3+3C+6Cl2=4FeCl3+3CO2Or
2Fe3O4+4C+9Cl2=6FeCl3+4CO2；Concurrent heating agent, the oxygen of corresponding proportion can also be passed through according to the number of ferrochrome phosphorus content
Or air, oxygen release a large amount of heat energy with the carbon reaction in ferrochrome, fluidizing chlorination furnace temperature is maintained at 850-1050 DEG C, reaction equation
For：C+02=CO2Or 2C+02=2CO。
Preferably, the anhyd chromic chloride and iron chloride of described chlorination reaction generation, different using the boiling point of chloride,
Separated by controlling condenser temperature, wherein 400-600 DEG C of recovery chlorine of first order warm condenser control outlet temperature
Change chromium, 100-150 DEG C of recovery iron chloride of second level low-temperature condenser control outlet temperature.
Preferably, described anhyd chromic chloride can be passed through the inert gas of heating, gas temperature in vacuum purification furnace
Degree control makes low boiling impurity volatilization condense again, can so removed the chloride impurities such as iron, silicon, aluminium, so at 700-900 DEG C
After reheat inert gas, circulate this process, be allowed to purify solid chlorine chromium, high-quality pure chromium chloride is obtained, after purification
Chromium chloride can be used directly as chromium system industrial chemicals, (950-1100 DEG C) calcining of high temperature can also be passed through and produce high pure oxygen
Change chrome green.
Preferably, described anhyd chromic chloride can be by adding watery hydrochloric acid to be dissolved in sour impurity except de-iron etc., after filtering
Add catalyst to be allowed to solid and be dissolved in water to become liquid, then the impurity of the indissolubles such as silicon acid is removed by filtration, then neutralized with ammoniacal liquor
Chromium hydroxide precipitation is generated, then through (950-1100 DEG C) calcining production chrome oxide green of high temperature.
Preferably, it is metal and quaternary ammonium cation that described anhyd chromic chloride, which is dissolved in the catalyst added during water,.
Beneficial effects of the present invention：The technological process of production is short, cost of goods manufactured is low, and quality is good, and production process does not have Cr6+
Produce, completely solve Cr6+Pollution problem, be typical new cleanproduction process, economic benefit and social benefit are notable.
Embodiment
To be easy to understand the technical means, the inventive features, the objects and the advantages of the present invention, with reference to
Embodiment, the present invention is expanded on further.
Present embodiment uses following technical scheme：Ferrochrome (chrome-bearing alloy) fluidizing chlorination method produces anhyd chromic chloride
And the process of chrome oxide green, its processing step are：Ferrochrome and concurrent heating agent (iron oxide and ferroso-ferric oxide) are crushed, by than
Example is added in boiling chloridizing furnace after being sufficiently mixed；Or it is added to after ferrochrome (chrome-bearing alloy) is crushed in boiling chloridizing furnace same
When add appropriate concurrent heating agent, oxygen or air, and be passed through chlorine and carry out chlorination reaction, temperature is maintained at 850-1050 DEG C, generation
Anhyd chromic chloride and iron chloride, by controlling the Isolating chlorinated chromium of condenser temperature and iron chloride, main reaction formula is：2Cr+3Cl2=
2CrCl3；Chromium chloride can also pass through high temperature (950- by can be used after refined purification directly as chromium system industrial chemicals
1100 DEG C) calcining production chrome oxide green；Catalysis can also be added after filtering by adding watery hydrochloric acid to be dissolved in sour impurity except de-iron etc.
Agent is allowed to solid and is dissolved in water to become liquid, then the impurity of the indissolubles such as silicon acid is removed by filtration, then with ammoniacal liquor and generation hydrogen-oxygen
Change chromium precipitation, then through (950-1100 DEG C) calcining production chrome oxide green of high temperature；Iron chloride can further produce poly-ferric chloride
The products such as water purification agent, the ceramic material (colour glaze) containing chromium, iron oxide red pigment, spherical iron oxide；Described ferrochrome uses to be closed containing chromium
Gold etc..
