CN101125297A - Oxychlorination catalyst and application thereof - Google Patents
Oxychlorination catalyst and application thereof Download PDFInfo
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- CN101125297A CN101125297A CNA2007101212981A CN200710121298A CN101125297A CN 101125297 A CN101125297 A CN 101125297A CN A2007101212981 A CNA2007101212981 A CN A2007101212981A CN 200710121298 A CN200710121298 A CN 200710121298A CN 101125297 A CN101125297 A CN 101125297A
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- Prior art keywords
- catalyst
- oxychlorination
- hydrogen chloride
- copper
- oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 106
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 44
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 25
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 23
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000460 chlorine Substances 0.000 claims abstract description 20
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 16
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 15
- 239000005977 Ethylene Substances 0.000 claims abstract description 8
- -1 rare earth metal salt Chemical class 0.000 claims abstract description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 43
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical group [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 235000021317 phosphate Nutrition 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 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
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 235000011180 diphosphates Nutrition 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 125000005341 metaphosphate group Chemical group 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 2
- 229940048084 pyrophosphate Drugs 0.000 claims description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 20
- 239000000047 product Substances 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 10
- 239000001103 potassium chloride Substances 0.000 description 10
- 235000011164 potassium chloride Nutrition 0.000 description 10
- 229910052684 Cerium Inorganic materials 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 5
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 238000007138 Deacon process reaction Methods 0.000 description 1
- 239000005819 Potassium phosphonate Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
Abstract
The invention discloses an oxychlorination catalyst and application and preparing method which belong to the catalyst preparing domain. The catalyst comprises the copper, phosphorus and alkali metals, the rare earth metal salt or oxide and inertia carrier, wherein, the content of the copper element takes two to fifteen wt percent of the catalyst, the phosphorus takes one to ten wt percent, the alkali metal element takes one to ten wt percent, the rare earth metal element takes zero to five wt percent, and the surplus is the inertia carrier. The catalyst of the invention is applicable to the chlorine preparing by the chlorine hydride catalyzing and oxidizing and the process of the ethylene and ethane oxychlorination. The catalyst has the advantages of high activity, good selectivity and long service life.
Description
Technical field
The invention belongs to catalyst preparation technology and range of application, be particularly related to a kind of oxychlorination catalyst and application thereof, specifically, relate to catalyst and the application thereof that is used for chloration hydro-oxidation preparing chlorine gas, ethylene oxychlorination system dichloroethanes and ethane oxychlorination preparing chloroethylene.
Background technology
In chlorine industry, chlorine and caustic soda are two big major products of chlorine industry, and the output of these two kinds of products has close contact.When market during to the increase in demand of chlorinated products, the output of caustic soda also will rise.If can not handle both relations well, make the demand of chlorine and caustic soda present unbalanced development, then will produce harmful effect to the economic benefit and the sustainable development of chlorine industry.At present, the demand of chlorinated products constantly increases, and replenishes the surplus that the undersupply of chlorine certainly will cause caustic soda by developing chlorine industry merely, and therefore, the problem of chemical industry chlor-alkali expending equilibrium is very important.
Industrial many processes are that raw material produces hydrogen chloride by-product with chlorine, and by-product hydrogen chloride be a kind of low price, demand is little, corrosivity is strong, the chemicals of intractable.Therefore, people wish to find a kind of not only economy but also safe hydrogen chloride preparing chlorine gas process.This not only can solve the pollution problem of hydrogen chloride to environment, and also can satisfy industrial to the ever-increasing demand of chlorine to a certain extent.In many documents and patent, report the method that hydrogen chloride prepares chlorine, mainly contained electrolysis, inorganic oxidizer direct oxidation method, catalyst air/oxygen oxidizing process (as the Deacon process).The electrolysis energy consumption is too big, the cost height; The shortcoming of inorganic oxidizer direct oxidation method is the equipment more complicated, the product separation difficulty, and energy consumption is bigger simultaneously.
