TW201627067A - 用於製造烯烴的催化劑與製程 - Google Patents
用於製造烯烴的催化劑與製程 Download PDFInfo
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- TW201627067A TW201627067A TW105103017A TW105103017A TW201627067A TW 201627067 A TW201627067 A TW 201627067A TW 105103017 A TW105103017 A TW 105103017A TW 105103017 A TW105103017 A TW 105103017A TW 201627067 A TW201627067 A TW 201627067A
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- Prior art keywords
- metathesis catalyst
- zeolite
- catalyst according
- group
- weight
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 27
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title description 14
- 230000008569 process Effects 0.000 title description 10
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 32
- 239000010457 zeolite Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000005649 metathesis reaction Methods 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 11
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical group [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 229940006460 bromide ion Drugs 0.000 claims 1
- 150000004673 fluoride salts Chemical class 0.000 claims 1
- 150000004694 iodide salts Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 230000000694 effects Effects 0.000 abstract description 5
- 230000009849 deactivation Effects 0.000 abstract description 4
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 19
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 18
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 7
- 238000011069 regeneration method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- -1 iodine Ions Chemical class 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000005865 alkene metathesis reaction Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011335 coal coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910021476 group 6 element Inorganic materials 0.000 description 1
- 229910021474 group 7 element Inorganic materials 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
