CN108910928A - Co-production method of two metal chlorides and two metal chlorides - Google Patents
Co-production method of two metal chlorides and two metal chlorides Download PDFInfo
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- CN108910928A CN108910928A CN201811087401.XA CN201811087401A CN108910928A CN 108910928 A CN108910928 A CN 108910928A CN 201811087401 A CN201811087401 A CN 201811087401A CN 108910928 A CN108910928 A CN 108910928A
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- 229910001510 metal chloride Inorganic materials 0.000 title claims abstract description 137
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 76
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 76
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 23
- 239000000460 chlorine Substances 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 17
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 14
- 238000003763 carbonization Methods 0.000 claims abstract description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 9
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 9
- 238000000605 extraction Methods 0.000 claims description 60
- 238000000926 separation method Methods 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 25
- 238000009833 condensation Methods 0.000 claims description 21
- 230000005494 condensation Effects 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 239000002006 petroleum coke Substances 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 13
- 238000001816 cooling Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 238000004134 energy conservation Methods 0.000 abstract 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 56
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 26
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 26
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 23
- 239000007789 gas Substances 0.000 description 19
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 15
- 239000007787 solid Substances 0.000 description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 10
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 229910052737 gold Inorganic materials 0.000 description 8
- 238000003837 high-temperature calcination Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229960004424 carbon dioxide Drugs 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 239000003518 caustics Substances 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- -1 automobile sensor Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/50—Carbon dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/04—Halides
- C01G3/05—Chlorides
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a co-production method of two metal chlorides and a co-production method of the two metal chlorides, which comprises the following steps: 1) mixing the first metal, the second metal oxide and the carbon reducing agent, introducing chlorine, heating, generating first metal chloride through heat release of the chlorination reaction of the first metal, and generating second metal chloride, carbon monoxide and/or carbon dioxide through the carbonization and chlorination reaction of the second metal oxide. The co-production method of two metal chlorides provided by the invention can be used for simultaneously producing two metal chlorides, the first metal chlorination reaction is a strong exothermic reaction, the second metal oxide carbonization chlorination reaction is a reaction with little heat absorption or heat release, the two reactions are simultaneously carried out and coupled, the heat required by a system where materials are located can be made up, the dependence on an external heating system or a cooling system can be reduced, and the energy conservation and consumption reduction are realized.
Description
Technical field
The invention belongs to metal chloride production technical fields, and in particular to the co-production and two of two kinds of metal chlorides
Kind metal chloride.
Background technique
High purity metal oxides such as zirconium oxide, aluminium oxide etc., due to becoming important spy with excellent physicochemical characteristic
One of kind functional material.High purity metal oxides are systems since it has the physics, calorifics, the optics, mechanical property that are unsurpassed in excellence
Make advanced ceramics material, automobile sensor, catalyst carrier, semiconductor and liquid crystal display, precision instrument and aviation optics device
The important foundation material of part etc., it has also become the tip materials that yield is big in 21 century new material, output value highest, purposes are most wide it
One.In recent years, high purity metal oxides such as zirconium oxide, aluminium oxide etc. are in ink-jet printer paper and coating, display material, energy
Source, automobile, semiconductor and PC domain obtain expanding application, the fast-developing and national illuminating engineering of especially whole world LED
Implement, demand is increased sharply, and yield increases rapidly.
At present the common preparation method of high purity metal oxides be by relevant metal or metal oxide and acid or alkali into
After row reaction, then carry out repeatedly purifying that the hydroxide of corresponding metal is converted into after removal of impurities again, then by the hydroxide of metal
Object is calcined obtain the oxide of metal at high temperature.Most this method is intermittent reaction, and a kind of technique road
Line can only produce a kind of metal oxide, not only the energy consumption original text in technique, but also can also generate in process of production a large amount of useless
Acid and salkali waste.
Summary of the invention
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide two kinds of metal chlorine
The co-production of compound and two kinds of metal chlorides, the co-production can be produced at the same time two kinds of metal chlorides, the first metal
Chlorination reaction is strong exothermal reaction, and the second metal oxide carbonization chlorination reaction is the seldom reaction of neither endothermic nor exothermic, by two
It reaction while carrying out, heat required for the system where material can be made up.
