CN103328417A - Process for converting lower alkanes to aromatic hydrocarbons and ethylene - Google Patents
Process for converting lower alkanes to aromatic hydrocarbons and ethylene Download PDFInfo
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- CN103328417A CN103328417A CN2011800652974A CN201180065297A CN103328417A CN 103328417 A CN103328417 A CN 103328417A CN 2011800652974 A CN2011800652974 A CN 2011800652974A CN 201180065297 A CN201180065297 A CN 201180065297A CN 103328417 A CN103328417 A CN 103328417A
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- Prior art keywords
- ethane
- product stream
- aromatic hydrocarbons
- aromatics
- propane
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- 238000000034 method Methods 0.000 title claims abstract description 90
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims description 82
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title description 44
- 230000008569 process Effects 0.000 title description 13
- 239000005977 Ethylene Substances 0.000 title description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 113
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 98
- 229930195733 hydrocarbon Natural products 0.000 claims description 55
- 150000002430 hydrocarbons Chemical class 0.000 claims description 53
- 239000001294 propane Substances 0.000 claims description 49
- 239000012188 paraffin wax Substances 0.000 claims description 33
- 238000000926 separation method Methods 0.000 claims description 7
- 241000282326 Felis catus Species 0.000 claims description 2
- 238000005899 aromatization reaction Methods 0.000 abstract description 34
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 151
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 75
- 238000011056 performance test Methods 0.000 description 47
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 38
- 238000010606 normalization Methods 0.000 description 33
- 239000000203 mixture Substances 0.000 description 30
- 239000000047 product Substances 0.000 description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 25
- 229910052739 hydrogen Inorganic materials 0.000 description 25
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 23
- 239000007789 gas Substances 0.000 description 20
- 239000004215 Carbon black (E152) Substances 0.000 description 19
- 238000005336 cracking Methods 0.000 description 16
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 15
- 239000010457 zeolite Substances 0.000 description 15
- 150000002431 hydrogen Chemical class 0.000 description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910052697 platinum Inorganic materials 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 10
- 229910000323 aluminium silicate Inorganic materials 0.000 description 10
- 235000013844 butane Nutrition 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000001273 butane Substances 0.000 description 9
- 230000002349 favourable effect Effects 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000004587 chromatography analysis Methods 0.000 description 8
- 230000009977 dual effect Effects 0.000 description 6
- 229910052733 gallium Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 238000006900 dealkylation reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 241001120493 Arene Species 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000009533 lab test Methods 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- -1 polyethylene, ethylene Polymers 0.000 description 4
- 238000002203 pretreatment Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005235 decoking Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical group [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical class [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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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
- 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
- B01J29/42—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 iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/44—Noble metals
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present application describes a method comprising: contacting in a first stage a lower alkane feed with an aromatization catalyst under first stage reaction conditions to produce a first stage product stream comprising ethane and aromatics; separating aromatics from the first stage product stream to form an aromatics product stream and a non-aromatics product stream; introducing a first portion of the non-aromatic product stream to an alkane cracker; and contacting a second portion of the non-aromatic product stream with an aromatization catalyst in a second stage under second stage reaction conditions to produce a second stage product stream comprising aromatics.
Description
Technical field
The present invention relates to produce from lower paraffin hydrocarbons the integral method of aromatic hydrocarbons and ethene.More particularly, the present invention relates to produce from lower paraffin hydrocarbons the integral method of the low fund of having of benzene and ethene and running cost.
Background technology
Benzene and ethene are two kinds in the most important basic product of modern petrochemical product industry.Benzene is used for making important petroleum chemicals for example vinylbenzene, phenol, nylon and urethane etc.Ethene is for the manufacture of other petroleum chemicals for example polyethylene, ethylene oxide, ethylene dichloride and ethylbenzene etc.
Usually, benzene and other aromatic hydrocarbons are by utilizing solvent extration, the feedstock fraction (reformate that for example produces by catforming and the pyrolysis gasoline by the generation of naphtha cracking method) that is rich in aromatic substance are separated obtaining with non-aromatics.Yet, in order to make great efforts to tackle the aromatic hydrocarbons short supply of this expection, after deliberation specially be used for from each molecule contain six or still less the alkane of carbon atom produce many Catalyst And Methods of aromatic hydrocarbons (comprising benzene).The easness that individual alkane changes into aromatic hydrocarbons increases and increases along with carbon number, has therefore considered the mixed alkanes charging.For example, U.S.5,258,564 have described C
2To C
6Aliphatic hydrocrbon changes into the method for aromatic hydrocarbons, described method is included under dehydrogenation cyclodimerisation (deehydrocyclodimerization) condition charging is contacted with catalyzer, and wherein said catalyzer comprises Si: the Al ratio greater than 10 and the aperture be zeolite, gallium component and the phosphate aluminium adhesive of 5-6 dust.