Catalytic oxidation of hydrogen chloride for preparing chlorine gas, catalyst adopts oxide and/or chloride or its mixture of cupric usually, also can adopt the catalyst (CN95118842.9) of chromium-containing oxide and contain the catalyst (CN03803294.5) of other metals (Fe, Ru, Ce, Bi, Ni, Co, Ca, Ni).Cu-contained catalyst also comprises alkali metal salt (as potassium chloride), other rare earth elements and carrier composition usually.Because catalytic oxidation of hydrogen chloride for preparing chlorine gas need carry out under higher temperature, and active ingredient copper runs off easily under higher temperature, therefore, above-mentioned Cu-contained catalyst is difficult to obtain commercial Application.
Similar with the catalytic oxidation of hydrogen chloride for preparing chlorine gas process, vinyl chloride is produced related ethene or ethane oxychlorination process, usually also adopt Cu-contained catalyst, particularly ethane oxychlorination process also under higher temperature, to carry out usually, also have the losing issue of active ingredient copper.The Monsanto company of the U.S. has proposed the loaded catalyst ethane oxychlorination process (US4 that a kind of employing contains copper chloride, potassium phosphate and a small amount of platinum metal, 300,005), this process is carried out under 400 ℃-650 ℃, the more existing ethylene oxychlorination catalyst of catalyst stability is good, but this catalyst contains noble metal, and price is higher.
Based on above-mentioned background, the present invention proposes a kind of oxychlorination catalyst, be used for processes such as chloration hydro-oxidation preparing chlorine gas, ethylene oxychlorination system dichloroethanes and ethane oxychlorination preparing chloroethylene.
Summary of the invention
The objective of the invention is the deficiency at existing Cu-contained catalyst, a kind of catalyst that contains inert carrier, copper, phosphorus, alkali metal and rare earth metal is provided, this catalyst is used for the catalytic oxidation of hydrogen chloride for preparing chlorine gas process, has the advantage of active height, good stability.
Technical scheme of the present invention is as follows:
A kind of oxychlorination catalyst, comprise the salt of copper, alkali metal, rare earth metal and/or oxide, phosphorous compound and inert carrier, it is characterized in that the content of copper accounts for that 2~15wt% of catalyst weight, phosphorus element content account for 1~10wt%, alkali metal content accounts for 1~10wt%, thulium content accounts for 0~5wt%, remains to be inert carrier.
Described inert carrier is a kind of in aluminium oxide, alumina, diatomite, zeolite and the silica.
Oxide that copper is in the described catalyst or mantoquita;
The oxide of described copper is cupric oxide, cuprous oxide or their mixture.
The chloride of described copper is selected from CuCl or CuCl
2, or their mixture.
Described phosphorous compound is with phosphoric acid, pyrophosphoric acid, polyphosphoric acids, metaphosphoric acid, phosphorous acid, the oxide of phosphate, pyrophosphate, polyphosphate, metaphosphate, phosphite, phosphorus or their any two kinds and two or more mixtures.
Phosphorus-containing compound joins in the catalyst with oxide, phosphorous acid, solubility phosphite and/or the soluble phosphoric acid salt form of phosphoric acid, phosphorus in the preferred described catalyst.
Phosphorus element-containing described in the preferred catalyst joins among the oxychlorination catalyst with the phosphate of copper, thulium and/or alkali metal and/or their phosphite forms.
Described alkali metal is a kind of in sodium, the potassium.Preferred alkali metal exists with chloride and/or phos-phate forms.
Preferred catalyst middle rare earth metal is to be selected from least a in the lanthanide series metal, joins among the catalyst with chloride and/or oxide form.
Described Application of Catalyst is in the process of chloration hydro-oxidation preparing chlorine gas, ethylene oxychlorination system dichloroethanes and ethane oxychlorination preparing chloroethylene.