The co-production that technical solution used by present invention problem is to provide two kinds of metal chlorides is solved, including
Following steps：
1) the first metal, the second metal oxide, carbonaceous reducing agent are mixed, is passed through chlorine, heated, the first metal chlorination is anti-
Heat release is answered to generate the first metal chloride, the second metal oxide carbonization chlorination reaction generates the second metal chloride, an oxidation
Carbon and/or carbon dioxide,
Wherein, the first metal be Zr, Al, Ti, Fe, Cu in any one, the second metal oxide be Zr, Al, Ti,
Any one in the oxide of Fe, Cu, the first metal chloride are different metal chlorides from the second metal chloride.
Preferably, the heating temperature in the step 1) is 500~1400 DEG C.
Preferably, the step 1) obtains the first synthesis gas, and the method also includes steps 2) to press the first synthesis gas
It according to the difference of the first metal chloride, the condensation point of the second metal chloride, is condensed and separated, is collected into the first metal respectively
Chloride isolate, the second metal chloride isolate.
Preferably, extraction extractant used is ethyl acetate, butyl acetate, tributyl phosphate, three alkane in step 2)
One or more of base oxygen phosphorus.
It preferably, further include that the first metal chloride isolate is separated by extraction step m) after the step 2)
Chlorine therein out, then the second metal chloride being separated by extraction in the first metal chloride.
Preferably, extraction extractant used is ethyl acetate, butyl acetate, tributyl phosphate, three alkane in step m)
One or more of base oxygen phosphorus.
It preferably, further include that the second metal chloride isolate is separated by extraction step n) after the step 2)
Chlorine therein out, then the first metal chloride being separated by extraction in the second metal chloride.
It preferably, further include that step i) passes through the first synthesis gas condensation and separation of the first metal after the step 3)
The later tail gas of chloride isolate, the second metal chloride isolate is passed into lye, removes therein one by lye
Carbonoxide, chlorine, obtain carbon monoxide, and carbon monoxide is used as the carbonaceous reducing agent in step 1).
Preferably, the first metal in the step 1), the second metal oxide mass ratio be (2~0.5):1.
Preferably, the mass ratio of the second metal oxide and carbonaceous reducing agent is (4~1) in the step 1)：1.
Preferably, carbonaceous reducing agent is one or more of petroleum coke, active carbon, cleaned coal, carbon monoxide.
The present invention also provides two kinds of metal chlorides, two kinds of metal chlorides are respectively the first metal chloride, the second gold medal
Belong to chloride, the first metal chloride, the second metal chloride by above-mentioned metal chloride method coproduction.
The co-production of two kinds of metal chlorides provided by the invention, can be produced at the same time two kinds of metal chlorides, and first
Metal chlorination reaction is strong exothermal reaction, and the second metal oxide carbonization chlorination reaction is the seldom reaction of neither endothermic nor exothermic, will
Two reactions carry out simultaneously, and two reactions couple, and can make up heat required for the system where material, can reduce external
The dependence of portion either heating system or cooling system, realizes energy-saving.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the device of two kinds of metal chlorides of coproduction in the embodiment of the present invention 2.
In figure：1- blender；2- reactor；The first condenser of 3-；The second condenser of 4-；The first extractor of 5-；6- second
Extractor；7- third extractor；The 4th extractor of 8-；9- caustic treater.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, with reference to the accompanying drawing and specific embodiment party
Present invention is further described in detail for formula.
Embodiment 1
The present embodiment provides the co-productions of two kinds of metal chlorides, which is characterized in that includes the following steps：
1) the first metal, the second metal oxide, carbonaceous reducing agent are mixed, is passed through chlorine, heated, the first metal chlorination is anti-
Heat release is answered to generate the first metal chloride, the second metal oxide carbonization chlorination reaction generates the second metal chloride, an oxidation
Carbon and/or carbon dioxide,
Wherein, the first metal be Zr, Al, Ti, Fe, Cu in any one, the second metal oxide be Zr, Al, Ti,
Any one in the oxide of Fe, Cu, the first metal chloride are different metal chlorides from the second metal chloride.