The catalyzer that uses is normally dual functional, and containing zeolite or molecular screen material provides acidity and one or more metals such as Pt, Ga, Zn, Mo etc. that dehydrogenation activity is provided.For example, United States Patent (USP) 4,350,835 have described the crystalline zeolite catalyzer that utilizes the ZSM-5-type family of containing a small amount of Ga, and the gaseous feed that will contain ethane changes into the method for aromatic hydrocarbons.As another example, United States Patent (USP) 7,186,871 have described utilization contains the catalyzer of Pt and ZSM-5 to C
1-C
4The aromizing of alkane.
Ethene usually in high temperature thermally splitting device or catalytic cracking apparatus from ethane and/or more higher hydrocarbon manufacturing.Making alkene by the hydrocarbon pyrolysis is the industrial method of establishing, and it is described in Ludwig Kniel " Ethylene:Keystone to The Petrochemical Industry ", among the Marcel Dekker Publisher (1980).
When ethane adds one or more more the charging of higher hydrocarbon changes into alkene in the cracker device, except ethene, also can produce other alkene.Described alkene comprises propylene, butylene, divinyl, amylene etc., depends on the composition of cracker raw material.Because have the multiple olefin product that must separate to meet with other similar molecules (for example corresponding paraffinic hydrocarbons) under many circumstances product specification, so the product separation scheme of such parallel feeding cracker is tending towards complexity.Net result is that fund expenditure and the running cost of such cracker machinery is higher than the cracker that only produces ethene from main ethane feed far away.
A kind of lower paraffin hydrocarbons dehydroaromatizationof method advantageously is provided, the ethene of (a) generation lower cost is transformed basically as by product and the charging of (b) supplying with the dehydrogenation and aromatization device in the method, thereby has avoided any charging recirculation also thus so that fund and running cost are lower.
Summary of the invention
The invention provides a kind of method, described method comprises: a.) in the fs lower paraffin hydrocarbons charging is contacted under the fs reaction conditions with aromatized catalyst, produce the fs product stream that comprises ethane and aromatic hydrocarbons; B.) from fs product stream aromatics separation, form aromatic product stream and non-aromatics product stream; C.) first part's non-aromatics product stream is introduced the alkane cracker; With d.) second section non-aromatics product stream is contacted under the subordinate phase reaction conditions in subordinate phase with aromatized catalyst, produce the subordinate phase product stream that comprises aromatic hydrocarbons.
In another embodiment, benzene can with the toluene and/or dimethylbenzene and the C that reclaim in the step (b)
9+Aromatic hydrocarbons separates, and can reclaim described benzene.Described toluene and/or dimethylbenzene then can hydrodealkylations, produce extra benzene.
Description of drawings
Fig. 1 is schema, and it illustrates the circulation of mixing lower paraffin hydrocarbons and turns to aromatic hydrocarbons and ethane, and ethane then cracking produces ethene or is fed into the second aromatization reactor.
Fig. 2 is schema, and it illustrates the circulation of mixing lower paraffin hydrocarbons and turns to aromatic hydrocarbons and ethane, and ethane then cracking produces ethene, and wherein benzene separates with dimethylbenzene with toluene, and toluene and dimethylbenzene hydrodealkylation produce more benzene.
Detailed Description Of The Invention
The present invention relates to produce from mixing lower alkyl hydrocarbon stream (being called " mixing lower paraffin hydrocarbons " or " lower paraffin hydrocarbons " herein) the integrated processing scheme of benzene (and other aromatic hydrocarbons) and ethene, described mixing lower alkyl hydrocarbon stream can contain C
2, C
3, C
4And/or C
5Alkane for example derives from the logistics that is rich in ethane/propane/butane of the logistics (comprising waste streams) of Sweet natural gas, refinery or petroleum chemicals.The example of incoming flow that may be suitable comprises that (but being not limited to) is from the residual ethane of Sweet natural gas (methane) purifying and propane, common pure ethane, propane and the butane logistics (also claiming natural gas liquids) that produces in the natural gas liquids place, from the C of the common associated gas that produces of crude production
2-C
5Stream, from the unreacted ethane " refuse " of steam cracker stream with from the C of naphtha reformer
1-C
3Byproduct stream.Described lower paraffin hydrocarbons charging can be specially with the gas of relative inertness nitrogen and/or dilute with various light hydrocarbons and/or with the low-level additive that improves catalyst performance and need for example.The product that method of the present invention is mainly wanted is benzene,toluene,xylene and ethene.
