CN109745990A - oxychlorination catalyst and its preparation method and application - Google Patents
oxychlorination catalyst and its preparation method and application Download PDFInfo
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- CN109745990A CN109745990A CN201711065940.9A CN201711065940A CN109745990A CN 109745990 A CN109745990 A CN 109745990A CN 201711065940 A CN201711065940 A CN 201711065940A CN 109745990 A CN109745990 A CN 109745990A
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- oxychlorination
- coating
- carrier
- catalyst
- oxychlorination catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 238000000576 coating method Methods 0.000 claims abstract description 42
- 239000002671 adjuvant Substances 0.000 claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005977 Ethylene Substances 0.000 claims abstract description 12
- 239000007769 metal material Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004411 aluminium Substances 0.000 claims abstract description 6
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 claims abstract description 5
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract 2
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 5
- 150000002910 rare earth metals Chemical class 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- DCRIQAAPAFMPKP-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[O-2].[Al+3].[Ti+4] DCRIQAAPAFMPKP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 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 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 23
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 14
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 14
- 238000007598 dipping method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- 239000011592 zinc chloride Substances 0.000 description 7
- 235000005074 zinc chloride Nutrition 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 alkali metal salt Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000011017 operating method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 230000001568 sexual effect Effects 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
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Abstract
The present invention provides a kind of oxychlorination catalysts and its preparation method and application.Oxychlorination catalyst provided by the invention includes monolithic substrate, coating, active component and adjuvant component, wherein the monolithic substrate is metal material, preferably stainless steel, the ferrite containing aluminium or Fe-Cr-Al alloy.Oxychlorination catalyst provided by the invention is applied to ethylene oxychlorination, has obtained excellent activity, and overcome prior art and wear big disadvantage.
Description
Technical field
The present invention relates to a kind of oxychlorination catalysts and its preparation method and application.
Background technique
Ethylene and oxygen hcl reaction generate 1,2- dichloroethanes, commonly referred to as dichloroethanes (EDC), are a kind of industry
The compound of upper annual production millions of tons, is converted into vinyl chloride and hydrogen chloride after compound cracking, vinyl chloride monomer can gather
Synthesize the polyvinyl chloride (PVC) of extensive use.For many years, the whole world has developed through oxychlorination process and has produced chlorine
For the Catalyst And Method of hydrocarbon, and large-scale application is carried out on commercial plant.Currently, according to the difference of raw material route,
Industrially use two different production methods: one is B.F.Goodrich companies, the U.S. for the air method of representative, this method
It is to carry out oxi-chlorination by raw material of air, ethylene and hydrogen chloride, another kind is using Mitsui Dong Ya Co., Ltd. as generation
The oxygen method of table, this method carry out oxi-chlorination by raw material of pure oxygen, ethylene and hydrogen chloride.Chloro is being produced with process for oxychlorination
During hydrocarbon, catalyst successfully applies many years.
Oxi-chlorination is passed usually using fluidized bed or fixed-bed process, but since this reaction is exothermic reaction for guarantee
Heat more evenly, advantageously using fluidized-bed process, i.e., in a fluidized bed by the mixing of ethylene, hydrogen chloride and oxygen or oxygen-containing gas
Object carries out gas phase reaction.But the particle that fluidized bed main problem is the catalyst of fluidisation will cause the abrasion of catalyst and right
The abrasion of reactor, and be possible to therefore and the parking that causes the accident, and therefore increase production cost.
Summary of the invention
For the situation of the prior art, the purpose of the present invention is to provide a kind of oxychlorination catalyst and preparation method thereof and
Using.Oxychlorination catalyst provided by the invention is applied to ethylene oxychlorination, has obtained excellent activity, and overcome existing
The big disadvantage of process wear.
In the first aspect, the present invention provides a kind of oxychlorination catalysts comprising monolithic substrate, coating, activity
Component and adjuvant component, wherein the monolithic substrate is metal material.The preferred stainless steel of the metal material, the iron containing aluminium
Ferritic or Fe-Cr-Al alloy.Preferably, catalyst of the invention is by monolithic substrate, coating, active component and auxiliary agent group
It is grouped as.