The present embodiment also provides two kinds of metal chlorides, and two kinds of metal chlorides are respectively the first metal chloride, second
Metal chloride, the first metal chloride, the second metal chloride by above-mentioned metal chloride method coproduction.
The co-production of two kinds of metal chlorides provided in this embodiment can be produced at the same time two kinds of metal chlorides, the
The reaction of one metal chlorination is strong exothermal reaction, and the second metal oxide carbonization chlorination reaction is the seldom reaction of neither endothermic nor exothermic,
Two reactions are carried out simultaneously, two reactions couple, and can make up heat required for the system where material, can reduce pair
The dependence of external either heating system or cooling system, realizes energy-saving.
Embodiment 2
As shown in Figure 1, the present embodiment provides the devices of two kinds of metal chlorides of coproduction, including：
Blender 1 is used for mixing,
Reactor 2 is connect with blender 1, and reactor 2 is used for material reaction,
Specifically, the reactor 2 in the present embodiment is fluidized bed furnace.Fluidized bed furnace can use graphite founding materials, can also be with
It is capable of the material of high temperature resistant and chlorine-resistant gas corrosion using refractory brick etc., the fluidized bed furnace in specific the present embodiment is cast using graphite
Material.The heating method of fluidized bed furnace is induction heating or radiant heating, the heating method of the fluidized bed furnace in specific the present embodiment
For induction heating.Fluidized bed furnace includes furnace body, further includes the jacket type heat exchange equipment being set on furnace body, built-in cyclone separator,
Gas distribution grid, feeding line, deslagging pipeline.
First condenser 3, connect with reactor 2, and the first condenser 3 is for condensing and separating；
Second condenser 4 is connect with the first condenser 3, and the second condenser 4 is for condensing and separating；
First extractor 5 is connect with the outlet at bottom of the first condenser 3, and the first extractor 5 is used for the first condenser 3
The condensate of discharge carries out level-one extraction and separation；
Second extractor 6 is connect with the first extractor 5, and the second extractor 6 is used for second level extraction and separation；
Third extractor 7 is connect with the outlet at bottom of the second condenser 4, and third extractor 7 is used for the second condenser 4
The condensate of discharge carries out second level extraction and separation；
4th extractor 8 is connect with third extractor 7, and the 4th extractor 8 is used for second level extraction and separation；
Caustic treater 9 is connect with the top exit of the second condenser 4, and caustic treater 9 is discharged for the second condenser of alkali cleaning 4
Tail gas.
The present embodiment provides the co-productions for using above-mentioned apparatus to carry out two kinds of metal chlorides, include the following steps：
1) the first metal, the second metal oxide are powder, and the first metal, the second metal oxide are granulated, made
Obtain the first metal, the partial size of the second metal oxide is 20~200 mesh.Carbonaceous reducing agent charging is crushed and is sieved, so that carbon is also
The partial size of former agent is 20~100 mesh.
2) the first metal, the second metal oxide, carbonaceous reducing agent carry out mixing in blender 1.
3) the first metal mixed, the second metal oxide, carbonaceous reducing agent are passed into reactor 2, the first metal,
The mass ratio of second metal oxide is 2：1, the mass ratio of the second metal oxide and carbonaceous reducing agent is 1：1.
It is passed through chlorine into reactor 2, heats, heating temperature is 800 DEG C, and the first metal chlorination exothermic heat of reaction generates first
Metal chloride, the second metal oxide carbonization chlorination reaction, generates the second metal chloride, carbon monoxide, carbon dioxide, obtains
To the first synthesis gas.
Wherein, the first metal is aluminium, and carbonaceous reducing agent is petroleum coke.Second metal oxide is titanium oxide.
