CN1050535C - 用于生产不饱和芳烃的脱氢催化剂 - Google Patents
用于生产不饱和芳烃的脱氢催化剂 Download PDFInfo
- Publication number
- CN1050535C CN1050535C CN95113340A CN95113340A CN1050535C CN 1050535 C CN1050535 C CN 1050535C CN 95113340 A CN95113340 A CN 95113340A CN 95113340 A CN95113340 A CN 95113340A CN 1050535 C CN1050535 C CN 1050535C
- Authority
- CN
- China
- Prior art keywords
- gram
- catalyzer
- dehydrogenation catalyst
- oxide
- aromatic hydrocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 27
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 6
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229910052779 Neodymium Inorganic materials 0.000 claims description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 7
- 229910052775 Thulium Inorganic materials 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052706 scandium Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 5
- 150000004706 metal oxides Chemical class 0.000 abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 50
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 9
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 9
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 7
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 7
- 235000015320 potassium carbonate Nutrition 0.000 description 7
- 239000004568 cement Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229960004643 cupric oxide Drugs 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical class [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002823 nitrates Chemical class 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QXQZBDRCFKSYAA-UHFFFAOYSA-N [Cr].[K].[Fe] Chemical compound [Cr].[K].[Fe] QXQZBDRCFKSYAA-UHFFFAOYSA-N 0.000 description 2
- KIYAAZAHNBDNEG-UHFFFAOYSA-N [Tm].[Mg].[Mo].[K].[Fe] Chemical compound [Tm].[Mg].[Mo].[K].[Fe] KIYAAZAHNBDNEG-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- UHTYDNCIXKPJDA-UHFFFAOYSA-H oxalate;praseodymium(3+) Chemical class [Pr+3].[Pr+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHTYDNCIXKPJDA-UHFFFAOYSA-H 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 102000040350 B family Human genes 0.000 description 1
