CN106163661A - 用于芳香化c3‐c4气体、轻质烃级分和脂肪醇以及它们的混合物的催化剂和方法 - Google Patents
用于芳香化c3‐c4气体、轻质烃级分和脂肪醇以及它们的混合物的催化剂和方法 Download PDFInfo
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- CN106163661A CN106163661A CN201480074251.2A CN201480074251A CN106163661A CN 106163661 A CN106163661 A CN 106163661A CN 201480074251 A CN201480074251 A CN 201480074251A CN 106163661 A CN106163661 A CN 106163661A
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- catalyst
- zeolite
- gas
- weight
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000005899 aromatization reaction Methods 0.000 title claims abstract description 36
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 32
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 29
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 150000002191 fatty alcohols Chemical class 0.000 title claims description 10
- 239000010457 zeolite Substances 0.000 claims abstract description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000002994 raw material Substances 0.000 claims abstract description 53
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 45
- 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 45
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 15
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 15
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 14
- -1 octane hydrocarbon Chemical class 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000011777 magnesium Substances 0.000 claims abstract 2
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract 2
- 239000007789 gas Substances 0.000 claims description 38
- 239000003502 gasoline Substances 0.000 claims description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 22
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000012141 concentrate Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000000395 magnesium oxide Substances 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- HOWJQLVNDUGZBI-UHFFFAOYSA-N butane;propane Chemical compound CCC.CCCC HOWJQLVNDUGZBI-UHFFFAOYSA-N 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 238000010025 