It 4) is gaseous state from the first synthesis gas that the outlet of reactor 2 comes out, the first synthesis gas includes：First metal chlorination
Object, the second metal chloride, carbon monoxide, carbon dioxide, chlorine, by the first synthesis gas according to the first metal chloride, second
The difference of the condensation point of metal chloride, is condensed and separated, the condensation point of aluminium chloride at 185 DEG C hereinafter, titanium tetrachloride it is cold
Condensation point is at 130 DEG C hereinafter, the first synthesis gas is passed sequentially through the first condenser 3, the second condenser 4, the condensation of the first condenser 3
Temperature is 150 DEG C, is collected into solid aluminium chloride isolate by the first condenser 3, the condensation temperature of the second condenser 4 is
100 DEG C, solid titanium chloride isolate is collected by the second condenser 4.
5) tail gas that the second condenser 4 exports is passed into the lye in caustic treater 9, carbon dioxide, chlorine in tail gas
Gas is absorbed, and remaining carbon monoxide is returned in reactor 2 after drying and is used as carbonaceous reducing agent.
6) aluminium chloride isolate is subjected to extraction and separation using ethyl acetate in the first extractor 5, chlorine leach is in second
In acetoacetic ester, the chlorine in aluminium chloride isolate is separated by extraction, the ethyl acetate dissolved with chlorine is heated, chlorine
Gas is absorbed after overflowing in ethyl acetate with lye, and ethyl acetate can be recycled；
At this point, the concentration of the titanium chloride in aluminium chloride isolate is 1~5mas%, then by aluminium chloride isolate in the second extraction
It takes in device 6 and continues extraction and separation using ethyl acetate, the titanium chloride in aluminium chloride isolate is dissolved in ethyl acetate, is led to
It crosses the titanium chloride that extraction and separation go out in aluminium chloride isolate to extract 2~3 times, the aluminium chloride in finally obtained aluminium chloride isolate
Purity be not less than 99mas%.
7) titanium chloride isolate is subjected to extraction and separation using ethyl acetate in third extractor 7, chlorine leach is in second
In acetoacetic ester, the chlorine in titanium chloride isolate is separated by extraction, the ethyl acetate dissolved with chlorine is heated, chlorine
Gas is absorbed after overflowing in ethyl acetate with lye, and ethyl acetate can be recycled；
At this point, the concentration of the aluminium chloride in titanium chloride isolate is 1~5mas%, then by titanium chloride isolate in the 4th extraction
It takes in device 8 and continues extraction and separation using ethyl acetate, the aluminium chloride in titanium chloride isolate is dissolved in ethyl acetate, is led to
It crosses the aluminium chloride that extraction and separation go out in titanium chloride isolate to extract 2~3 times, the titanium chloride in finally obtained titanium chloride isolate
Purity be not less than 99mas%.
The present embodiment also provides two kinds of metal chlorides, and two kinds of metal chlorides are respectively the first metal chloride, second
Metal chloride, the first metal chloride, the second metal chloride by above-mentioned metal chloride method coproduction.
The first metal oxide that the co-production of above two metal chloride is obtained, the second metal oxide difference
High-temperature calcination is carried out, obtains final high pure oxide, the purity of high pure oxide is 99mas% or more.
The co-production of two kinds of metal chlorides provided in this embodiment can be produced at the same time two kinds of metal chlorides, the
The reaction of one metal chlorination is strong exothermal reaction, and the second metal oxide carbonization chlorination reaction is the seldom reaction of neither endothermic nor exothermic,
Two reactions are carried out simultaneously, two reactions couple, and can make up heat required for the system where material, can reduce pair
The dependence of external either heating system or cooling system, realizes energy-saving.
Thermic load in the present embodiment is 200~300kw, compared to the amount of identical substance and the first gold medal of reaction condition
Belong to and chlorination reaction individually occurs generates the first metal chloride, the second metal oxide individually to occur to be carbonized chlorination reaction generation the
For the sum of two two thermic loads individually reacted of metal chloride, the thermic load in the present embodiment reduces by 20~60%.
Embodiment 3
The present embodiment provides the devices of two kinds of metal chlorides of the coproduction used in embodiment 2 to carry out two kinds of metal chlorides
Co-production, method in the present embodiment is distinguished as with the method in embodiment 2：
First metal is iron, and the second metal oxide is titanium oxide, and corresponding reaction generates iron chloride, titanium chloride, carbon respectively
Reducing agent is carbon monoxide.