It is worth noting that, described ferrochrome uses high, medium and low, chromic carbide iron and chrome-bearing alloy, according to carbon containing
The concurrent heating agent brown iron oxide of how much supplying corresponding proportions of amount, brown iron oxide are released a large amount of heat energy with carbon and chlorine hybrid reaction, made
Fluidizing chlorination furnace temperature is maintained at 850-1050 DEG C, and reaction equation is：2FeO+C+3Cl2=2FeCl3+CO2 2Fe2O3+3C+6Cl2=
4FeCl3+3CO2Or 2Fe3O4+4C+9Cl2=6FeCl3+4CO2；Corresponding proportion can also be passed through according to the number of ferrochrome phosphorus content
Concurrent heating agent oxygen or air, the carbon reaction in oxygen and ferrochrome releases a large amount of heat energy, fluidizing chlorination furnace temperature is maintained at 850-
1050 DEG C, reaction equation is：C+02=CO2Or 2C+02=2CO。
The anhyd chromic chloride and iron chloride of present embodiment chlorination reaction generation, it is different using the boiling point of chloride,
Separated by controlling condenser temperature, wherein 400-600 DEG C of recovery chlorine of first order warm condenser control outlet temperature
Change chromium, 100-150 DEG C of recovery iron chloride of second level low-temperature condenser control outlet temperature.
Described anhyd chromic chloride can be passed through the inert gas of heating in vacuum purification furnace, and gas temperature control exists
700-900 DEG C, low boiling impurity volatilization is condensed again, the chloride impurities such as iron, silicon, aluminium can so be removed, then reheated
Inert gas, this process is circulated, be allowed to purify solid chlorine chromium, obtain high-quality pure chromium chloride, the chromium chloride after purification
It can be used directly as chromium system industrial chemicals, high-purity chrome oxide green can also be produced by (950-1100 DEG C) calcining of high temperature.
Anhyd chromic chloride can add catalyst by adding watery hydrochloric acid to be dissolved in sour impurity except de-iron etc., after filtering and be allowed to solid
Body is dissolved in water and becomes liquid, then be removed by filtration the indissolubles such as silicon acid impurity, then with ammoniacal liquor and generation chromium hydroxide precipitation,
Again through (950-1100 DEG C) calcining production chrome oxide green of high temperature.
It is metal and quaternary ammonium cation that anhyd chromic chloride, which is dissolved in the catalyst added during water,.
Present embodiment integrated artistic route is since chromite：That is chromite (Cr3+) → ferrochrome (Cr0) → trichlorine
Change chromium (Cr3+) → chrome oxide green (Cr3+), during there is no Cr6+Produce, completely solve existing process Cr6+Pollution problem,
Compared with existing process, the technological process of production is short, and manufacturing cost is low, good product quality, no Cr6+Pollution, be typical
New cleanproduction process, economic benefit and social benefit are notable.
Embodiment 1：Carbon containing 7-8% high carbon ferro-chrome and iron oxide are crushed to 200-325 mesh, ferrochrome is pressed with iron oxide
100：It is added to after 25-30 is well mixed in preheated more than 850 DEG C of boiling chloridizing furnace, is passed through chlorine and carries out chlorination reaction,
Temperature is maintained at 850-1050 DEG C；400-600 DEG C of recovery chromium chloride of first order warm condenser control outlet temperature, the second level are low
Warm 100-150 DEG C of recovery iron chloride of condenser control outlet temperature；Chromium chloride is passed through 700-900 DEG C of heating in vacuum purification furnace
Inert gas, make low boiling impurity volatilization condense again, the chloride impurities such as iron, silicon, aluminium can so be removed, then reheated
Inert gas, this process is circulated, be allowed to purify solid chlorine chromium, obtain high-quality pure chromium chloride；Chromium chloride after purification
It can be used directly as chromium system industrial chemicals, (950-1100 DEG C) calcining production chrome oxide green of high temperature can also be passed through.
Embodiment 2：Carbon containing 7%-8% high carbon ferro-chrome is crushed and arrives 200-325 mesh, is added to preheated more than 850 DEG C
In boiling chloridizing furnace, it is passed through chlorine and carries out chlorination reaction, while it is (or corresponding empty to add oxygen of the ferrochrome weight than 25-30%
Gas), temperature is maintained at 850-1050 DEG C；400-600 DEG C of recovery chromium chloride of first order warm condenser control outlet temperature, second
100-150 DEG C of recovery iron chloride of grade low-temp condenser control outlet temperature；Chromium chloride is passed through the lazy of heating in vacuum purification furnace
Property gas, gas temperature control at 700-900 DEG C, make low boiling impurity volatilization condense again, so can be by chlorinations such as iron, silicon, aluminium
Thing impurity removes, and then reheats inert gas, circulates this process, be allowed to purify solid chlorine chromium, obtains high-quality pure
Chromium chloride；Chromium chloride after purification can use directly as chromium system industrial chemicals, can also pass through high temperature (950-1100 DEG C)
Calcining production chrome oxide green.