steaming Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- IHICGCFKGWYHSF-UHFFFAOYSA-N C1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1C Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1.CC1=CC=CC=C1C IHICGCFKGWYHSF-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 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 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- 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
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- 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
- B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/065—Catalytic reforming characterised by the catalyst used containing crystalline zeolitic molecular sieves, other than aluminosilicates
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
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Abstract
本发明涉及加工烃原料的技术,尤其涉及用于芳香化C3‐C4烃气体、轻质低辛烷烃级分以及含氧化合物(C1‐C3脂肪醇)以及其混合物的催化剂和技术,以便生产芳族烃浓缩物(AHCC)。催化剂包含两种沸石的机械混合物,其中第一沸石的特征在于SiO2/Al2O3摩尔比=20,其采用碱性水溶液预处理,并且采用量为基于所述第一沸石质量0.5‐2.0重量%的稀土元素氧化物改性。第二沸石的特征在于SiO2/Al2O3摩尔比=82,并含有基于所述第二沸石质量0.04重量%的残余量的氧化钠,并且被氧化镁以基于所述第二沸石质量0.5‐5.0重量%的量改性。此外,所述沸石以1.7/1‐2.8/1的重量比使用,其中该催化剂还至少含有氧化硅的粘结剂,并且以基于催化剂的质量20‐25重量%的量使用所述粘结剂。所述方法使用所建议的催化剂在等温反应器中进行,不用进行源自分离阶段的气体的再循环,使固定催化剂床与气体原料接触,气体原料在预热器中被蒸发和预热。得到的技术效果在于,实现了更高的芳族烃收率,同时保证HC原料和含氧物的几乎完全转化,保证了作为AHCC的一部分的二甲苯的增加的选择性,同时简化所述工艺的技术设置,原因在于使用了减低的压力(尤其是大气压)。
Description
本发明涉及加工烃原料的技术,尤其涉及用于芳香化C3‐C4烃气体、轻质低辛烷烃级分(特别是天然气液(NGL)、气体冷凝物和直馏汽油以及费‐托法等工艺的石脑油)以及含氧化合物(C1‐C3脂肪醇)以及其混合物的催化剂和技术,以便生产芳族化合物浓缩物(AC)。
本发明可用于炼油和烃加工工业,用于使用所得的高辛烷AC掺混直馏汽油,以及用于得到单个的芳族烃类(苯、甲苯、二甲苯),所述烃类是在AC精馏期间被分离的,并且是广泛应用的溶剂和试剂,用于得到更复杂的有机物,例如异丙苯。
在传统的芳香化方法中,原料是用于进行芳族烃形成反应所必须的热能的载体。为了实现高的原料转化度,需要与反应温度有关的显著地使所述原料过热,这导致催化剂和换热器管的快速结焦。在本发明中,芳香化链烷烃(H/C)的吸热反应的供热问题通过向反应区中直接引入氧合物(C1‐C3的脂肪醇)而得以解决,所述氧合物经由脱水释放出热能,该热能被提供给H/C原料至芳族烃(ArH)的转化,是其高度转化所需要的。
尝试进行轻质链烷烃的芳香化的方法开始于在二十世纪九十年代初期。最著名和成熟的是“Cyclar”工艺,其是由英国石油British Petroleum和Universal Oil Products联合开发的。所述工艺采用由Universal Oil Products Company开发的具有流化的催化剂床的装置,再生反应器外部结焦的催化剂以及再循环未转化的产品。对于该工艺中的氢分离,建议使用低温工段。主要是丙烷和丁烷的液化石油气被用作原料。基于转化的原料的芳族烃收率为55‐63重量%,具体取决于原料的组成。该工艺达到了试验‐工业的水平,然后由于其工业实施的经济上的不合适而被搁置。