First metal in step 3), the second metal oxide mass ratio be 0.5:1, the second metal oxide and carbon restore
The mass ratio of agent is 2：1, heating temperature is 500 DEG C.Second metal oxide carbonization chlorination reaction, generates the second metal chlorination
Object, carbon monoxide obtain the first synthesis gas.
The condensation temperature of the first condenser of step 4) is 250 DEG C, is collected into solid iron chloride point by the first condenser
From object, the condensation temperature of the second condenser is 100 DEG C, is collected into solid titanium chloride isolate by the second condenser.
Chlorine in step 5) in tail gas is absorbed.
Iron chloride isolate is subjected to extraction and separation using butyl acetate in the first extractor in step 6), in the second extraction
It takes in device and carries out extraction and separation using butyl acetate, the purity for finally obtaining the iron chloride in iron chloride isolate is not less than
99mas%.
Titanium chloride isolate is subjected to extraction and separation, the 4th extraction using butyl acetate in third extractor in step 7)
Extraction and separation are carried out using butyl acetate in device, the purity of the titanium chloride in finally obtained titanium chloride isolate is not less than
99mas%.
Thermic load in the present embodiment is 220~300kw, compared to the amount of identical substance and the first gold medal of reaction condition
Belong to and chlorination reaction individually occurs generates the first metal chloride, the second metal oxide individually to occur to be carbonized chlorination reaction generation the
For the sum of two two thermic loads individually reacted of metal chloride, the thermic load in the present embodiment at least reduces by 30%.
The first metal oxide that the co-production of above two metal chloride is obtained, the second metal oxide difference
High-temperature calcination is carried out, obtains final high pure oxide, the purity of high pure oxide is 99mas% or more.
Embodiment 4
The present embodiment provides the devices of two kinds of metal chlorides of the coproduction used in embodiment 2 to carry out two kinds of metal chlorides
Co-production, method in the present embodiment is distinguished as with the method in embodiment 2：
First metal is aluminium, and the second metal oxide is zirconium oxide, and corresponding reaction generates aluminium chloride, zirconium chloride, carbon respectively
Reducing agent is active carbon.
First metal in step 3), the second metal oxide mass ratio be 0.7:1, the second metal oxide and carbon restore
The mass ratio of agent is 4：1, heating temperature is 1000 DEG C.
The condensation temperature of the first condenser of step 4) is 320 DEG C, is collected into solid zirconium chloride point by the first condenser
From object, the condensation temperature of the second condenser is 150 DEG C, is collected into solid aluminium chloride isolate by the second condenser.
Zirconium chloride isolate is subjected to extraction and separation using butyl acetate in the first extractor in step 6), in the second extraction
It takes in device and carries out extraction and separation using butyl acetate, the purity for finally obtaining the zirconium chloride in zirconium chloride isolate is not less than
99mas%.
Aluminium chloride isolate is subjected to extraction and separation, the 4th extraction using butyl acetate in third extractor in step 7)
Extraction and separation are carried out using butyl acetate in device, the purity of the aluminium chloride in finally obtained aluminium chloride isolate is not less than
99mas%.
Thermic load in the present embodiment is 200~280kw, compared to the amount of identical substance and the first gold medal of reaction condition
Belong to and chlorination reaction individually occurs generates the first metal chloride, the second metal oxide individually to occur to be carbonized chlorination reaction generation the
For the sum of two two thermic loads individually reacted of metal chloride, the thermic load in the present embodiment at least reduces by 40%.
The first metal oxide that the co-production of above two metal chloride is obtained, the second metal oxide difference
High-temperature calcination is carried out, obtains final high pure oxide, the purity of high pure oxide is 99mas% or more.
Embodiment 5
The present embodiment provides the devices of two kinds of metal chlorides of the coproduction used in embodiment 2 to carry out two kinds of metal chlorides
Co-production, method in the present embodiment is distinguished as with the method in embodiment 2：
First metal is aluminium, and the second metal oxide is copper oxide, and corresponding reaction generates aluminium chloride, copper chloride, carbon respectively
Reducing agent is cleaned coal.
First metal in step 3), the second metal oxide mass ratio be 1:1, the second metal oxide and carbonaceous reducing agent
Mass ratio be 3：1, heating temperature is 1200 DEG C.Second metal oxide carbonization chlorination reaction, the second metal chloride of generation,
Carbon monoxide obtains the first synthesis gas.