Embodiment 3：Carbon containing 7%-8% high carbon ferro-chrome and iron oxide are crushed to 200-325 mesh, ferrochrome is pressed with iron oxide
100：It is added to after 25-30 is well mixed in preheated more than 850 DEG C of boiling chloridizing furnace, is passed through chlorine and carries out chlorination reaction,
Temperature is maintained at 850-1050 DEG C；400-600 DEG C of recovery chromium chloride of first order warm condenser control outlet temperature, the second level are low
Warm 100-150 DEG C of recovery iron chloride of condenser control outlet temperature；Chromium chloride agitator treating 1-2 in 5%-10% hydrochloric acid solution
Hour, then using filter press press filtration or vacuum dehydration, except de-iron etc. is dissolved in the impurity of acid, filter cake is that chromium chloride passes through addition
Catalyst metals or quaternary ammonium cation are allowed to be dissolved in water, and the chromium trichloride aqueous solution is made, and the indissolubles such as silicon acid is removed by filtration in solution
Impurity, then with ammoniacal liquor and generation chromium hydroxide precipitation, then through (950-1100 DEG C) of high temperature calcining production chrome oxide green.
Embodiment 4：Carbon containing 3% medium carbon ferrochrome and iron oxide are crushed to 200-325 mesh, ferrochrome presses 100 with iron oxide：
14 it is well mixed after be added in preheated more than 850 DEG C of boiling chloridizing furnace, be passed through chlorine and carry out chlorination reaction, temperature holding
At 850-1050 DEG C；400-600 DEG C of recovery chromium chloride of first order warm condenser control outlet temperature, second level low-temperature condenser
Control 100-150 DEG C of recovery iron chloride of outlet temperature；Chromium chloride agitator treating 1-2 hours in 5%-10% hydrochloric acid solution, so
Filter press press filtration or vacuum dehydration are used afterwards, and except de-iron etc. is dissolved in the impurity of acid, filter cake is chromium chloride by adding catalyst
Metal or quaternary ammonium cation are allowed to be dissolved in water, and the chromium trichloride aqueous solution is made, and the impurity of the indissolubles such as silicon acid is removed by filtration in solution,
Then chromium hydroxide precipitation is used in ammoniacal liquor and generates, then through (950-1100 DEG C) calcining production chrome oxide green of high temperature.
Embodiment 5：Carbon containing 0.5% low-carbon ferrochromium is crushed to 200-325 mesh, is added to preheated more than 850 DEG C of boiling
Rise in chlorination furnace, be passed through chlorine and carry out chlorination reaction, while add oxygen (or corresponding air) of the ferrochrome weight than 2%, temperature
It is maintained at 850-1050 DEG C；400-600 DEG C of recovery chromium chloride of first order warm condenser control outlet temperature, second level low temperature cold
100-150 DEG C of recovery iron chloride of condenser control outlet temperature；Chromium chloride agitator treating 1-2 in 5%-10% hydrochloric acid solution is small
When, then using filter press press filtration or vacuum dehydration, except de-iron etc. is dissolved in the impurity of acid, filter cake is that chromium chloride is urged by addition
Agent metal or quaternary ammonium cation are allowed to be dissolved in water, and the chromium trichloride aqueous solution is made, and the indissolubles such as silicon acid is removed by filtration in solution
Impurity, then with ammoniacal liquor and generation chromium hydroxide precipitation, then through (950-1100 DEG C) of high temperature calcining production chrome oxide green.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (6)
1. ferrochrome fluidizing chlorination method produces the process of anhyd chromic chloride and chrome oxide green, it is characterised in that its processing step
For：Ferrochrome and concurrent heating agent (iron oxide and ferroso-ferric oxide) are crushed, are added to after being sufficiently mixed in proportion in boiling chloridizing furnace；
Or be added to after ferrochrome is crushed in boiling chloridizing furnace while add appropriate concurrent heating agent, oxygen or air, and be passed through chlorine and enter
Row chlorination reaction, temperature are maintained at 850-1050 DEG C, anhyd chromic chloride and iron chloride are generated, by controlling condenser temperature to separate
Chromium chloride and iron chloride, main reaction formula are：2Cr+3Cl2=2CrCl3；Chromium chloride is by can be directly as chromium system after refined purification
Industrial chemicals uses, and can also pass through (950-1100 DEG C) calcining production chrome oxide green of high temperature；Can also be by adding watery hydrochloric acid to remove
De-iron etc. is dissolved in the impurity of acid, and catalyst is added after filtering and is allowed to solid and is dissolved in water to become liquid, then the difficulties such as silicon are removed by filtration
Molten sour impurity, then with ammoniacal liquor and generation chromium hydroxide precipitation, then through (950-1100 DEG C) of high temperature calcining production chromium oxide
It is green；Described ferrochrome can also use chrome-bearing alloy.