Hydrocarbon in the raw material can comprise ethane, propane, butane and/or C
5Alkane or its any combination.Preferably, the major part of mixed alkanes is ethane and propane in the raw material.Raw material can comprise in addition other and contain 3 and 8 open-chain hydrocarbons between the carbon atom as co-reactant.The object lesson of this other co-reactant is propylene, Trimethylmethane, n-butene and iso-butylene.Described hydrocarbon feed preferably comprises at least about 30 % by weight, preferably at least about the C of 50 % by weight
2-4Hydrocarbon.
The first step of described integral method comprises from being rich in the catalytic material that mixes lower paraffin hydrocarbons and produces benzene, during this period, and all C basically
3+Hydrocarbon is converted in one way in this first step.In one embodiment, at least about 90 % by weight, preferably at least about 95 % by weight, most preferably propane and the heavy hydrocarbon at least about 99 % by weight is converted into aromatic hydrocarbons and by product in the raw material.Described reaction can for example be carried out in the presence of the catalyst composition of benzene being suitable for promoting the lower paraffin hydrocarbons reaction to become aromatic hydrocarbons.Reaction conditions can comprise approximately 450 ℃ to approximately 750 ℃ temperature and approximately 0.01MPa to the about pressure of 0.5MPa absolute pressure.If necessary, can move the first step of described method, with effective generation ethane, ethane can make the generation of ethene increase.
After the product separation scheme of the methane/hydrogen that reclaims aromatic hydrocarbons and choose wantonly, the remaining rich C of a part
2Stream is sent to the ethane cracking step, and it can be conventional ethane cracker (preferred catalytic or thermally splitting device), to produce ethene, the remaining rich C of a part
2Stream is sent to the subordinate phase aromatization reactor, to produce aromatic hydrocarbons.By this way, the fs alkane reactor that is converted into benzene has served as basically removed all C from the raw material of sending into the ethane cracker
3+The device of hydrocarbon, thus the design of ethane cracker simplified considerably.By cancelling separating of necessary a small amount of propylene and ethene, significantly reduced fund and the running cost of ethane cracker machinery, and described a small amount of propylene and ethene be separated in the C that the charging of supplying with cracker contains significant quantity
3+Necessary during hydrocarbon.In addition, the process that fs alkane is converted into benzene also is once-through process (is not converted charging and do not carry out recirculation), so that fund and the running cost of described total integrated processing scheme further reduce.
The subordinate phase aromatization reactor provides the handiness that allows to produce by described method product mixtures.The subordinate phase aromatization reactor can use any catalyzer and the processing condition of the suitable fs aromatization reactor of description.
Can promote the lower paraffin hydrocarbons reaction to become aromatic hydrocarbons with any of various catalyzer.A kind of such catalyzer is described in U.S.4, and in 899,006, it incorporates this paper into by reference with its full content.The catalyst composition of describing therein comprise the aluminosilicate that deposited gallium on it and/or wherein positively charged ion with the aluminosilicate of gallium ion exchange.The molar ratio of silicon-dioxide and aluminum oxide is at least 5: 1.
The another kind of catalyzer that can be used for the inventive method has been described among the EP 0 244 162.This catalyzer comprises the catalyzer described in the leading portion and the VIII family metal of selected from rhodium and platinum.Described aluminosilicate it is believed that preferably MFI or MEL type structure, and can be ZSM-5, ZSM-8, ZSM-11, ZSM-12 or ZSM-35.
U.S.7 has described other catalyzer that can be used for the inventive method in 186,871 and U.S.7,186,872, and these two patents are incorporated this paper into by reference with its full content.First patent has been described the ZSM-5 crystalline zeolite of platiniferous, its by preparation in skeleton, contain the zeolite of aluminium and silicon, at described zeolite deposition platinum and calcine described zeolite and synthesize.Second patent described the catalyzer that comprises gallium and substantially do not contain aluminium in skeleton.
Other catalyzer that can be used for the inventive method comprise U.S.5, those that describe in 227,557, and described patent is incorporated this paper into by reference with its full content.These catalyzer comprise the MFI zeolite and add at least a platinum family precious metal and at least a other metals that are selected from tin, germanium, lead and indium.