The condensation temperature of the first condenser of step 4) is 400 DEG C, is collected into solid copper chloride point by the first condenser
From object, the condensation temperature of the second condenser is 150 DEG C, is collected into solid aluminium chloride isolate by the second condenser.
Chlorine in step 5) in tail gas is absorbed.
Copper chloride isolate is subjected to extraction and separation using butyl acetate in the first extractor in step 6), in the second extraction
It takes in device and carries out extraction and separation using butyl acetate, the purity for finally obtaining the copper chloride in copper chloride isolate is not less than
99mas%.
Aluminium chloride isolate is subjected to extraction and separation, the 4th extraction using butyl acetate in third extractor in step 7)
Extraction and separation are carried out using butyl acetate in device, the purity of the aluminium chloride in finally obtained aluminium chloride isolate is not less than
99mas%.
Thermic load in the present embodiment is 220~320kw, compared to the amount of identical substance and the first gold medal of reaction condition
Belong to and chlorination reaction individually occurs generates the first metal chloride, the second metal oxide individually to occur to be carbonized chlorination reaction generation the
For the sum of two two thermic loads individually reacted of metal chloride, the thermic load in the present embodiment at least reduces by 70%.
The first metal oxide that the co-production of above two metal chloride is obtained, the second metal oxide difference
High-temperature calcination is carried out, obtains final high pure oxide, the purity of high pure oxide is 99mas% or more.
Embodiment 6
The present embodiment provides the devices of two kinds of metal chlorides of the coproduction used in embodiment 2 to carry out two kinds of metal chlorides
Co-production, method in the present embodiment is distinguished as with the method in embodiment 2：
First metal is zirconium, and the second metal oxide is aluminium oxide, and corresponding reaction generates zirconium chloride, aluminium chloride, carbon respectively
Reducing agent is petroleum coke and active carbon (mass ratio 1:1).
First metal in step 3), the second metal oxide mass ratio be 0.8:1, the second metal oxide and carbon restore
The mass ratio of agent is 1.5：1, heating temperature is 1400 DEG C.
The condensation temperature of the first condenser is 300 DEG C in step 4), is collected into solid zirconium chloride by the first condenser
Isolate, the condensation temperature of the second condenser are 150 DEG C, are collected into solid aluminium chloride isolate by the second condenser.
Zirconium chloride isolate is subjected to extraction and separation using butyl acetate in the first extractor in step 6), in the second extraction
It takes in device and carries out extraction and separation using butyl acetate, the purity for finally obtaining the zirconium chloride in zirconium chloride isolate is not less than
99mas%.
Aluminium chloride isolate is subjected to extraction and separation, the 4th extraction using butyl acetate in third extractor in step 7)
Extraction and separation are carried out using butyl acetate in device, the purity of the aluminium chloride in finally obtained aluminium chloride isolate is not less than
99mas%.
Thermic load in the present embodiment is 200~300kw, compared to the amount of identical substance and the first gold medal of reaction condition
Belong to and chlorination reaction individually occurs generates the first metal chloride, the second metal oxide individually to occur to be carbonized chlorination reaction generation the
For the sum of two two thermic loads individually reacted of metal chloride, the thermic load in the present embodiment at least reduces by 50%.
The first metal oxide that the co-production of above two metal chloride is obtained, the second metal oxide difference
High-temperature calcination is carried out, obtains final high pure oxide, the purity of high pure oxide is 99mas% or more.
Embodiment 7
The present embodiment provides the devices of two kinds of metal chlorides of the coproduction used in embodiment 2 to carry out two kinds of metal chlorides
Co-production, method in the present embodiment is distinguished as with the method in embodiment 2：
First metal is titanium, and the second metal oxide is iron oxide, and corresponding reaction generates titanium chloride, iron chloride, carbon respectively
Reducing agent is active carbon.
First metal in step 3), the second metal oxide mass ratio be 1.5:1, the second metal oxide and carbon restore
The mass ratio of agent is 2.5：1, heating temperature is 1200 DEG C.