- 108091072128 B family Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- DIGZKZLYDYJFHH-UHFFFAOYSA-N [K].[Mo].[Ce].[Fe] Chemical compound [K].[Mo].[Ce].[Fe] DIGZKZLYDYJFHH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 alkenyl arene Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- VEFXTGTZJOWDOF-UHFFFAOYSA-N benzene;hydrate Chemical compound O.C1=CC=CC=C1 VEFXTGTZJOWDOF-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 210000000080 chela (arthropods) Anatomy 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- VKLDOHAGZQSOPP-UHFFFAOYSA-H neodymium(3+);oxalate Chemical class [Nd+3].[Nd+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VKLDOHAGZQSOPP-UHFFFAOYSA-H 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical class [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical class [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical class [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-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
- 239000000376 reactant Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
本发明是一种用于生产不饱和芳烃的脱氢催化剂，其组成是在铁-钾-钼-镁-稀土金属元素体系中，加入了多种金属氧化物。其中，稀土金属元素在催化剂中至少含有二种的组合，加入的金属氧化物中的元素选自IB-VIIIB族和IIIA-VA族中的至少一种或几种。制得的催化剂具有更高的活性与选择性，自再生能力很强，可广泛用于饱和芳烃的脱氢。
Description
本发明涉及一种用于烷基芳烃的脱氢催化剂，这种催化剂可用于乙苯脱氢制苯乙烯、二乙苯脱氢制二乙烯苯，亦可用于甲基乙苯脱氢制甲基苯乙烯。
众所周知，通常工业上生产烯基芳烃是由烷基芳烃催化脱氢制得，然而，该生产方法的关键之一是选择一种高效的脱氢催化剂，据有关文献资料报道，以催化剂的主要组成来划分，可分为二大类：第一类催化剂是由铁-钾-铬为主要成分，再添加其他元素，其特点是投料水比(水蒸汽与乙苯比)低，选择性不高，一般不超过94％，转化率也低，苯乙烯总收率较低。如US4533650文献公开了铁-钾-铬为主要成份，再添加稀土金属元素的催化剂体系。该体系一方面含铬这有毒成份，另一方面该催化剂体系的苯乙烯总收率也较低，最高也仅62.2％。第二类催化剂是以铁-钾-铈-钼为主要成分，再添加其他元素，如已公开的中国专利ZL91109968.9，这类催化剂选择性、转化率比前者高，但其苯乙烯总收率也仅70％左右。
以工业上乙苯脱氢生产苯乙烯的规模而言，其年产量大都是万吨至几十万吨，因此，对脱氢催化剂在性能上作微小的改进，就可使生产企业获得巨大的收益。即使是催化剂的收率增加一个百分点或者二个百分点，对一个万吨级规模的工业装置来说，不需改动任何设备，不需增加投资，年就净增加数百吨的产品，提高了装置操作效率，降低了原料消耗。为此，在寻求适用于低水比的催化剂同时，提高催化剂的转化率和选择性，是人们一直关注的研究课题。
本发明的目的是提供一种用于生产不饱和芳烃的脱氢催化剂，比目前工业上使用的脱氢催化剂具有更高的活性与产物收率，又有较强的自再生能力，正常使用中不需再生，适于在低水比(水比小于1.5)条件下使用，特别是在反应过程中，即使短时间(20分钟之内)，突然停止水蒸汽进料，也不会造成催化剂失活。
本发明提供的脱氢催化剂是以铁-钾-钼-镁-稀土金属元素为主要组份，加入了多种金属氧化物，其金属元素可从元素周期表中的碱土金属、IB-VIIIB族和IIIA-VA族中选用，再添加致孔剂和粘结剂制成催化剂。其中催化剂中含有至少二种稀土金属元素。
具体地说，本发明的脱氢催化剂的组成为(重量百分比)：Fe2O340～70％、K2O10～40％、稀土金属氧化物2～15％、MoO30～5％，MgO0.05～5％，其中所用的铁以氧化铁的形式加入，氧化铁由酸性亚铁盐经氧化制得。所用的钾以钾盐形式加入，所用的镁以镁的氧化物形式加入，其含量较好范围为0.5～4％。所用的稀土金属以氧化物、氢氧化物或稀土金属盐形式加入，所用的稀土金属元素为选自Co、La、Pr、Nd、Sm中的至少二种，其加入的含量范围以氧化物计，较好为3～8％。钼以钼盐或氧化物形式加入，同时又加入了多种金属氧化物，可以从下面选自Cu、Zn、Sc、Ti、W、Mn、Ni、Pd、Al、P、Bi、B、Sn、Pb、Si元素的氧化物中任意选用至少一种或几种，其含量为0.001～5％，较好范围为0.002～2％(重量)，其余为致孔剂和粘结剂，致孔剂可以是聚苯乙烯微球，石墨或羧甲基纤维素。