RF专利第2377230号描述了一种芳香化含有介于一个和四个碳原子的轻质烷烃的方法,其涉及使气体原料与含有沉积在MFI沸石上的铂的Pt/ZSM‐5催化剂接触,催化剂的晶格由铝、硅和氧构成。该催化剂在芳香化烷烃的工艺中的使用抑制甲烷的形成,并且增加基于苯‐甲苯‐二甲苯级分的选择性。在轻质气体级分中相对于甲烷的量的较高的乙烷量使得能够使用尾气作为用于裂解器的原料。
芳香化轻质链烷的C5‐C7烃的工艺也如丙烷‐丁烷级分的情形,并基于以下反应:裂解、低聚、歧化、脱氢环化和脱烷基化。基于裂解反应的结果,形成了C2‐C4的烯烃,该烯烃进入低聚反应以形成烯烃类的C6‐C12烃,后者在后来在脱氢环化反应的过程中形成芳族烃。
在RF专利第2163623号中,低辛烷直馏汽油级分在单原子醇或二醇的存在下进行重整,醇或二醇的量是0.2‐5.0重量%。该工艺的催化剂是两种催化剂的机械混合物:含沸石的催化剂以及铝‐钴(镍)‐钼氧化物催化剂。所述工艺在温度为460‐510℃、在原料供应液体空速为0.3‐0.9h‐1下进行。所述方法的优点在于能够显著增加(10‐15个点)汽油辛烷值;但所述方法的缺点是工艺的高温和低容量,原因在于低的原料供应液体空速,以及氧化物催化剂对含硫杂质的高度敏感性。
RF专利第2337127号描述了一种在含氢气体存在下、在由多个连续连接的反应器所形成的具有含铂催化剂的系统中、在升高的压力和温度下催化重整汽油级分的方法,所述方法在三个阶段中进行。在第一阶段中,环烷烃和烷烃的芳香化通过使烃组分与铝‐铂‐铼催化剂接触而进行,基于催化剂质量的原料供应的质量速度为4‐8h‐1,反应温度460‐480℃;在第二阶段中,在含铂的锆石‐硫酸盐催化剂上进行芳烃、环烷烃和烷烃的氢化异构化,基于催化剂质量的原料供应的质量速度为不小于8h‐1,反应温度为150‐200℃;在第三阶段中,再次进行在铝‐铂‐铼催化剂上的环烷烃的芳香化,基于催化剂质量的原料供应的质量速度为不小于8h‐1,且反应温度为360‐400℃;而且,在重整反应器系统的入口的压力是1.5MPa,含氢气体进入到反应器系统的入口,其量对应于氢气/原料的摩尔比为至少8。所述方法的缺点之处在于使用含有贵金属的昂贵催化剂,以及工艺流程方案的复杂性,因为建议使用多个连续相连接的在增压下操作的反应器。
RF专利第2307117号描述了一种生产用于在分子中具有2‐6个碳原子的烷烃的芳香化的催化剂和方法。描述了烃芳香化的方法,其包括:(a)使在分子中具有2‐6个碳原子的烷烃与至少一种催化剂接触,所述催化剂含有铝‐硅‐锗沸石,其上沉积有铂;以及(b)将芳香化产物分开。描述了一种用于合成铝‐硅‐锗‐铂沸石催化剂的方法,其包括以下阶段:(1)得到含有铝、硅和锗的沸石;(2)将铂沉积在微孔的铝‐硅‐锗沸石上;(3)煅烧所述沸石。还描述了一种预处理芳香化烃类的催化剂的方法,其包括以下阶段:(1)将铂沉积在铝‐硅‐锗沸石上;(2)所述催化剂另外用氢气处理,然后用硫化合物处理;以及(3)所述催化剂第二次用氢气处理。技术效果是增加的催化剂稳定性。但是,这种以及其它芳香化(重整)的传统方法的大量缺点是低的ArH收率,以及在催化剂组成中使用的贵金属。
RF专利第2372988号描述了一种用于将C2‐C12脂族烃和/或C1‐C12脂族含氧化合物转变成为高辛烷汽油或芳族烃的催化剂,所述催化剂包括五元高硅沸石型沸石、芳香化促进剂例如锌,以及粘结剂。所述沸石特征在于SiO2/Al2O3摩尔比的数值范围是20‐80,残余钠离子含量不低于0.1%;所述芳香化促进剂通过使用任何已知方法引入,其具有以下的组分比:沸石‐30.0‐90.0重量%;锌‐0.5‐8.0重量%;粘结剂‐残余量;此外,所述催化剂在其中引入锌以后另外用氟化铝溶液进行处理。
技术效果是产生了高活性且稳定的催化剂,其可用于加工宽广范围的含烃原料。所述催化剂的缺点是其活性的快速下降,结果是需要频繁的进行催化剂的氧化再生。
作为开发方法的现有技术是RF专利第2440189号,其描述了相似的用于生产具有低含量的苯和均四甲苯的高辛烷汽油的方法,其中在芳香化初始原料中的链烷H/C的过程中实现了成品汽油辛烷评分的提升,以便生产芳族H/C的高辛烷级分(FAH)。一种机械混合物被用作催化剂,该混合物包含SiO2/Al2O3摩尔比=18‐25的五元高硅沸石型沸石,不包含改性剂,并且使用碱性水溶液预处理,并包含SiO2/Al2O3摩尔比=70‐90的五元高硅沸石型沸石,其采用氧化镁进行改性,氧化镁的量为0.5‐3.0重量%,所述沸石以介于1/1和1/10之间的比例使用,所述催化剂中还有粘结剂,其量为所述催化剂质量的20‐25重量%。还描述了一种生产具有高(至多50重量%)芳族化合物含量的高辛烷汽油的方法。所述催化剂在具有热管道的等温反应器中加热至温度280‐320℃,同时,使原料与在具有热管道的等温反应器中加热的催化剂的接触在压力为0.1‐1MPa下、在以空速1‐5h‐1(就液体而言)供应原料至所述反应器以及在预热器在原料蒸发后以1000‐10,000h‐1的气体空速供应惰性气体下进行。所建议方法的大量缺陷在于这样的事实,为了在随后从汽油生产其中ArH含量不高于50.2%的单独的ArH(苯、甲苯、二甲苯),需要采用相当复杂的萃取分级,因为在FAH的组成中存在脂肪族H/C。