Being used for a kind of preferred catalyst of the present invention describes at U.S. Patent Application Publication No.2009/0209795.This application is incorporated this paper into by reference with its full content.This application has been described a kind of catalyzer, it comprises: (1) is based on the metal meter, approximately 0.005 to about 0.1wt% (% by weight), preferred approximately 0.01 to the about platinum of 0.05wt%, (2) a certain amount of weakening type (attenuating) metal that is selected from tin, lead and germanium, the amount that described amount is lower than platinum is no more than 0.02wt%; Based on the metal meter, preferably be no more than the 0.2wt% of described catalyzer; (3) based on described aluminosilicate meter, approximately 10 to about 99.9wt%, preferred approximately 30 to the about aluminosilicate of 99.9wt%, preferred zeolite is preferably selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23 or ZSM-35, preferably is converted into the H+ form, preferred SiO
2/ Al
2O
3Mol ratio is approximately 20: 1 to approximately 80: 1, and (4) tackiness agent, is preferably selected from silicon-dioxide, aluminum oxide and composition thereof.
Be used for another kind of preferred catalyst of the present invention and be described in the U.S. Patent application No.12/867973 that submitted on August 17th, 2010.This application is incorporated this paper into by reference with its full content.A kind of catalyzer has been described in described application, it comprises: (1) is based on the metal meter, approximately 0.005 to about 0.1wt% (% by weight), preferred approximately 0.01 to about 0.06wt%, most preferably from about 0.01 to the about platinum of 0.05wt%, (2) a certain amount of iron, described amount is equal to or greater than the amount of platinum, but be based on the metal meter, be no more than the approximately 0.50wt% of catalyzer, preferably be no more than catalyzer approximately 0.20wt%, be most preferably not exceeding the approximately 0.10wt% of catalyzer; (3) based on described aluminosilicate meter, approximately 10 to about 99.9wt%, preferred approximately 30 to the about aluminosilicate of 99.9wt%, preferred zeolite is preferably selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23 or ZSM-35, preferably is converted into the H+ form, preferred SiO
2/ Al
2O
3Mol ratio is approximately 20: 1 to approximately 80: 1, and (4) tackiness agent, is preferably selected from silicon-dioxide, aluminum oxide and composition thereof.
Be used for another kind of preferred catalyst of the present invention and be described in U.S. Patent Application Publication No.2009/0209794.This announcement is incorporated this paper into by reference with its full content.A kind of catalyzer has been described in this announcement, it comprises: (1) is based on the metal meter, approximately 0.005 to about 0.1wt% (% by weight), preferred approximately 0.01 to about 0.05wt%, most preferably from about 0.02 to the about platinum of 0.05wt%, (2) a certain amount of gallium, described amount is equal to or greater than the amount of platinum, based on the metal meter, preferably be no more than approximately 1wt%, be most preferably not exceeding approximately 0.5wt%; (3) based on described aluminosilicate meter, approximately 10 to about 99.9wt%, preferred approximately 30 to the about aluminosilicate of 99.9wt%, preferred zeolite is preferably selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23 or ZSM-35, preferably is converted into the H+ form, preferred SiO
2/ Al
2O
3Mol ratio is 20: 1 to 80: 1, and (4) tackiness agent, is preferably selected from silicon-dioxide, aluminum oxide and composition thereof.
Hydrodealkylation relate to toluene, dimethylbenzene, ethylbenzene and more higher aromatics and H-H reaction produce extra benzene and lighting end and comprise methane and ethane from aromatic ring, to remove alkyl, methane is separated with benzene with ethane.This step has increased the total recovery of benzene significantly, is highly favourable therefore.
Heat and catalytic hydrodealkylation process all are known in the art.Hot dealkylation can be such as U.S.4,806,700 described carrying out, and described document is incorporated this paper into by reference with its full content.In described thermal means, the working temperature of hydrodealkylation can be from approximately 500 to approximately 800 ℃ in the ingress of hydrodealkylation device.Pressure can be from about 2000kPa to about 7000kPa.Can utilize based on the long-pending meter of the available content of reaction vessel, approximately 0.5 to about 5.0 liquid hourly space velocity.
Because the exothermal nature of described reaction often need to be carried out described reaction in two or more stages, cool off or quenching reactant the centre.Therefore can connect and use two or three or more reaction vessel.Cooling can realize by indirect heat exchange or interstage cooling.When using two reaction vessels in the hydrodealkylation district, preferred the first reaction vessel there is no any internal structure, and second container contains enough internal structures, to promote reactant with a part of container of piston flow process.