本发明的另一技术方案是催化剂组成以重量百分比计含有Fe2O3：40～70％，K2O：10～40％，MoO3：0～5％，MgO：0.05～5％，及0.001～5％的至少一种选自Cu、Zn、Sc、Ti、W、Mn、Ni、Pd、Al、P、Bi、B、Sn、Pb、Si元素的氧化物，其中催化剂中还含有除铈以外的至少一种稀土金属，其含量以氧化物计为2～15％。
上述催化剂组成中，稀土金属元素的优选元素为La，Pr，Nd，Sm，催化剂中稀土金属元素的含量优选范围以氧化物计为3～8％(重量)。
本发明的催化剂制备方法：
将按配比称量的Fe、K、稀土金属元素、Mo、碱土金属、B族元素、A族元素、粘结剂、致孔剂混合均匀后，加入适量的脱离子水，制成有粘性、适合挤条的面团状物，经挤条、切粒成直径为3毫米、长8～10毫米的颗粒，然后，在500～1000℃下焙烧3～10小时，就可获得成品催化剂。
本发明的脱氢催化剂，在一定的工艺条件下，可适用于乙苯、二乙苯、甲基乙苯脱氢生成苯乙烯、二乙烯苯和甲基苯乙烯。
按上述方法制得的催化剂在等温式固定床中进行活性评价。对乙苯脱氢制苯乙烯活性评价而言，过程简述如下：
将脱离子水和乙苯分别经计量泵输入预热混合器，预热混合成气态后进入反应器。反应器采用电热丝加热，使之达到预定温度。反应器内径为1″的不锈钢管，内可装填100毫升、粒径为3毫米的催化剂。由反应器流出的反应物经水冷凝后用气相色谱仪分析其组成。
乙苯转化率和苯乙烯选择性按以下公式计算：
乙苯转化率％＝反应前乙苯浓度(wt％)-反应后乙苯浓度(wt％)/反应前乙苯浓度(wt％)。
苯乙烯选择性％＝生成的苯乙烯浓度(wt％)/反应前乙苯浓度(wt％)-反应后乙苯浓度(wt％)。
下面实施例进一步描述本发明：
【实施例1】将279克氧化铁、54克碳酸钾、50克草酸铈、10克草酸钕、9克氧化镁、0.9克氧化铜、35克水泥、4.1克羧甲基纤维素在捏和机中搅拌1～6小时，取出挤条、挤成直径为3毫米、长8～10毫米的颗粒。然后置于焙烧炉中，于600℃焙烧6小时制得催化剂。将100毫升、粒径为3毫米的催化剂放入内径1″的等温反应器，进行活性评价，评价条件是反应温度620℃，水比(水/乙苯)2.0(重量比)。评价结果：乙苯转化率77.15％，苯乙烯选择性95.35％，苯乙烯收率为73.56％。
【实施例2】将175克氧化铁、97克碳酸钾、30克草酸铈(7.38％)、30克草酸镨、5.5克钼酸铵、6克氧化镁、0.5克硝酸钴，15克水泥、6克羧甲基纤维素，按实施例1方法制成催化剂，按实施例1的评价条件进行评价，评价结果：乙苯转化率78.35％，苯乙烯选择性95.60％，苯乙烯收率为74.90％。
【实施例3】将275克氧化铁、80克碳酸钾、3克钼酸铈、4克钼酸谱、3克钼酸钕、8克氧化镁、20克硝酸铋、0.9克氧化铜、22克水泥、8克羧甲基纤维素，按实施例1方法制得催化剂，按实施例1的同样条件评价活性，评价结果：乙苯转化率78.64％，苯乙烯选择性95.41％，苯乙烯收率为75.03％。
【实施例4】将270克氧化铁、72克硝酸铈、30克硝酸钐、10克硝酸镧、16克钼酸铵、130克碳酸钾、8克氧化镁、9克氧化镍、0.9克氧化铜、0.1克氧化硼、0.9克氧化钛、0.1克氧化锡、0.1克氧化钨、22克水、9克羧甲基纤维素，按实施例1方法制得催化剂，按实施例1的评价条件进行评价，不同的是反应温度为600℃，水比为1.5(重量比)，评价结果：乙苯转化率67.23％，苯乙烯选择性96.12％，苯乙烯收率为64.62％。
【实施例5】将270克氧化铁、130克碳酸钾、8克钳酸铵、48克硝酸铈、50克硝酸镨、20克硝酸钕、10克硝酸镧、5克氧化镁、2.35克氧化锌、0.1克氧化钯、0.1克氧化铅、22克水泥、9克羧甲基纤维素，按实施例1方法制得催化剂，按实施例1的评价条件进行评价，乙苯转化率79.10％，苯乙烯选择性96.08％，苯乙烯收率为76.0％，如果将水比降低到1.3(重量比)，则乙苯转化率75.63％，苯乙烯选择性95.30％苯乙烯收率为72.08％。
【实施例6】按实施例4的催化剂组成，使用实施例1的评价条件，评价结果：乙苯转化率78.62％，选择性95.38％，苯乙烯收率为74.99％。然后，仍按实施例1的评价条件，继续通乙苯，停供水蒸汽20分钟后，继续通入水蒸汽进行反应，评价结果：乙苯转化率78.40％，选择性95.25％，苯乙烯收率为74.68％，说明本发明的催化剂具有很强的自再生能力。
从实施例说明，本发明的催化剂，在铁-钾-钼-镁-稀土金属元素(至少二种)体系中，添加了多种金属氧化物及其致孔剂和粘结剂，所制成的脱氢催化剂达到了适用于低水比(如水比为1.3时)仍具有高的转化率和选择性以及产物苯乙烯收率，又有很强的自再生能力，同时，本发明的催化剂还具有制备简单、反应诱导期短、操作弹性大等优点。
【实施例7】
将290克氧化铁、60克碳酸钾、30克草酸镨、8.5克氧化钼、7克氧化镁、0.9克氧化铜、37克水泥、4.5克羧甲基纤维素，按实施例1的各步骤制成催化剂，且进行活性评价。评价结果：乙苯转化率72.8％，苯乙烯选择性95.28％，苯乙烯收率69.36％。
【实施例8】
将275克氧化铁、70克碳酸钾、3.8克钼酸镨、4.1克硝酸镧、6克氧化镁、0.5克硝酸钴、1.0克氧化铜、25克水泥、7克羧甲基纤维素，按实施例1的方法制得催化剂，按实施例1的评价条件评价活性，评价结果：乙苯转化率76.65％，苯乙烯选择性95.40％，苯乙烯收率为73.12％。