2. the process of ferrochrome fluidizing chlorination method production anhyd chromic chloride according to claim 1 and chrome oxide green, its
It is characterised by, described ferrochrome uses high, medium and low, chromic carbide iron and chrome-bearing alloy, according to how much supplying phases of phosphorus content
The concurrent heating agent brown iron oxide of ratio is answered, brown iron oxide releases a large amount of heat energy with carbon and chlorine hybrid reaction, makes fluidizing chlorination furnace temperature
850-1050 DEG C is maintained at, reaction equation is：2FeO+C+3Cl2=2FeCl3+CO2、2Fe2O3+3C+6Cl2=4FeCl3+3CO2Or
2Fe3O4+4C+9Cl2=6FeCl3+4CO2；Concurrent heating agent, the oxygen of corresponding proportion can also be passed through according to the number of ferrochrome phosphorus content
Or air, oxygen release a large amount of heat energy with the carbon reaction in ferrochrome, fluidizing chlorination furnace temperature is maintained at 850-1050 DEG C, reaction equation
For：C+02=CO2Or 2C+02=2CO。
3. the process of ferrochrome fluidizing chlorination method production anhyd chromic chloride according to claim 1 and chrome oxide green, its
It is characterised by, the anhyd chromic chloride and iron chloride of the generation of described chlorination reaction are different using the boiling point of chloride, pass through control
Condenser temperature is separated, wherein 400-600 DEG C of recovery chromium chloride of first order warm condenser control outlet temperature, and second
100-150 DEG C of recovery iron chloride of grade low-temp condenser control outlet temperature.
4. the process of ferrochrome fluidizing chlorination method production anhyd chromic chloride according to claim 1 and chrome oxide green, its
It is characterised by, described anhyd chromic chloride can be passed through the inert gas of heating in vacuum purification furnace, and gas temperature control exists
700-900 DEG C, low boiling impurity volatilization is condensed again, the chloride impurities such as iron, silicon, aluminium can so be removed, then reheated
Inert gas, this process is circulated, be allowed to purify solid chlorine chromium, obtain high-quality pure chromium chloride, the chromium chloride after purification
It can be used directly as chromium system industrial chemicals, high-purity chrome oxide green can also be produced by (950-1100 DEG C) calcining of high temperature.
5. the process of ferrochrome fluidizing chlorination method production anhyd chromic chloride according to claim 1 and chrome oxide green, its
It is characterised by, described anhyd chromic chloride can add catalysis by adding watery hydrochloric acid to be dissolved in sour impurity except de-iron etc. after filtering
Agent is allowed to solid and is dissolved in water to become liquid, then the impurity of the indissolubles such as silicon acid is removed by filtration, then with ammoniacal liquor and generation hydrogen-oxygen
Change chromium precipitation, then through (950-1100 DEG C) calcining production chrome oxide green of high temperature.
6. the process of ferrochrome fluidizing chlorination method production anhyd chromic chloride according to claim 1 and chrome oxide green, its
It is characterised by, it is the reducing agents such as metal and quaternary ammonium cation that described anhyd chromic chloride, which is dissolved in the catalyst added during water,.
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