与本发明最接近的现有技术是RF专利第2277524号,其特征在于从含有脂族烃的烃原料生产芳族烃。当实施所述方法时,要使用根据RF专利第2165293号生产的催化剂,所述催化剂具有以重量百分数计的以下组成:五元高硅沸石型沸石(SiO2/Al2O3=60,氧化钠含量低于0.1重量%)‐62;氧化锌‐1.8;氧化铈‐0.3;氧化镧‐1.5;氧化镁‐0.2;氧化铝‐34.2。芳香化的方法包括在原料与催化剂接触时转化原料(丙烷‐丁烷级分,含0.8重量%的乙烷,14.0重量%的丙烷,1.5重量%的异丁烷和80.6重量%的正丁烷及3.1重量%的戊烷),所述接触分两个区,区的差别在于脂族烃至芳族烃的转化条件不同,为了从所得产物中分离含有芳族烃的C5+烃类(AC),原料被导向低温区域,以便转化更活泼的脂族烃;一股C5+烃类料流从所得产物中分离,在所述低温区的剩余烃产物被导向一高温区域,其用于转化不太活泼的脂族烃。原料一次经过的AC收率不超过38.4%,其中在AC中的二甲苯含量为21.8%。相反,当使用原料的52.6%收率的分离气体进行再循环时(在料流13中),产生的AC的总芳族化合物含量为94.1%(苯14.1%,甲苯45.3%,二甲苯23.0%,C9+10.7%)。
以上所建议方法的缺点在于,原料在换热器和炉子中被加热的非常高的温度(高达575℃),这导致换热器的结焦,以及所述工艺自身的高温(520‐550℃)。所述工艺的复杂实施也应注意,因为在所述两个反应区(反应器)中使用了升高的压力(0.8‐2.0MPa),以及分离气体的再循环。此外,当不采用气体再循环时,对于含有85重量%C4+烃类的原料,观察到了较低的ArH收率。
本发明要解决的技术问题包括产生高度有效的催化剂,用于芳香化H/C原料和脂肪醇,其可在所得的AC中提供增加的ArH收率,以及提供一种更简单和不太耗能方法,所述方法可用于芳香化C3‐C4气体和与C1‐C3脂肪醇的混合物的轻质低辛烷烃级分,其区别在于增加含量的高度追求的二甲苯。
当实施建议的本发明时,得到的技术效果是包括实现更高的ArH收率,几乎完全转化的H/C原料和氧合物,就AC组成中形成二甲苯而言的增加的选择性,以及同时简化所述工艺的技术实施,原因在于使用了降低的压力(包括大气压)。
此外,通过在H/C原料组成中使用额外量的脂肪醇以及采用更高的体积气体原料空速,实现了更高的ArH生产率数值。
为了实现所述的技术效果,建议的催化剂包含两种具有不同的SiO2/Al2O3摩尔比的五元高硅沸石型沸石的机械混合物:(1)SiO2/Al2O3摩尔比=20的第一沸石,其使用碱性水溶液预处理,并且用稀土元素(REE)氧化物改性,量为第一沸石质量的0.5‐2.0重量%;和(2)SiO2/Al2O3=82的第二沸石,其用氧化镁改性,氧化镁的量为第二沸石质量的0.5‐5.0重量%,两种沸石以质量比1.7/1‐2.8/1被取用;剩余为粘结剂(优选氧化硅,潜在地加入量为所述粘结剂质量的至多25重量%的氧化铝),粘结剂的量为催化剂质量的20‐25重量%。
使用碱的预处理和使用REE和氧化镁的沸石改性在室温下进行,同时用碱性水溶液(NaOH)、REE或硝酸镁来浸渍所述沸石(通过初期润湿)。
所述催化剂的区别特征在于,在所建议的催化剂中,两种五元高硅沸石型沸石的机械混合物的组成由具有增加的酸度的SiO2/Al2O3=20的低模量沸石为主,在所述方法中的升高的温度下,其使得原料的H/C部分能够更完全的芳香化,以便形成AC,另外,组合的硅石‐氧化铝催化剂同时对苯与转化氧合物过程中形成的C2‐C4烯烃(原位)的芳香化反应和烷基化反应都具有活性,这导致能够产生具有增加含量的二甲苯的AC。
优选使用氧化硅作为用于催化剂的粘结剂,所述氧化硅不具有酸性性质,与现有技术发明中所用的粘结剂即氧化铝相比,显著区别于所述催化剂因为其在裂解反应中降低的活性,其导致更大的ArH选择性。此外,所述催化剂在操作期间在高温区域中以及在反应水的存在下具有更大的机械强度。
为了实现所述的技术结果,建议使用芳香化C3‐C4气体、低辛烷烃级分和脂肪醇以及其混合物的方法,在本发明中建议,根据所述方法,具有以上所述组成的催化剂在等温反应器(参见要求保护的发明的最接近的现有技术)中被加热至温度为400‐500℃,气体原料与催化剂的接触过程则在大气压和升高的压力(至多18atm)下以300‐1500h‐1的空速进行(对气体而言),其中所述气体原料在预热器中被蒸发,并被加热至温度150‐250℃。
脂肪醇和烃原料混合物的使用促进了芳香化过程在更温和条件下的进行,因为进行中的放热转化反应所释放的热量伴随着芳香化过程,所述转化为二甲醚(DME)(醇脱水期间形成的中间产物)至烯烃的转化、烯烃的低聚和最低级芳族化合物通过氧合物和由所述氧合物形成的烯烃的烷基化,所述释放的热量进而为烃芳香化吸热反应提供热量。因此,同样由于反应混合物中水的存在所致,显著减少了甲烷和焦炭形成的发生,其导致催化剂稳定操作的时间区段增加,其中所述水是在醇的脱水期间形成的。