According to the present invention, the oxychlorination catalyst is by the carrier of metal material, coating, active component and auxiliary agent group
The integral catalyzer being grouped as.
Embodiment according to the present invention, the ingredient of the coating include aluminium oxide or aluminium oxide-titanium oxide mixture.It is excellent
Selection of land, the coating are made of aluminium oxide-titanium oxide, and preferably the content of titanium oxide is 0-50wt%, preferably 2-20wt%.
Embodiment according to the present invention, the quality of the coating are the 1-20%, preferably 5- of the carrier quality
15%.
Embodiment according to the present invention, the active component are copper.
Embodiment according to the present invention, the active component content are calculated as 3-8wt%, preferably 4- with coating gross mass
7wt%.
Embodiment according to the present invention, the adjuvant component include, 0.1-10wt% selected from lanthanum, cerium, neodymium, praseodymium and
At least one alkali of at least one of rare earth metal of yttrium, one of the transition metal of 0.1-10wt% and 0.1-10wt%
Metal or alkaline-earth metal, the above mass percentage is on the basis of coating quality.
Embodiment according to the present invention, the adjuvant component are that rare earth metal is lanthanum and/or cerium, and the transition metal is
Zinc, the alkali or alkaline earth metal are potassium, sodium or magnesium.
In the second aspect, the present invention provides the preparation methods of the integral catalyzer comprising following steps:
S1 provides the monolithic substrate of metal material；
S2 provides the colloid for being used to prepare coating；
Colloid described in S2 is carried on carrier described in S1, then dried by S3, calcining, to obtain cated carrier；
S4 provides the mixed solution containing active component and adjuvant component；
S5, by cated carrier impregnation in the mixed solution, to obtain loading sexual component and adjuvant component
Carrier；
S6, by carrier drying, the activation of the sexual component of the load and adjuvant component, to obtain the catalyst.
Embodiment according to the present invention, the monolithic substrate of metal material described in step S1 can by preparation or
Purchase obtains.Preferably, the metal material is corrosion resistant metal material carrier, such as Fe-Cr-Al stainless steel carrier, and
Calcining 1~for 24 hours is carried out under 800~1500 degrees Celsius.
Embodiment according to the present invention, colloid described in step S2 are aluminium ti-based coating colloid.
Preferably, the production method of the colloid is selected from one of following four: (1) preparing soluble titanium salting liquid A
With sodium aluminate solution B, and two kinds of solution are mixed, obtains co-precipitate, filter, washing.Then in sediment, nitre is added
Acid solution simultaneously adjusts pH value formation colloidal sol.(2) the nitric acid mixed solution of aluminium and titanium is used, and ammonium hydroxide is added, after forming precipitating, mistake
Then filter, washing are added nitric acid solution and adjust pH value formation colloidal sol.(3) sol-gel method is used, from Aluminum sol system
Standby colloidal sol.Process is as follows, according to stoichiometric ratio, prepares certain density titanium salt aqueous solution and 10wt% Aluminum sol.Strong
The two is mixed under stirring, stirs 0.5h.(4) soluble titanium salting liquid A and sodium aluminate solution B are prepared, and by two kinds of solution
Mixing, obtains co-precipitate, filters, and washs, dry, calcining.Then by powder mull and the ethyl alcohol and levulinic of 1:1 are dispersed in
In ketone mixed liquor, colloidal sol is made in presoma content about 10wt%, ball milling 10h.