Claims (7)
1、一种用于生产不饱和芳烃的脱氢催化剂，其组成以重量百分比计含有Fe2O3：40～70％，K2O：10～40％，MoO3：0～5％，MgO：0.05～5％，及0.001～5％的至少一种选自Cu、Zn、Sc、Ti、W、Mn、Ni、Pd、Al、P、Bi、B、Sn、Pb、Si元素的氧化物，其特征在于催化剂中还含有至少二种稀土金属元素Ce、La、Pr、Nd、Sm的化合物，其含量以氧化物计为2～15％。
2、根据权利要求1所述用于生产不饱和芳烃的脱氢催化剂，其特征在于MgO的重量百分含量为0.5～4％。
3、根据权利要求1所述用于生产不饱和芳烃的脱氢催化剂，其特征在于至少一种选自Cu、Zn、Sc、Ti、W、Mn、Ni、Pd、Al、P、Bi、B、Sn、Pb、Si元素的氧化物的含量以重量百分比计为0.002～2％。
4、根据权利要求1所述用于生产不饱和芳烃的脱氢催化剂，其特征在于催化剂中的稀土金属元素为La、Pr、Nd、Sm。
5、根据权利要求1所述用于生产不饱和芳烃的脱氢催化剂，其特征在于催化剂中稀土金属元素化合物，其含量以氧化物计为3～8％。
6、一种用于生产不饱和芳烃的脱氢催化剂，其组成以重量百分比计含有Fe2O3：40～70％，K2O：10～40％，MoO3：0～5％，MgO：0.05～5％，及0.001～5％的至少一种选自Cu、Zn、Sc、Ti、W、Mn、Ni、Pd、Al、P、Bi、B、Sn、Pb、Si元素的氧化物，其特征在于催化剂中还含有除铈以外的至少一种稀土金属元素La、Pr、Nd、Sm，其含量以氧化物计为2～15％。
7、根据权利要求6所述用于生产不饱和芳烃的脱氢催化剂，其特征在于催化剂中稀土金属元素La、Pr、Nd、Sm，以重量百分比计其含量以氧化物计为3～8％。
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95113340A CN1050535C (zh) | 1995-11-15 | 1995-11-15 | 用于生产不饱和芳烃的脱氢催化剂 |
| TW085113954A TW343932B (en) | 1995-11-15 | 1996-11-14 | A catalyst for the dehydrogenation of unsaturated aromatic hydrocarbon and a process for producing unsaturated hydrocarbon using said catalyst |
| EP96937974A EP0956899B1 (en) | 1995-11-15 | 1996-11-14 | A catalyst for manufacturing alkyl aromatics and production method and use thereof |
| DE69626139T DE69626139T2 (de) | 1995-11-15 | 1996-11-14 | Katalysator fur die herstellung von alkylaromaten und verfahren zu dessen herstellung und dessen verwendung |
| PCT/CN1996/000101 WO1997018034A1 (en) | 1995-11-15 | 1996-11-14 | A catalyst for manufacturing alkyl aromatics and production method and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95113340A CN1050535C (zh) | 1995-11-15 | 1995-11-15 | 用于生产不饱和芳烃的脱氢催化剂 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1150062A CN1150062A (zh) | 1997-05-21 |
| CN1050535C true CN1050535C (zh) | 2000-03-22 |
Family
ID=5079955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95113340A Expired - Lifetime CN1050535C (zh) | 1995-11-15 | 1995-11-15 | 用于生产不饱和芳烃的脱氢催化剂 |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0956899B1 (zh) |
| CN (1) | CN1050535C (zh) |
| DE (1) | DE69626139T2 (zh) |
| TW (1) | TW343932B (zh) |
| WO (1) | WO1997018034A1 (zh) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6242379B1 (en) * | 1998-04-01 | 2001-06-05 | United Catalysts Inc. | Dehydrogenation catalysts |