Concrete application is as follows:
1. described catalyst is used for the chloration hydro-oxidation preparing chlorine gas, and hydrogen chloride contacts generation chemical reaction with catalyst with oxygen (perhaps air) in reactor, can obtain the chlorine product; Its reaction condition is: the mol ratio 1: 2~10: 1 of 320~500 ℃ of temperature, pressure 0.05~0.5Mpa, hydrogen chloride and oxygen (air), the weight space velocity 0.05h of hydrogen chloride
-1~1.0h
-1
2. described catalyst is used for ethylene oxychlorination system dichloroethanes, and ethene, hydrogen chloride contact generation chemical reaction with catalyst with oxygen (perhaps air) in reactor, can obtain dichloroethanes; Its reaction condition is: the mol ratio that 180~300 ℃ of pressure of temperature are 0.05~0.5Mpa, ethene and hydrogen chloride is that the mol ratio of 1: 2~2: 1, hydrogen chloride and oxygen (air) is that 1: 2~5: 1, the weight space velocity of hydrogen chloride are 1~10h
-1
3. described catalyst is used for the ethane oxychlorination preparing chloroethylene, and ethane, hydrogen chloride contact generation chemical reaction with catalyst with oxygen (perhaps air) in reactor, obtain vinyl chloride; Its reaction condition is: 320~500 ℃ of temperature, pressure are that the mol ratio of 0.05~0.5Mpa, ethane and hydrogen chloride is 1: 5~5: 1, and the mol ratio of hydrogen chloride and oxygen (air) is 1: 5~5: 1.
Catalyst of the present invention is compared with existing cupric ethylene oxychlorination catalyst technology, and P elements adds the stability that helps improving catalyst; Compare with the Monsanto company ethane oxychlorination catalyst (US 4,300,005) of the U.S., alkali metal and rare earth element help increasing the stable and active of catalyst.Therefore, the present invention combines the advantage of existing cupric oxychlorination catalyst, and major advantage and beneficial effect are that catalyst stability is good, the long-term activity of using is constant substantially, therefore, often need not more catalyst changeout, the catalyst cost is low, production process continous-stable operation for a long time.
The specific embodiment
Following embodiment 1~7 is used for the example of preparing chlorine gas for catalyst
Embodiment 1,
In fixed-bed micro-reactor, add a certain amount of catalyst.Main active component in the catalyst is the copper chloride and the potassium chloride of load on aluminium oxide.The content of copper accounts for catalyst weight in the catalyst 10wt%, alkali metal potassium content account for 7wt%, and all the other are carrier.
Charging is that the mol ratio of hydrogen chloride and oxygen is 1: 1; Temperature in the reactor is 400 ℃, and pressure is 0.1MPa; The weight space velocity of hydrogen chloride charging is 0.8 hour
-1, product chlorine yield is 38.4%.
Embodiment 2 catalyst are used for the chloration hydro-oxidation preparing chlorine gas,
In fixed-bed micro-reactor, add a certain amount of catalyst.Main active component in the catalyst is copper chloride, potassium chloride and the cerium chloride of load on aluminium oxide.10wt%, the alkali metal potassium content that the content of copper accounts for catalyst weight in the catalyst accounts for 7wt%, the rare earth metal cerium content accounts for 2wt%, and all the other are carrier.
Charging is that the mol ratio of hydrogen chloride and oxygen is 1: 1; Temperature in the reactor is 400 ℃, and pressure is 0.1MPa; The weight space velocity of hydrogen chloride charging is 0.8 hour
-1, product chlorine yield is 78.8%.Catalyst uses continuously that activity begins to descend after 200 hours.
Embodiment 3
In fixed-bed micro-reactor, add a certain amount of catalyst.Main active component in the catalyst is copper chloride, potassium chloride and the cerium chloride of load on aluminium oxide, handles with this loaded catalyst of phosphoric acid then.10wt%, the phosphorus content that the content of copper accounts for catalyst weight in the catalyst after phosphoric acid is handled accounts for that 8wt%, alkali metal potassium content account for 7wt%, the rare earth metal cerium content accounts for 2wt%, and all the other are carrier.