此外,在所建议的方法中一次通过的原料的转化率以及不用使分离气体再循环显著降低了与实施所述过程相关的成本。
建议的芳香化方法的区别特征还在于更宽泛范围的H/C原料可以以如下混合物形式:链烷烃和烯烃C3‐C4气体,NGL,各种汽油(沸点至多200℃)和氧合物,以及H/C与氧合物(C1‐C3的脂肪醇)的混合物,其中氧合物含量为10‐50体积%。
所建议的方法可以用于以下所述的领域,其中包括气体冷凝物领域,相关的汽油气,以及低辛烷汽油来源和醇生产废料。由所建议的方法生产的AC可用于得到单独的ArH(包括所关心的二甲苯),以及后者进一步用于化学合成工艺中。
本发明通过以下实施例来加以举例说明:
实施例1.含两种沸石的机械混合物的催化剂‐在催化剂组成中占75重量%:(1)SiO2/Al2O3摩尔比=20的沸石,用碱性水溶液预处理(Na2O,基于沸石的含量为0.5重量%),并且用2.0重量%的氧化镧改性,以及(2)SiO2/Al2O3摩尔比=82的沸石,残余量的氧化钠为0.04重量%,用0.5重量%的氧化镁改性,两种沸石以2.8/1的比率被取用;剩余部分为25重量%的氧化硅粘结剂。
实施例2.含两种沸石的机械混合物的催化剂‐催化剂组成中占80重量%:(1)SiO2/Al2O3摩尔比=20的沸石,用碱性水溶液预处理(Na2O,其基于沸石的含量为0.5重量%),并且用0.5重量%的氧化铈改性,以及(2)SiO2/Al2O3摩尔比=82的沸石,残余量的氧化钠为0.04重量%,用5.0重量%的氧化镁改性,两种沸石以1.7/1的比率被取用;剩余部分为20重量%的粘结剂(氧化铝和氧化硅的混合物,其质量比为1/4)。
实施例3‐9.所述方法在等温流式反应器中进行,反应器具有电加热,压力是1‐18atm,使100cm3的根据实施例1和2制备并且被加热至400‐500℃的催化剂(催化剂床的高度是25cm)与原料气体接触,所述原料气体在预加热器中被预热至150‐250℃,并且是以下形式:C3‐C4H/C气体,各种低辛烷烃级分(NGL)或汽油和氧合物(甲醇、乙醇、异丙醇),以及H/C与醇的混合物,气体原料的空速为300‐1500h‐1。
反应期间得到的AC累积24小时的时间段,然后根据ASTM 6729用色谱法确定其组成。在实施例6和10(比较性的)中,进行300小时的连续试验。
原料的烃组成列于下表1中。
实施例10(比较实施例).进行如根据实施例3的方法,例外之处是所述方法在温度为520℃、压力为8atm下进行(如现有技术的发明),其中以丙烷‐丁烷级分作为原料,不含氧合物(甲醇)添加剂。
表1原料组成,重量%
表2包含涉及不同类型的低辛烷烃原料的气体和液体及脂肪醇,以及它们的混合物的转化率的具体数据,后者依赖于芳香化工艺的条件。
表2.芳族化的物料平衡
*‐因为氧合物(含氧醇)被用于所述原料组成中,AC收率是针对原料的H/C部分进行计算的(例如,在甲醇分子CH3OH中,烃部分是CH2,即,其占43.8重量%)。
实施所建议的本发明所得到的技术效果涉及实现增加的AC收率(原料一次性通过,不进行分离气体的再循环)以及增加的对二甲苯的选择性。这样,与现有技术(比较实施例号10,没有氧合物添加剂)比较根据所建议的方法(实施例号6)的丙烷‐丁烷级分指示物的芳香化反应,其中加入氧合物(甲醇)至H/C原料中,明显的是,根据所要求保护的本发明中建议的催化剂,在更低的温度(500℃而不是520℃)和压力(6atm而不是8atm)下,在原料一次性通过的情形下得到了更高的AC收率(38.1%对29.2%)。此外,根据所建议的方法的ArH组成主要是广泛希望得到的二甲苯(AC组成中C8芳族化合物级分高达41.6%),而在实施例10中,所述浓度不超过22.7%。
相似的关系在芳香化NGL期间也观察到。从实施例7和4的比较可以知道,显然添加25体积%的甲醇至H/C原料中导致AC收率增加5.8%,其中包含二甲苯的C8级分在AC组成中的浓度从22.8%增加至38.1%;此外,使用的是大气压,且实施例7(添加了氧合物)中的温度也要低10℃。还应该注意的是,在联合处理含烯烃混合级分(PPF+BBF)与异丙醇(实施例9)时,在甚至相对更低的温度450℃下AC收率也达到了78.2%。
所建议的本发明的显著结果是混合气体H/C原料与氧合物消除了将所述原料预热至大约温度550‐575℃的需要,而这是现有技术的发明中芳香化丙烷‐丁烷级分时所需要的,因为在氧合物的转化期间,释放了额外的热量,而这热量是进行芳香化反应所必须的。在反应器入口处的原料料流仅仅应加热至150‐250℃,而这可以由反应器出口的产品的热气体料流所回收热量来提供,这使得能够避免多分区炉子(燃烧加热器)的使用。
所建议的方法消除了在具有不同的温度模式的分开的连续区域中转化单个的C3+和C5+H/C的需求以及再循环气体的需求。这导致能耗的显著下降,同时使得所述方法的技术实施得以简化。