Embodiment according to the present invention will use the method for dipping that colloidal sol is loaded to carrier up in step S3, so
Afterwards, dry, calcining calculates carrier quality increment.Drying means includes being not limited to spontaneously dry, low-temperature vacuum drying, program
The methods of heating drying, the drying condition more mitigated is more advantageous to the combination of catalyst coat, and drying temperature should be controlled 150
Degree Celsius or less.Low heating rate should be used to be heated when calcining, preferably heating rate is 0.5~8 degrees celsius/minute, is forged
Burning temperature is 500~1000 degrees Celsius.Carrier quality increment is finally calculated, mass incremental and coating layer thickness should carry out calculating and table
Sign.If not reaching requirement, this step should be repeated until increment is met the requirements.Run-of-the-mill increment should be vehicle weight
1.5~10wt%.
According to the present invention, mantoquita, alkali metal salt or alkali salt, rare earth metal salt, transition metal salt are used in step S4
Mixed solution is made by mixing with water.
According to the present invention, mantoquita, alkali metal salt or alkali salt, rare earth metal salt, transition metal salt are used in step S5
Solution impregnation steps S3 coating obtained carrier.It is preferable to use incipient impregnation methods to be operated.The present invention
The activity and selectivity that can be required according to the condition of production of catalyst, the flexible addition for determining adjuvant component in catalyst
Amount, still, in final catalyst copper content be 3~8wt%, adjuvant component content be 0.1~10wt% rare earth metal, 0.1
The transition metal of~10wt% and the alkali or alkaline earth metal of 0.1~10wt%, the above mass percentage is with coating matter
On the basis of amount.
According to the present invention, drying means includes being not limited to spontaneously dry in step S6, low-temperature vacuum drying, temperature programming
Dry, the methods of normal drying, the drying condition more mitigated is more advantageous to the combination of catalyst coat, and drying temperature should control
At 150 degrees Celsius or less.
According to the present invention, integral catalyzer prepared by above-mentioned steps has good thermal stability.According to the present invention,
The test method of thermal stability are as follows: sample is placed in Muffle furnace, 20min is roasted at 400 DEG C, taking-up cools down in air
To room temperature, a heat stability testing is then repeated, finally weighs weight, calculates weightless dose rate, i.e., weightless quality accounts for totality
The mass percent of quality.
In the third aspect, the application the present invention provides the integral catalyzer in ethylene oxychlorination.
Catalyst of the invention can be used for air method ethylene oxychlorination system.Typical ethylene oxychlorination
Operating condition is temperature: 210-230 DEG C, pressure 0.25-0.35MPa, feed gas molar ratio C2H4:HCl:O2=1:(1.8-
2.0):(0.5-0.6)。
By using oxychlorination catalyst of the invention, the hydrogen chloride conversion ratio of ethylene oxychlorination can achieve for
99.0% or more, oxycarbide content is 0.5~2% in tail gas.
Specific embodiment
The present invention is described in detail with reference to embodiments, but the present invention is not limited by following embodiments.
Embodiment 1
It prepares the integral catalyzer of Fe-Cr-Al material in advance, and calcines 5h under 1000 degrees Celsius.Then painting is prepared
Layer.It is added in 150ml sodium hydroxide solution using 30ml titanium tetrachloride solution A, 80g aluminium-hydroxide powder at 100 degrees Celsius,
The sodium aluminate solution B of sodium hydroxide/aluminium oxide (weight ratio)=1.4~1.6 is made in stirring, is 6.0~9.0 in room temperature, pH
Under conditions of carry out coprecipitation reaction.After precipitating, it is filtered washing drying, roasts, obtains at 600 degrees Celsius after dry
The aluminium oxide-titanium oxide mixture of the titanium oxide containing 23wt%.Then mixture is ground and be dispersed in mass ratio 1:1 ethyl alcohol and
In acetylacetone,2,4-pentanedione mixed liquor, colloidal sol is made in presoma content about 10wt%, ball milling 10h.Colloidal sol is loaded using the method for dipping
It goes on to carrier, is then dried in vacuo at 80 degrees celsius, 500 degree of temperature programmings are calcined, and 1 degrees celsius/minute of heating rate is complete
At rear calculating carrier quality increment.Colloidal sol is supported on process on carrier and needs three times, and mass incremental is the 16wt% of vehicle weight.