| CZ20003590A3 (cs) * | 1998-04-01 | 2001-08-15 | Süd-Chemie Inc. | Dehydrogenační katalyzátor |
| US6756339B1 (en) | 1998-04-01 | 2004-06-29 | Sud-Chemie Inc. | Dehydrogenation catalysts |
| FR2844790B1 (fr) | 2002-09-20 | 2004-10-22 | Inst Francais Du Petrole | Procede de coproduction de paraxylene et de styrene |
| CN100418937C (zh) * | 2005-08-15 | 2008-09-17 | 中国石油化工股份有限公司 | 二乙苯脱氢制备二乙烯苯的方法 |
| CN100443170C (zh) * | 2005-09-01 | 2008-12-17 | 中国石油天然气股份有限公司 | 乙苯脱氢制苯乙烯催化剂及其制备方法 |
| CN100430133C (zh) * | 2005-12-14 | 2008-11-05 | 中国石油化工股份有限公司 | 低水比乙苯脱氢催化剂 |
| JP5528040B2 (ja) * | 2008-10-03 | 2014-06-25 | Ｄｏｗａエレクトロニクス株式会社 | 排ガス浄化触媒用複合酸化物とその製造方法および排ガス浄化触媒用塗料とディーゼル排ガス浄化用フィルタ |
| US8163971B2 (en) * | 2009-03-17 | 2012-04-24 | Lummus Technology Inc. | Method of providing heat for chemical conversion and a process and system employing the method for the production of olefin |
| CN101992092B (zh) * | 2009-08-31 | 2013-06-05 | 中国石油化工股份有限公司 | 乙苯脱氢制备苯乙烯的催化剂及其制备方法 |
| CN101992094B (zh) * | 2009-08-31 | 2012-10-10 | 中国石油化工股份有限公司 | 低水比乙苯脱氢催化剂及其制备方法 |
| CN102040463B (zh) * | 2009-10-13 | 2012-10-10 | 中国石油化工股份有限公司 | 乙苯脱氢制苯乙烯的方法 |
| EP2522418A1 (de) * | 2011-05-11 | 2012-11-14 | Sachtleben Pigment GmbH | Rohstoffe für vanadiumfreie oder vanadiumreduzierte DeNOx-Katalysatoren und Verfahren zu ihrer Herstellung |
| CN102950005A (zh) * | 2011-08-24 | 2013-03-06 | 中国石油化工股份有限公司 | 一种用于甲基乙苯脱氢制备甲基苯乙烯的催化剂及制备方法 |
| JP6335788B2 (ja) | 2011-12-22 | 2018-05-30 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | 炭化水素の脱水素化のための触媒 |
| CN102614864A (zh) * | 2012-03-01 | 2012-08-01 | 河南科技大学 | 异丁烷脱氢催化剂及其制备方法 |
| CN104525213B (zh) * | 2014-12-29 | 2016-06-22 | 厦门大学 | 由混合铁源制备乙苯脱氢Fe-K系催化剂的方法 |
| RU2626238C1 (ru) * | 2016-06-08 | 2017-07-25 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Ярославский государственный технический университет" (ФГБОУВО "ЯГТУ") | Катализатор для дегидрирования алкилароматических углеводородов |
| CN107790146B (zh) * | 2016-09-06 | 2020-04-17 | 中国石油化工股份有限公司 | 制备二乙烯苯的催化剂及其制备方法和应用 |
| CN112239389B (zh) * | 2019-07-19 | 2023-04-07 | 中国石油化工股份有限公司 | 烷烯基芳烃的制造方法 |
| CN112657503B (zh) * | 2019-10-15 | 2023-09-29 | 中国石油化工股份有限公司 | 铁系催化剂及其制备方法与应用 |
| CN113877593B (zh) * | 2020-07-02 | 2024-02-23 | 中国石油化工股份有限公司 | 高强度烷基芳烃脱氢催化剂及其制备方法和应用以及烷基芳烃脱氢方法 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260520A (en) * | 1978-11-16 | 1981-04-07 | Hoechst Aktiengesellschaft | Carrier-supported catalyst and process for making it |