Classifications
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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- B01J27/25—Nitrates
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- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- C—CHEMISTRY; METALLURGY
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- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
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- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
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- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/163—X-type faujasite
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
本發明提供一種催化劑，包含一過渡金屬、一無機載體、一沸石、以及一層狀雙氫氧化物。於烯烴製造製程中使用根據本發明之催化劑，可展現高活性、高選擇性、及降低的去活化速率，因此可表現較長的反應循環，且延長了催化劑壽命。
Description
本發明係關於用於藉由烯烴複分解(metathesis)反應以製造烯烴的催化劑與製程。
複分解是石化工業中的重要反應之一，尤其是乙烯與丁烯的交錯複分解，其用於製造有大量需求的丙烯而具經濟意義。
在典型的工業複分解製程中，複分解催化劑隨時間去活化，因此需要週期性地再生。再生製程通常涉及將去活化的催化劑在高溫下以氧化氣體處理，以燒除反應當中產生的毒性物質及重質沉積物。催化劑只應接受受限次數的該等再生製程，因為其所使用的極端條件會改變催化劑的某些特殊性質，例如表面積，且因此降低它的效率。
已發現在乙烯與丁烯反應製造丙烯的反應中，形成了1,3-丁二烯的副產物。即使在系統中僅有低濃度的1,3-丁二烯，也會引發煤焦(coke)形成在催化劑表面上，導致催化劑去活化。為了降低1,3-丁二烯所造成去活化速率的此種效果，可以在氫氣存在下進行複分解製程，例如於美國專利公開號US 20100145126 A1、US 20130252804 A1、及US 20100191030 A1中所揭露者。然
而，氫氣的存在會導致丙烯產物的氫化，而因此降低丙烯的產物產率。
本發明之一目的在於提供一種改進的催化劑以克服先前技術之缺陷。特定而言，本發明之一目的在於提供一種催化劑，其特徵為產物產率降低較慢，以避免經常再生該催化劑。另一目的在於提供一種用於烯烴複分解反應的催化劑，其能夠抑制不欲的副產物生成，例如在乙烯與丁烯反應中的1,3-丁二烯。
此目的係由一種複分解催化劑達成，該催化劑包含：a)一選自元素週期表中第VIA族及VIIA族的過渡金屬；b)一無機載體；c)0.1至60重量份之一沸石；以及d)0.1至80重量份之一層狀雙氫氧化物(layered double hydroxide)。
本發明亦提供一種改進的烯烴製造的製程，包含將一包含烯烴的進料流與根據本發明之複分解催化劑接觸。
於烯烴製造製程中使用根據本發明之催化劑，可展現高活性、高選擇性、及降低的去活化速率，因此可表現較長的反應循環，且延長了催化劑壽命。
根據本發明的複分解催化劑包含：a)一選自元素週期表中第VIA族及VIIA族的過渡金屬；b)一無機載體；c)0.1至60重量份之一沸石；以及d)0.1至80重量份之一層狀雙氫氧化物。
在一較佳實施態樣中，關於本發明催化劑組成的重
量份指重量百分率。
在本發明前後文中，用語「VIA族」指鉻族的第6族元素，特指Cr、Mo、及W。同樣地，用語「VIIA族」指錳族的第7族元素，特指Mn、Tc、及Re。
較佳地，用於此催化劑的過渡金屬選自鉬、鎢、及錸，其於複分解反應中具高度活性。過渡金屬可以多種形式存在，包括金屬元素、以及過渡金屬的氧化物、硫化物、氫化物、及氫氧化物。特定而言，較佳為例如WO3、MoO3、及Re2O7的氧化物，且WO3甚至為更佳的。在一實施態樣中，本發明催化劑包含1至15重量份，較佳7至11重量份之該過渡金屬。