此外,在建议的芳香化C3‐C4气体、低辛烷H/C级分和脂肪醇以及其混合物的方法中,催化剂稳定操作的时间显著延长,原因在于在氧合物转化期间形成了反应水,所述方法在更温和的条件(就温度和压力而言)下进行。这点也得到了ArH收率减少20%时的时间的证实,该数据存在于表2中,且根据本发明建议的方法,其增加了至少1.5倍。
Claims (4)
1.用于芳香化C3‐C4气体、轻质烃级分和脂肪醇以及它们的混合物的包含五元高硅沸石型沸石的催化剂,特征在于其包含两种沸石的机械混合物,其中第一沸石的特征在于SiO2/Al2O3摩尔比=20,其采用碱性水溶液预处理,并且采用量为基于所述第一沸石质量0.5‐2.0重量%的稀土元素氧化物改性;第二沸石的特征在于SiO2/Al2O3摩尔比=82,含有基于所述第二沸石质量0.04重量%的残余量的氧化钠,并且被氧化镁以基于所述第二沸石质量0.5‐5.0重量%的量改性,其中所述沸石以介于1.7/1和2.8/1之间的质量比使用,该催化剂还含有粘结剂,该粘结剂至少含有氧化硅,并且以基于所述催化剂的质量20‐25重量%的量使用。
2.根据权利要求1所述的催化剂,其特征在于,所述粘结剂另外地含有氧化铝,其量不超过所述粘结剂质量的25重量%。
3.芳香化C3‐C4气体、低辛烷烃级分和脂肪醇以及它们的混合物的方法,其包括使加热的气体原料与含沸石的催化剂在升高的温度和压力下接触的阶段,所述方法的特征在于使用了根据权利要求1中所述的催化剂,且过程是在等温反应器中在催化剂温度为400‐500℃下、在压力为1.0‐18atm下是通过使固定床催化剂与气体原料接触而进行,未采用分离气体的再循环,其中所述气体原料以300‐1500h‐1的供给气空速度在预热器中被蒸发,并被加热至150‐250℃的温度。
4.根据权利要求3所述的催化剂,其特征在于所用的原料是链烷烃和烯属的C3‐C4气体、天然气液、各种具有至多200℃的沸点的汽油和氧合物的混合物,以及烃与氧合物的混合物,为此目的,使用了C1‐C3脂肪醇,且氧合物的含量为10‐50体积%。
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- 2014-12-17 WO PCT/RU2014/000953 patent/WO2015115932A1/ru active Application Filing
- 2014-12-17 CA CA2945839A patent/CA2945839A1/en not_active Abandoned
- 2014-12-17 EP EP14881043.5A patent/EP3100784A4/en not_active Withdrawn
- 2014-12-17 CN CN201480074251.2A patent/CN106163661B/zh active Active
- 2014-12-17 US US15/113,147 patent/US10131592B2/en active Active
- 2014-12-17 AU AU2014380443A patent/AU2014380443B2/en active Active
- 2014-12-17 EA EA201600533A patent/EA031119B1/ru not_active IP Right Cessation
- 2014-12-17 BR BR112016017158A patent/BR112016017158A2/pt not_active Application Discontinuation
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US10894752B2 (en) | 2021-01-19 |
AU2014380443A1 (en) | 2016-08-25 |
EA201600533A1 (ru) | 2016-11-30 |
RU2544017C1 (ru) | 2015-03-10 |
EP3100784A1 (en) | 2016-12-07 |
US20170007992A1 (en) | 2017-01-12 |
CA2945839A1 (en) | 2015-08-06 |
BR112016017158A2 (pt) | 2017-10-03 |
EP3100784A4 (en) | 2017-09-27 |
AU2014380443B2 (en) | 2018-08-02 |
EA031119B1 (ru) | 2018-11-30 |
WO2015115932A1 (ru) | 2015-08-06 |
US10131592B2 (en) | 2018-11-20 |
US20190100477A1 (en) | 2019-04-04 |
CN106163661B (zh) | 2019-09-06 |
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