| US4308175A (en) * | 1978-11-16 | 1981-12-29 | Hoechst Aktiengesellschaft | Carrier-supported catalyst and process for making it |
| US4533650A (en) * | 1982-12-14 | 1985-08-06 | Institut Francais Du Petrole | Process for manufacturing a catalyst containing iron, chromium and potassium oxides and at least one rare earth metal oxide, for use in dehydrogenation reactions |
| US4628136A (en) * | 1985-12-17 | 1986-12-09 | Lummus Crest, Inc. | Dehydrogenation process for production of styrene from ethylbenzene comprising low temperature heat recovery and modification of the ethylbenzene-steam feed therewith |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3904552A (en) * | 1973-03-08 | 1975-09-09 | Girdler Chemical | Dehyrogenation catalyst |
| US4458098A (en) * | 1980-11-17 | 1984-07-03 | Uop Inc. | Hydrocarbon dehydrogenation method and nonacidic multimetallic catalytic composite for use therein |
| FR2617060A1 (fr) * | 1987-06-29 | 1988-12-30 | Shell Int Research | Catalyseur de deshydrogenation, application a la preparation de styrene et styrene ainsi obtenu |
| JP2701065B2 (ja) * | 1989-03-23 | 1998-01-21 | 日東化学工業株式会社 | モリブデン―ビスマス含有複合酸化物触媒の製法 |
| US5023225A (en) * | 1989-07-21 | 1991-06-11 | United Catalysts Inc. | Dehydrogenation catalyst and process for its preparation |
| JPH04277030A (ja) * | 1991-03-05 | 1992-10-02 | Nissan Gaadoraa Shokubai Kk | エチルベンゼン脱水素触媒 |
| CN1028495C (zh) * | 1991-10-30 | 1995-05-24 | 中国石油化工总公司 | 用于烷基芳烃的脱氢催化剂 |
-
1995
- 1995-11-15 CN CN95113340A patent/CN1050535C/zh not_active Expired - Lifetime
-
1996
- 1996-11-14 DE DE69626139T patent/DE69626139T2/de not_active Expired - Lifetime
- 1996-11-14 TW TW085113954A patent/TW343932B/zh not_active IP Right Cessation
- 1996-11-14 WO PCT/CN1996/000101 patent/WO1997018034A1/zh not_active Ceased
- 1996-11-14 EP EP96937974A patent/EP0956899B1/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260520A (en) * | 1978-11-16 | 1981-04-07 | Hoechst Aktiengesellschaft | Carrier-supported catalyst and process for making it |
| US4308175A (en) * | 1978-11-16 | 1981-12-29 | Hoechst Aktiengesellschaft | Carrier-supported catalyst and process for making it |