過渡金屬被負載在無機載體上。本技術領域中已知多種無機載體。無機載體的種類並無特別限制。在一較佳實施態樣中，無機載體係選自氧化矽、氧化鋁、氧化鈦、氧化鋯、及其混合物，較佳為氧化矽。
該複分解催化劑包含0.1至60重量份之沸石。沸石的種類並無特別限制，但可較佳選自ZSM-5、X-沸石、Y-沸石、β-沸石、MCM-22、鎂鹼沸石(ferrierite)、及其混合物。在一較佳實施態樣中，沸石係選自ZSM-5、Y-沸石、及鎂鹼沸石，更佳為Y-沸石。
且在另一較佳實施態樣中，基於催化劑的總重，複分解催化劑的沸石含量在0.5至30重量份的範圍內，更佳1至20重量份的範圍內。
層狀雙氫氧化物(LDH)又稱為陰離子黏土或水滑石類(hydrotalcite-like)材料，是一系列具有特殊結構的材料，
具有帶正電的層與電性中和的陰離子及水中間層。層狀雙氫氧化物的化學通式可寫作：[My+ 1-xM’z+ x(OH)2]a+(Ar-)n．b(H2O)其中M 為第一金屬；M’ 為第二金屬；A 為陰離子；x 為一數值，較佳於0.1至0.9範圍；y 為第一金屬的電荷數，較佳等於1或2；z 為第二金屬的電荷數，較佳等於3或4；a 由x、y、及z決定，較佳a=(1-x)y+xz-2；r 為陰離子的電荷數；n 由a及r決定，較佳n=a/r；b 為水分子數，較佳於0至10範圍。
第一金屬(M)與第二金屬(M’)可為鹼金屬、鹼土金屬、過渡金屬、或其他金屬。在一較佳實施態樣中，第一金屬選自Li、Ca、Mg、Mn、Fe、Co、Ni、Cu、Zn、及其混合物，較佳Ca及/或Mg。在另一較佳實施態樣中，第二金屬選自Al、Ga、In、Mn、Fe、Co、Cr、Ni、V、Ti、Zr、Y、及其混合物，較佳Al。
陰離子的實例包括氯離子、溴離子、碳酸根、碳酸氫根、磷酸氫根、磷酸二氫根、亞硝酸根、硼酸根、硝酸根、硫酸根、磷酸根、氫氧根、氟離子、碘離子、及其混合物。在一尤其較佳的實施態樣中，陰離子選自碳酸根及硝酸根。
層狀雙氫氧化物在催化劑轉換率、選擇性、及副產物生成的效應即使在低濃度的狀況下仍可觀測到。在一實施態樣中，基於催化劑的總重，複分解催化劑包含0.5至50重量份，更佳1至30重量份之層狀雙氫氧化物。
根據本發明的複分解催化劑的組分可以多種方式共存。舉例而言，無機載體、沸石、及LDH可在沉積過渡金屬前混合。另一例中，可於與沸石及無機載體混合前將過渡金屬沉積在LDH上。
本發明之目的進一步由本發明的複分解催化劑所達成，該複分解催化劑由一製備製程獲得，該製備製程包含：a)混合一無機載體與一沸石，以獲得一混合物；b)將一過渡金屬沉積於該無機載體與該沸石之混合物上，以獲得一沉積混合物；以及c)混合該沉積混合物與該層狀雙氫氧化物，以獲得該複分解催化劑。
無機載體與沸石的混合物可簡單地由物理混合獲得。金屬沉積的技術可為本領域已知者且不受限制。在一典型實例中，過渡金屬化合物浸透無機載體與沸石的混合物。
在一特定實施態樣中，金屬沉積混合物在與層狀雙氫氧化物混合前被乾燥及/或煅燒。乾燥與鍛燒方法並未特別限制。在一特別較佳的實施態樣中，金屬沉積混合物在與層狀雙氫氧化物混合前，在空氣中以400℃至700℃煅燒0.5至12小時。
複分解催化劑的形狀與尺寸並未限制，且可基於製程需求適當選擇。為促進催化劑形成，適當的黏結組分例如無機氧化物、無機氧化物溶膠、或黏土可進一步加入催化劑中。
本發明之目的進一步由本發明的烯烴製造製程所達成，該製程包含將包含烯烴的進料流與本發明複分解催化劑接觸。
進料流可包括具有2至12個碳原子的直鏈或環狀烯烴。在一較佳實施態樣中，進料流包含一直鏈烯烴，該直鏈烯烴選自下列所組成之群組：C2直鏈烯烴、C3直鏈烯烴、C4直鏈烯烴、C5直鏈烯烴、C6直鏈烯烴、及其混合物。在一更佳實施態樣中，進料流包含乙烯及正丁烯或乙烯及正戊烯，其中丙烯為較佳的產物。其他化合物，例如石蠟類、二烯類、及炔類，可以在不會干擾將一種烯烴轉換為另一種烯烴的主要反應的濃度下，存在於進料流中。在一特定實施態樣中，製程亦可於氫存在下進行；然而，其並非實施本發明最佳態樣的要求。
實施本發明製程的操作條件包括溫度於100至600℃範圍，較佳200至450℃，以及壓力於0至50巴錶壓(bar gauge)。本發明製程的操作模式可由任何已知技術適當地選擇，包括固定床、流體化床、搖動床(swing bed)、及移動床，其中固定床一般為較佳。製程可在沒有任何額外的輔催化劑或護床的情況下有效率地實施。
在與烯烴進料接觸前，複分解催化劑可以惰性氣體、氧化氣體、或還原氣體在加熱環境下處理，較佳於200至700℃範圍。