Charging is that the mol ratio of hydrogen chloride and oxygen is 1: 1; Temperature in the reactor is 400 ℃, and pressure is 0.1MPa; The weight space velocity of hydrogen chloride charging is 0.8 hour
-1, product chlorine yield is 80.1%.Catalyst uses after 1000 hours active constant continuously.
Embodiment 4
In fluidized-bed reactor, add a certain amount of catalyst.Main active component in the catalyst is copper chloride, potassium phosphate, potassium chloride and the lanthanum chloride of load on aluminium oxide, and wherein the content of the copper 12wt%, the phosphorus content that account for catalyst weight accounts for that 2wt%, alkali metal potassium content account for 6wt%, rare earth lanthanum content accounts for 3wt%.
Charging is that the mol ratio of hydrogen chloride and oxygen is 1: 1; Temperature in the reactor is 390 ℃, and pressure is 0.1MPa; The weight space velocity of hydrogen chloride charging is 0.4 hour
-1Product chlorine yield is 70.5%.
Embodiment 5
In fluidized-bed reactor, add a certain amount of catalyst.Main active component in the catalyst is copper chloride, potassium phosphite, potassium chloride and the lanthanum chloride of load on aluminium oxide, and wherein the content of the copper 12wt%, the phosphorus content that account for catalyst weight accounts for that 2wt%, alkali metal potassium content account for 6wt%, rare earth lanthanum content accounts for 3wt%.
Charging is that the mol ratio of hydrogen chloride and oxygen is 1: 1; Temperature in the reactor is 390 ℃, and pressure is 0.1MPa; The weight space velocity of hydrogen chloride charging is 0.4 hour
-1Product chlorine yield is 68.2%.
Embodiment 6
In fluidized-bed reactor, add a certain amount of catalyst.Main active component in the catalyst is copper chloride, phosphorus pentoxide, potassium chloride and the lanthanum chloride of load on aluminium oxide, and wherein the content of the copper 12wt%, the phosphorus content that account for catalyst weight accounts for that 2wt%, alkali metal potassium content account for 6wt%, rare earth lanthanum content accounts for 3wt%.
Charging is that the mol ratio of hydrogen chloride and oxygen is 1: 1; Temperature in the reactor is 390 ℃, and pressure is 0.1MPa; The weight space velocity of hydrogen chloride charging is 0.4 hour
-1Product chlorine yield is 65.2%.
Embodiment 7
In two sections circulating fluid bed reactors, add a certain amount of catalyst.Main active component in the catalyst is copper chloride, potassium pyrophosphate, potassium chloride and the cerium chloride of load on aluminium oxide, and wherein the content of the copper 5wt%, the phosphorus content that account for catalyst weight accounts for that 1wt%, alkali metal potassium content account for 3wt%, the rare earth metal cerium content accounts for 1wt%.
Charging is that the mol ratio of hydrogen chloride and oxygen is 1: 2; The temperature of hypomere is 360 ℃ in the reactor, and the temperature of epimere is 220 ℃ in the reactor, and pressure is 0.1MPa; The weight space velocity of hydrogen chloride charging is 0.1 hour
-1Product chlorine yield is 95%.
Use in the embodiment 8 preparation ethane
In fluidized-bed reactor, add a certain amount of catalyst.Main active component in the catalyst is copper chloride, potassium chloride and the cerium chloride of load on aluminium oxide, handles with this loaded catalyst of phosphoric acid then.5wt%, the phosphorus content that the content of copper accounts for catalyst weight in the catalyst after phosphoric acid is handled accounts for that 1wt%, alkali metal potassium content account for 5wt%, the rare earth metal cerium content accounts for 2wt%.