Copper chloride, potassium chloride, cerium chloride, zinc chloride is soluble in water, and dipping is ready for the carrier of coating, and 120 is Celsius
Spend dry 2h.The catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt% are obtained, mass percentage is with coating
On the basis of quality.
Embodiment 2
The preparation manipulation of carrier and coating is same as Example 1.Copper chloride, potassium chloride, cerium chloride, zinc chloride are dissolved in water
In, dipping is ready for the carrier of coating, 120 degrees Celsius of dry 2h.Obtain cupric 4wt%, cerium 0.5wt%, potassium 2wt%, zinc
The catalyst of 1wt%, mass percentage is on the basis of coating quality.
Embodiment 3
The preparation manipulation of carrier and coating is same as Example 1.Copper chloride, potassium chloride, cerium chloride, zinc chloride are dissolved in water
In, dipping is ready for the carrier of coating, 120 degrees Celsius of dry 2h.Obtain cupric 5.5wt%, cerium 1wt%, potassium 1.5wt%,
The catalyst of zinc 1wt%, mass percentage is on the basis of coating quality.
Embodiment 3 '
The preparation manipulation of carrier and coating is same as Example 1.Copper chloride, potassium chloride, cerium chloride, zinc chloride are dissolved in water
In, dipping is ready for the carrier of coating, 120 degrees Celsius of dry 2h.Obtain cupric 1wt%, cerium 1wt%, potassium 1.5wt%, zinc
The catalyst of 1wt%, mass percentage is on the basis of coating quality.
Embodiment 3 "
The preparation manipulation of carrier and coating is same as Example 1.Copper chloride, potassium chloride, cerium chloride, zinc chloride are dissolved in water
In, dipping is ready for the carrier of coating, 120 degrees Celsius of dry 2h.Obtain cupric 10wt%, cerium 1wt%, potassium 1.5wt%, zinc
The catalyst of 1wt%, mass percentage is on the basis of coating quality.
Embodiment 4
The operating procedure of catalyst preparation is same as Example 1, and only the percentage composition of titanium oxide is changed to 1wt%.It obtains
The catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt%, mass percentage is on the basis of coating quality.
Embodiment 4 '
The operating procedure of catalyst preparation is same as Example 1, and only the percentage composition of titanium oxide is changed to 10wt%.It obtains
The catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt%, mass percentage is on the basis of coating quality.
Embodiment 4 "
The operating procedure of catalyst preparation is same as Example 1, and only the percentage composition of titanium oxide is changed to 0wt%.It obtains
The catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt%, mass percentage is on the basis of coating quality.
Embodiment 5
The operating procedure of catalyst preparation is same as Example 1, and it is five times that colloidal sol, which is supported on process on carrier to increase, quality
Increment is the 20wt% of vehicle weight.Obtain the catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt%, quality hundred
Divide content on the basis of coating quality.
Embodiment 6
Still using the integral catalyzer in embodiment 1, coating the preparation method is as follows: process is as follows, according to chemistry
Ratio is measured, certain density titanium salt aqueous solution and 10wt% Aluminum sol are prepared.The two is mixed under vigorous stirring, stirs 0.5h
Obtain colloidal sol.Colloidal sol is loaded into carrier up using the method for dipping, is then dried in vacuo at 80 degrees celsius, 500 degree of journeys
Sequence heating calcining, 1 degrees celsius/minute of heating rate calculate carrier quality increment after the completion.Colloidal sol is supported on process on carrier and needs
Will three times, mass incremental is the 4wt% of vehicle weight.
Copper chloride, potassium chloride, cerium chloride, zinc chloride is soluble in water, and dipping is ready for the carrier of coating, and 120 is Celsius
Spend dry 2h.The catalyst of cupric 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt% are obtained, mass percentage is with coating
On the basis of quality.