本發明之複分解催化劑可被再生，因此，烯烴製造製程可進一步包含再生步驟。典型的複分解催化劑再生程序涉及將衰減的催化劑與氧化氣體在高溫下接觸，以燒除反應期間產生在催化劑上的毒性物質及重質沉積物。可使用其他已知的再生技
術而不受限制。
本發明的複分解催化劑與使用該複分解催化劑的烯烴製造製程的優點在於提供了更為穩定的複分解反應，其藉由延長的循環時間而展現。此亦導致更為經濟有利的工業製程。本發明的實施態樣與有利效果於以下實施例中進一步例示，但並不用於限制本發明範疇。
實施例1[比較]
包含9重量%之WO3於氧化矽載體上的複分解催化劑被裝載在管式反應器中。包含乙烯與2-丁烯的進料流以1.4小時-1的每小時重量空間速度(WHSV)被供應至反應器，且催化劑床控制為350℃及22巴錶壓。
分析反應器的流出物。在5小時之流出流，正丁烯轉化率為50%且丙烯選擇性為92%。在15小時之流出流，正丁烯轉化率為27%且丙烯選擇性為89%。基於總流出流，平均1,3-丁二烯形成170ppm，且平均C5+形成少於5重量%。
實施例2[比較]
藉由將於氧化矽載體上的9重量%之WO3與Mg-Al-CO3層狀雙氫氧化物以重量比10：1物理混合以獲得複分解催化劑。催化劑被裝載在管式反應器中。包含乙烯與2-丁烯的進料流以1.4小時-1的每小時重量空間速度(WHSV)被供應至反應器，且催化劑床控制為350℃及22巴錶壓。
分析反應器的流出物。在5小時之流出流，正丁烯轉化率為65%且丙烯選擇性為94%。在15小時之流出流，正丁烯
轉化率為47%且丙烯選擇性為90%。基於總流出流，平均1,3-丁二烯形成198ppm，且平均C5+形成少於5重量%。
實施例3
藉由將於包含95重量%氧化矽與5重量%Y-沸石的載體上的9重量%之WO3與Mg-Al-CO3層狀雙氫氧化物以重量比10：1物理混合以獲得複分解催化劑。催化劑被裝載在管式反應器中。包含乙烯與2-丁烯的進料流以1.4小時-1的每小時重量空間速度(WHSV)被供應至反應器，且催化劑床控制為350℃及22巴錶壓。
分析反應器的流出物。在5小時之流出流，正丁烯轉化率為64%且丙烯選擇性為95%。在15小時之流出流，正丁烯轉化率為68%且丙烯選擇性為94%。基於總流出流，平均1,3-丁二烯形成9ppm，且平均C5+形成少於5重量%。
實施例4
藉由將於包含95重量%氧化矽與5重量%Y-沸石的載體上的9重量%之WO3與Mg-Al-CO3層狀雙氫氧化物以重量比10：0.5物理混合以獲得複分解催化劑。催化劑被裝載在管式反應器中。包含乙烯與2-丁烯的進料流以1.4小時-1的每小時重量空間速度(WHSV)被供應至反應器，且催化劑床控制為350℃及22巴錶壓。
分析反應器的流出物。在5小時之流出流，正丁烯轉化率為57%且丙烯選擇性為80%。在15小時之流出流，正丁烯轉化率為35%且丙烯選擇性為78%。基於總流出流，平均1,3-丁二烯形成19ppm，且平均C5+形成少於5重量%。
實施例5
藉由將於包含95重量%氧化矽與5重量%Y-沸石的載體上的9重量%之WO3與Mg-Al-CO3層狀雙氫氧化物以重量比1：1物理混合以獲得複分解催化劑。催化劑被裝載在管式反應器中。包含乙烯與2-丁烯的進料流以1.4小時-1的每小時重量空間速度(WHSV)被供應至反應器，且催化劑床控制為350℃及22巴錶壓。
分析反應器的流出物。在5小時之流出流，正丁烯轉化率為64%且丙烯選擇性為87%。在15小時之流出流，正丁烯轉化率為60%且丙烯選擇性為84%。基於總流出流，平均1,3-丁二烯形成64ppm，且平均C5+形成少於5重量%。
實施例6
藉由將於包含95重量%氧化矽與5重量%Y-沸石的載體上的9重量%之WO3與Ca-Al-CO3層狀雙氫氧化物以重量比10：1物理混合以獲得複分解催化劑。催化劑被裝載在管式反應器中。包含乙烯與2-丁烯的進料流以1.4小時-1的每小時重量空間速度(WHSV)被供應至反應器，且催化劑床控制為350℃及22巴錶壓。
分析反應器的流出物。在5小時之流出流，正丁烯轉化率為64%且丙烯選擇性為95%。在15小時之流出流，正丁烯轉化率為65%且丙烯選擇性為91%。基於總流出流，平均1,3-丁二烯形成37ppm，且平均C5+形成少於5重量%。
實施例7[比較]
藉由將於包含95重量%氧化矽與5重量%Y-沸石的
載體上的9重量%之WO3與氧化鎂以重量比1：1物理混合以獲得複分解催化劑。催化劑被裝載在管式反應器中。包含乙烯與2-丁烯的進料流以1.4小時-1的每小時重量空間速度(WHSV)被供應至反應器，且催化劑床控制為350℃及22巴錶壓。