The condensation temperature of the first condenser is 280 DEG C in step 4), is collected into solid iron chloride by the first condenser
Isolate, the condensation temperature of the second condenser are 100 DEG C, are collected into solid titanium chloride isolate by the second condenser.
Iron chloride isolate is subjected to extraction and separation using butyl acetate in the first extractor in step 6), in the second extraction
It takes in device and carries out extraction and separation using butyl acetate, the purity for finally obtaining the iron chloride in iron chloride isolate is not less than
99mas%.
Titanium chloride isolate is subjected to extraction and separation, the 4th extraction using butyl acetate in third extractor in step 7)
Extraction and separation are carried out using butyl acetate in device, the purity of the titanium chloride in finally obtained titanium chloride isolate is not less than
99mas%.
Thermic load in the present embodiment is 220~300kw, compared to the amount of identical substance and the first gold medal of reaction condition
Belong to and chlorination reaction individually occurs generates the first metal chloride, the second metal oxide individually to occur to be carbonized chlorination reaction generation the
For the sum of two two thermic loads individually reacted of metal chloride, the thermic load in the present embodiment at least reduces by 45%.
The first metal oxide that the co-production of above two metal chloride is obtained, the second metal oxide difference
High-temperature calcination is carried out, obtains final high pure oxide, the purity of high pure oxide is 99mas% or more.
Embodiment 8
The present embodiment provides the devices of two kinds of metal chlorides of the coproduction used in embodiment 2 to carry out two kinds of metal chlorides
Co-production, method in the present embodiment is distinguished as with the method in embodiment 2：
First metal is copper, and the second metal oxide is zirconium oxide, and corresponding reaction generates copper chloride, zirconium chloride, carbon respectively
Reducing agent is petroleum coke.
First metal in step 3), the second metal oxide mass ratio be 1.7:1, the second metal oxide and carbon restore
The mass ratio of agent is 3.5：1, heating temperature is 700 DEG C.
The condensation temperature of the first condenser is 460 DEG C in step 4), is collected into solid copper chloride by the first condenser
Isolate, the condensation temperature of the second condenser are 200 DEG C, are collected into solid zirconium chloride isolate by the second condenser.
Copper chloride isolate is subjected to extraction and separation using butyl acetate in the first extractor in step 6), in the second extraction
It takes in device and carries out extraction and separation using butyl acetate, the purity for finally obtaining the copper chloride in copper chloride isolate is not less than
99mas%.
Zirconium chloride isolate is subjected to extraction and separation, the 4th extraction using butyl acetate in third extractor in step 7)
Extraction and separation are carried out using butyl acetate in device, the purity of the zirconium chloride in finally obtained zirconium chloride isolate is not less than
99mas%.
Thermic load in the present embodiment is 200~300kw, compared to the amount of identical substance and the first gold medal of reaction condition
Belong to and chlorination reaction individually occurs generates the first metal chloride, the second metal oxide individually to occur to be carbonized chlorination reaction generation the
For the sum of two two thermic loads individually reacted of metal chloride, the thermic load in the present embodiment at least reduces by 30%.
The first metal oxide that the co-production of above two metal chloride is obtained, the second metal oxide difference
High-temperature calcination is carried out, obtains final high pure oxide, the purity of high pure oxide is 99mas% or more.
It is understood that the principle that embodiment of above is intended to be merely illustrative of the present and the exemplary implementation that uses
Mode, however the present invention is not limited thereto.For those skilled in the art, essence of the invention is not being departed from
In the case where mind and essence, various changes and modifications can be made therein, these variations and modifications are also considered as protection scope of the present invention.
Claims (10)
1. the co-production of two kinds of metal chlorides, which is characterized in that include the following steps：
1) the first metal, the second metal oxide, carbonaceous reducing agent are mixed, is passed through chlorine, heated, the reaction of the first metal chlorination is put
It is thermally generated the first metal chloride, the second metal oxide carbonization chlorination reaction generates the second metal chloride, carbon monoxide
And/or carbon dioxide,
Wherein, the first metal is any one in Zr, Al, Ti, Fe, Cu, and the second metal oxide is Zr, Al, Ti, Fe, Cu
Oxide in any one, the first metal chloride and the second metal chloride are different metal chlorides.