Charging is that the mol ratio of ethane, hydrogen chloride and oxygen is 1: 2: 1, and the temperature in the reactor is 450 ℃, and pressure is 0.1MPa; The conversion ratio of ethane is 95%.
Use in the embodiment 9 preparation ethene
In fluidized-bed reactor, add a certain amount of catalyst.Main active component in the catalyst is copper chloride, potassium chloride and the cerium chloride of load on aluminium oxide, handles with this loaded catalyst of phosphoric acid then.8wt%, the phosphorus content that the content of copper accounts for catalyst weight in the catalyst after phosphoric acid is handled accounts for that 2wt%, alkali metal potassium content account for 4wt%, the rare earth metal cerium content accounts for 3wt%.
Charging is that the mol ratio of ethene, hydrogen chloride and oxygen is 1.8: 2: 1, and the temperature in the reactor is 220 ℃, and pressure is 0.1MPa; The air speed of charging is 4 hours
-1, the conversion ratio of ethene is 25%.
Claims (12)
1. oxychlorination catalyst, the salt and/or oxide and the inert carrier that comprise copper, phosphorus, alkali metal, rare earth metal, it is characterized in that, 2~15wt%, the phosphorus element content that the content of copper accounts for catalyst weight accounts for that 1~10wt%, alkali metal content account for 1~10wt%, thulium content accounts for 0~5wt%, remains to be inert carrier.
2. oxychlorination catalyst according to claim 1 is characterized in that inert carrier is a kind of in aluminium oxide, alumina, diatomite, zeolite and the silica.
3. oxychlorination catalyst according to claim 1 is characterized in that, the oxide or the mantoquita of institute's cupric in the catalyst.
4. oxychlorination catalyst according to claim 1, it is characterized in that, institute's phosphorus element-containing is with phosphoric acid, pyrophosphoric acid, polyphosphoric acids, metaphosphoric acid, phosphorous acid in the catalyst, the oxide of phosphate, pyrophosphate, polyphosphate, metaphosphate, phosphite, phosphorus or their any two kinds and two or more mixtures.
5. oxychlorination catalyst according to claim 4 is characterized in that, one or more in the elements such as described various phosphate alkali metal containings, copper, rare earth.
6. oxychlorination catalyst according to claim 1 is characterized in that, alkali metal is sodium and/or potassium.
7. oxychlorination catalyst according to claim 1 is characterized in that, the rare earth metal in the catalyst is to be selected from least a in the lanthanide series metal.
8. oxychlorination catalyst according to claim 3 is characterized in that, the oxide of described copper is cupric oxide, cuprous oxide or their mixture.
9. oxychlorination catalyst according to claim 3 is characterized in that the chloride of described copper is selected from CuCl or CuCl
2, or their mixture.
10. oxychlorination catalyst is equipped with application in the chlorine technology at catalytic oxidation of hydrogen chloride for preparing, it is characterized in that reaction condition is: the mol ratio 1: 2~10: 1 of 320~500 ℃ of temperature, pressure 0.05~0.5Mpa, hydrogen chloride and oxygen (air), the weight space velocity 0.05h of hydrogen chloride
-1~1.0h
-1
11. oxychlorination catalyst prepares application in the dichloroethanes technology at ethylene oxychlorination, it is characterized in that reaction condition is: the mol ratio that 180~300 ℃ of pressure of temperature are 0.05~0.5Mpa, ethene and hydrogen chloride is that the mol ratio of 1: 2~2: 1, hydrogen chloride and oxygen (air) is that 1: 2~5: 1, the weight space velocity of hydrogen chloride are 1~10h-1.
12. oxychlorination catalyst prepares application in the vinyl chloride technology at ethane oxychlorination, it is characterized in that, reaction condition is: 320~500 ℃ of temperature, pressure are that the mol ratio of 0.05~0.5Mpa, ethane and hydrogen chloride is 1: 5~5: 1, and the mol ratio of hydrogen chloride and oxygen (air) is 1: 5~5: 1.
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