分析反應器的流出物。在5小時之流出流，正丁烯轉化率為65%且丙烯選擇性為91%。在15小時之流出流，正丁烯轉化率為60%且丙烯選擇性為72%。基於總流出流，平均1,3-丁二烯形成238ppm，且平均C5+形成少於8重量%。
以上實施例的結果統整於下方表1中。
由以上實施例的結果可見，將沸石與LDH併入複分解催化劑導致在複分解反應中較少的1,3-丁二烯形成，且可觀察到產物產率降低較慢。
上文敘述與後附申請專利範圍所揭露的特徵，可單獨或以任何組合方式作為以多樣形式實現本發明的材料。
Claims (14)
- 一種複分解(metathesis)催化劑，包含：a)一選自元素週期表中第VIA族及VIIA族的過渡金屬；b)一無機載體；c)0.1至60重量份之一沸石；以及d)0.1至80重量份之一層狀雙氫氧化物(layered double hydroxide)。
- 如請求項1所述之複分解催化劑，其中該過渡金屬係選自鉬、鎢、及錸。
- 如請求項1或2所述之複分解催化劑，其包含1至15重量份之該過渡金屬。
- 如請求項1或2所述之複分解催化劑，其中該無機載體係選自氧化矽、氧化鋁、氧化鈦、氧化鋯、及其混合物。
- 如請求項1所述之複分解催化劑，其中該沸石係選自ZSM-5、X-沸石、Y-沸石、β-沸石、MCM-22、鎂鹼沸石(ferrierite)、及其混合物。
- 如請求項1或5所述之複分解催化劑，包含0.5至30重量份之該沸石。
- 如請求項1所述之複分解催化劑，其中該層狀雙氫氧化物包含選自Li、Ca、Mg、Mn、Fe、Co、Ni、Cu、Zn、及其混合物的一第一金屬。
- 如請求項1或7所述之複分解催化劑，其中該層狀雙氫氧化物包含選自Al、Ga、In、Mn、Fe、Co、Cr、Ni、V、Ti、Zr、Y、及其混合物的一第二金屬。
- 如請求項1或7所述之複分解催化劑，其中該層狀雙氫氧化物包含選自氯離子、溴離子、碳酸根、碳酸氫根、磷酸氫根、磷酸二氫根、亞硝酸根、硼酸根、硝酸根、硫酸根、磷酸根、氫氧根、氟離子、碘離子、及其混合物的一陰離子。
- 如請求項1或7所述之複分解催化劑，其包含0.5至50重量份之該層狀雙氫氧化物。
- 如請求項1或2所述之複分解催化劑，其中該複分解催化劑係由一製備製程獲得，該製備製程包含：a)混合一無機載體與一沸石，以獲得一混合物；b)將一過渡金屬沉積於該無機載體與該沸石之混合物上，以獲得一沉積混合物；以及c)混合該沉積混合物與該層狀雙氫氧化物，以獲得該複分解催化劑。
- 如請求項11所述之複分解催化劑，其中該製備製程在步驟c)與該層狀雙氫氧化物混合之前，進一步包含乾燥及/或煅燒該沉積混合物。
- 一種烯烴製造製程，包含將一包含烯烴的進料流與如請求項1至12中任一項所述之複分解催化劑接觸。
- 如請求項13所述之烯烴製造製程，其中該進料流包含一直鏈烯烴，該直鏈烯烴選自下列所組成之群組：C2直鏈烯烴、C3直鏈烯烴、C4直鏈烯烴、C5直鏈烯烴、C6直鏈烯烴、及其混合物。
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| ES2856957T3 (es) * | 2015-03-20 | 2021-09-28 | Smh Co Ltd | Proceso para metátesis de olefina |
| EP3335790B1 (en) * | 2016-12-13 | 2021-02-24 | SMH Co., Ltd. | Process for the conversion of a hydrocarbon feed comprising a saturated hydrocarbon compound to olefin products |
| US11383225B2 (en) | 2016-12-13 | 2022-07-12 | SMH Co., Ltd | Hydrocarbon conversion catalyst system |
| ES2797802T3 (es) * | 2016-12-13 | 2020-12-03 | Smh Co Ltd | Catalizador para la conversión de una alimentación de hidrocarburos que comprende un compuesto de hidrocarburo saturado en productos olefínicos |
| CN109225252B (zh) * | 2018-09-29 | 2021-08-10 | 陕西科技大学 | 一种锰镍双金属氢氧化物双功能电催化剂的制备方法 |
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