2. the co-production of two kinds of metal chlorides according to claim 1, which is characterized in that adding in the step 1)
Hot temperature is 500~1400 DEG C.
3. the co-production of two kinds of metal chlorides according to claim 1 or 2, which is characterized in that the step 1)
To the first synthesis gas, the method also includes step 2) by the first synthesis gas according to the first metal chloride, the second metal chlorination
The difference of the condensation point of object, is condensed and separated, and is collected into the first metal chloride isolate, the second metal chloride point respectively
From object.
4. the co-production of two kinds of metal chlorides according to claim 3, which is characterized in that after the step 2) also
Chlorine therein is separated by extraction in the first metal chloride isolate including step m), then is separated by extraction first
The second metal chloride in metal chloride.
5. the co-production of two kinds of metal chlorides according to claim 3, which is characterized in that after the step 2) also
Chlorine therein is separated by extraction in the second metal chloride isolate including step n), then is separated by extraction second
The first metal chloride in metal chloride.
6. the co-production of two kinds of metal chlorides according to claim 3, which is characterized in that after the step 3) also
The first synthesis gas is passed through condensation and separation of the first metal chloride isolate, the second metal chloride isolate including step i)
Later tail gas is passed into lye, is removed carbon monoxide therein, chlorine by lye, is obtained carbon monoxide, by an oxidation
Carbon is used as the carbonaceous reducing agent in step 1).
7. the according to claim 1, co-production of two kinds of metal chlorides described in 2,4,5,6 any one, which is characterized in that
First metal in the step 1), the second metal oxide mass ratio be (2~0.5):1.
8. the according to claim 1, co-production of two kinds of metal chlorides described in 2,4,5,6 any one, which is characterized in that
The mass ratio of the second metal oxide and carbonaceous reducing agent is (4~1) in the step 1)：1.
9. the according to claim 1, co-production of two kinds of metal chlorides described in 2,4,5,6 any one, which is characterized in that
Carbonaceous reducing agent is one or more of petroleum coke, active carbon, cleaned coal, carbon monoxide.
10. two kinds of metal chlorides, which is characterized in that two kinds of metal chlorides are respectively the first metal chloride, the second metal
Chloride, the first metal chloride, the second metal chloride are by metal chloride described in any one of claim 1 to 9
Method coproduction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112661196A (en) * | 2020-12-29 | 2021-04-16 | 斯瑞尔环境科技股份有限公司 | Purification method of ferric trichloride |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990013680A1 (en) * | 1989-05-12 | 1990-11-15 | Kerr-Mcgee Chemical Corporation | A process for jointly producing metal chlorides |
| CN103060567A (en) * | 2012-12-21 | 2013-04-24 | 中南大学 | Method for processing waste lithium ion battery positive plate to extract valuable metal |
| WO2014044527A1 (en) * | 2012-09-18 | 2014-03-27 | Siemens Aktiengesellschaft | Method for obtaining at least one rare earth metal chloride and a rare earth metal |
| CN108217659A (en) * | 2016-12-09 | 2018-06-29 | 新疆知信科技有限公司 | A kind of method of comprehensive utilization of flyash |
-
2018
- 2018-09-18 CN CN201811087401.XA patent/CN108910928A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1990013680A1 (en) * | 1989-05-12 | 1990-11-15 | Kerr-Mcgee Chemical Corporation | A process for jointly producing metal chlorides |
| WO2014044527A1 (en) * | 2012-09-18 | 2014-03-27 | Siemens Aktiengesellschaft | Method for obtaining at least one rare earth metal chloride and a rare earth metal |
| CN103060567A (en) * | 2012-12-21 | 2013-04-24 | 中南大学 | Method for processing waste lithium ion battery positive plate to extract valuable metal |
| CN108217659A (en) * | 2016-12-09 | 2018-06-29 | 新疆知信科技有限公司 | A kind of method of comprehensive utilization of flyash |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661196A (en) * | 2020-12-29 | 2021-04-16 | 斯瑞尔环境科技股份有限公司 | Purification method of ferric trichloride |
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