Comparative example 1
The operating procedure of catalyst preparation is same as Example 1, and carrier is only changed to cordierite carrier.By copper chloride,
Potassium chloride, cerium chloride, zinc chloride are soluble in water, and dipping is ready for the carrier of coating, 120 degrees Celsius of dry 2h.Obtain cupric
The catalyst of 4wt%, cerium 1wt%, potassium 1.5wt%, zinc 1wt%, mass percentage is on the basis of coating quality.
The catalyst that embodiment is obtained, filling in the reactor, 220 degrees Celsius, 0.32MPa, feed gas molar ratio be
C2H4:HCl:O2It is reacted under conditions of=1:1.8~2.0:0.5~0.6, the results are shown in Table 1.
The evaluation response result of 1 catalyst of table
It is above-mentioned that exemplary embodiment is illustrated, it should not be construed as limiting the invention.Although having disclosed
Multiple exemplary embodiments, those skilled in the art are readily appreciated that possible various deformation in exemplary embodiment, and do not have
Have and inherently deviates novel teachings and advantage of the invention.Therefore, all these Amoebidas are included in such as claim
In defined the scope of the present invention.It is understood that aforementioned is the explanation to various exemplary embodiment, it is not limitation
The deformation and other exemplary embodiments of disclosed specific embodiments, open embodiment, it is therefore an objective to be contained in appended right and want
In the range asked.
Claims (10)
1. a kind of oxychlorination catalyst comprising monolithic substrate, coating, active component and adjuvant component, wherein described whole
Body formula carrier is metal material, preferably stainless steel, the ferrite containing aluminium or Fe-Cr-Al alloy.
2. oxychlorination oxychlorination catalyst according to claim 1, which is characterized in that the ingredient of the coating includes oxidation
Aluminium or aluminium oxide-titanium oxide mixture, the preferably content of titanium oxide are 0-50wt%, preferably 2-20wt%.
3. oxychlorination catalyst according to claim 2, it is characterised in that the quality of the coating is the carrier quality
1-20%, preferably 5-15%.
4. oxychlorination catalyst according to any one of claim 1-3, which is characterized in that the active component is copper.
5. oxychlorination catalyst described in any one of -4 according to claim 1, which is characterized in that in terms of coating gross mass, institute
Stating active component content is 3wt%-8wt%, preferably 4wt%-7wt%.
6. oxychlorination catalyst described in any one of -4 according to claim 1, which is characterized in that the adjuvant component packet
It includes, the transition metal of at least one of rare earth metal selected from lanthanum, cerium, neodymium, praseodymium and yttrium of 0.1-10wt%, 0.1-10wt%
One of and 0.1-10wt% at least one alkali or alkaline earth metal, the above mass percentage is with coating quality
Benchmark.
7. oxychlorination catalyst according to claim 6, which is characterized in that the adjuvant component is that rare earth metal is lanthanum
And/or cerium, the transition metal are zinc, the alkali or alkaline earth metal is potassium, sodium or magnesium.
8. the preparation method of oxychlorination catalyst described in any one of -7 according to claim 1 comprising:
Step S1 provides the monolithic substrate of metal material；
Step S2 provides the colloid for being used to prepare coating；
Colloid described in step S2 is carried on monolithic substrate described in step S1, then dried by step S3, calcining, with
To cated carrier；
Step S4 provides the mixed solution containing active component and adjuvant component；
Step S5, by the cated carrier impregnation in the mixed solution, to obtain loading active component and auxiliary agent
The carrier of component；
Step S6, by carrier drying, the activation of the active component of the load and adjuvant component, to obtain the catalyst.
9. oxychlorination catalyst described in any one of -7 or oxychlorination according to claim 8 are urged according to claim 1
Application of the oxychlorination catalyst that the preparation method of agent obtains in ethylene oxychlorination.
10. application according to claim 9, which is characterized in that the operating condition of the ethylene oxychlorination is temperature:
210 DEG C -230 DEG C, pressure 0.25MPa-0.35MPa, feed gas molar ratio C2H4: HCl:O2=1:(1.8-2.0): (0.5-
0.6)。
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