| US4533650A (en) * | 1982-12-14 | 1985-08-06 | Institut Francais Du Petrole | Process for manufacturing a catalyst containing iron, chromium and potassium oxides and at least one rare earth metal oxide, for use in dehydrogenation reactions |
| US4628136A (en) * | 1985-12-17 | 1986-12-09 | Lummus Crest, Inc. | Dehydrogenation process for production of styrene from ethylbenzene comprising low temperature heat recovery and modification of the ethylbenzene-steam feed therewith |
Also Published As
| Publication number | Publication date |
|---|---|
| WO1997018034A1 (en) | 1997-05-22 |
| TW343932B (en) | 1998-11-01 |
| DE69626139D1 (de) | 2003-03-13 |
| EP0956899A4 (zh) | 1999-12-08 |
| CN1150062A (zh) | 1997-05-21 |
| DE69626139T2 (de) | 2003-10-16 |
| EP0956899B1 (en) | 2003-02-05 |
| EP0956899A1 (en) | 1999-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1050535C (zh) | 用于生产不饱和芳烃的脱氢催化剂 | |
| CN1028495C (zh) | 用于烷基芳烃的脱氢催化剂 | |
| US6037301A (en) | Amorphous alloy catalyst containing boron, its preparation and use | |
| US4533650A (en) | Process for manufacturing a catalyst containing iron, chromium and potassium oxides and at least one rare earth metal oxide, for use in dehydrogenation reactions | |
| DE60100918T2 (de) | Verfahren zur Herstellung eines wasserstoffreichen Gases | |
| US10406508B2 (en) | Binder-free high strength, low steam-to-oil ratio ethylbenzene dehydrogenation catalyst | |
| CN102728371A (zh) | 一种高铈含量烷基芳烃脱氢催化剂及其制造方法 | |
| JPH05245383A (ja) | 固体酸アルキル化触媒組成物及びこれを使用するアルキル化方法 | |
| CN1055076C (zh) | 用于生产苯乙烯的脱氢工艺 | |
| CN102040466A (zh) | 乙苯脱氢制备苯乙烯的方法 | |
| CN1134385C (zh) | 烷基芳烃脱氢催化剂及其制备方法 | |
| CN101993336A (zh) | 低水比条件下乙苯脱氢制备苯乙烯的方法 | |
| CN1047097C (zh) | 用于生产烷烯基芳烃的脱氢催化剂 | |
| CN100430133C (zh) | 低水比乙苯脱氢催化剂 | |
| CN108097260B (zh) | 一种乙苯脱氢制苯乙烯催化剂及制备方法 | |
| CN110681390A (zh) | 低水比乙苯脱氢催化剂及其制备方法和应用 | |
| CN1160152C (zh) | 环已醇脱氢制环已酮催化剂及其制备方法 | |
| CN109569637B (zh) | 低水比乙苯脱氢催化剂及制备方法 | |
| CN112237919A (zh) | 用于制备苯乙烯的脱氢催化剂 | |
| CN1133494C (zh) | 烷基芳烃脱氢催化剂 | |
| CN1233604C (zh) | 一种烷基芳烃脱氢催化剂及其制备方法 | |
| CN1052431C (zh) | 乙烷氧化脱氢制乙烯的催化剂和应用 | |
| EP0768996B1 (de) | Katalysator und verfahren für die katalytische oxidative dehydrierung von alkylaromaten | |
| CN1268398A (zh) | 烷基芳烃催化脱氢催化剂 | |
| CN1113832A (zh) | 氨合成催化剂及制备方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20000322 |
|
| EXPY | Termination of patent right or utility model |