Perhaps, solid catalyst bed can be contained in described hydrodealkylation district, U.S.3 for example, and the catalyzer of describing in 751,503, described document is incorporated into by reference with its full content.Another kind of possible catalytic hydrodealkylation method is described in U.S.6, and in 635,792, described document is incorporated this paper into by reference with its full content.This patent has been described the hydrodealkylation processes that carries out also containing platinum and tin or plumbous zeolite containing catalyst.Described method preferably approximately 250 ℃ to approximately 600 ℃ temperature, approximately 0.5MPa is to the pressure of about 5.0MPa, approximately 0.5 to about 10hr
-1The liquid hydrocarbon feed speed of weight hourly space velocity and approximately 0.5 to approximately carrying out under 10 hydrogen/hydrocarbon feed molar ratio.
Light alkene, namely ethene and propylene can produce from lower paraffin hydrocarbons (ethane, propane and butane) by heat or catalytic cracking method.The thermally splitting method can be carried out in the presence of superheated vapour usually, and it is the most frequently used so far commercial implementation method.Steam cracking is a kind of thermally splitting method, and wherein stable hydrocarbon (being ethane, propane, butane or their mixture) is broken down into less unsaturated hydrocarbons, i.e. alkene and hydrogen.
In steam cracking, can dilute gaseous feed with steam, then of short duration heating in stove (not having oxygen).Usually, temperature of reaction can be very high---about 750 to 950 ℃---but only allow reaction that the very short time occurs.In the cracking furnace in modern times, in order to improve the yield of expectation product, residence time even can be reduced to millisecond (causing gas velocity to reach speed above velocity of sound).After reaching the cracking temperature, described gas can by rapidly quenching in transfer line exchanger, stop described reaction.
The product that produces in described reaction depends on ratio and cracking temperature and the residing time in furnace of composition, hydrocarbon and the steam of charging.Described method usually can be under low pressure, operate under about 140 to 500kPa, depends on the overall craft design.
Described method also may cause slowly depositing on reactor wall burnt, and it is a kind of form of carbon.This has reduced the efficient of reactor, therefore designs reaction conditions above-mentioned deposition Jiao is minimized.However, the time of steam cracker furnace between decoking can only be moved the several months usually.Decoking need to make stove break away from from technique, and then steam or Steam/air mixture stream at high temperature passes through the coil pipe of described stove.This is converted into carbon monoxide and carbonic acid gas with hard solid carbon-coating.In case this reaction is finished, described stove can recover to use.
In many commerciality operations, by at low temperatures repeated compression and distillation, ethene is separated from the complex mixture that generates with propylene.In the method for the invention, this can be unnecessary, mainly is comprised of ethane because supply with the charging of cracker.
The fs that alkene produces and purifies in the cracker machinery is: 1) steam cracking in aforesaid stove; 2) carry out first and the secondary heat recuperation with quenching; 3) the dilution steam generation recirculation between stove and quench system; 4) the first compression (stage compression) of reacted gas; 5) remove hydrogen sulfide and carbonic acid gas (acid gas removes); 6) second-compressed (1 or 2 grade); 7) drying of reacted gas; With 8) subzero treatment of dry reacted gas.
Then the cold cracking air-flow is processed in demethanizing tower.The overhead streams of demethanizing tower is comprised of hydrogen and methane, with its subzero treatment with hydrogen and methane separation.This separating step comprises temperature liquid methane approximately-150 ℃ usually.The economical operation of reclaiming fully for described olefin equipment of all methane is crucial.
The tower bottom flow of demethanizing tower is processed in deethanizing column.The overhead streams of deethanizing column comprises C all in the cracking air-flow
2' component.Described C
2Then ' component goes to C
2Separator (splitter).Obtain product ethene from the cat head of described tower, out ethane recycle is to described stove, by cracking again or go to one of aromatization stage from separator bottom.
Come from the tower bottom flow of deethanizing column and can go to depropanizing tower, but in the method for the invention, this can omit.The overhead streams of depropanizing tower comprises C all in the cracking air-flow
3' component.At C
3' component is sent to C
3Before the separator, should flow hydrogenation, to react away methylacetylene and propadiene.Then this stream is sent to C
3Separator.Come from C
3The overhead streams of separator is the product propylene, and comes from C
3The tower bottom flow of separator is propane, and propane can be sent back to and carry out cracking in the described stove or be used as fuel.
Come from the tower bottom flow of depropanizing tower and can go to debutanizing tower, but in the method for the invention, this also can omit.The overhead streams that comes from debutanizing tower is C all in the cracking air-flow
4' component.The tower bottom flow that comes from debutanizing tower comprises C all in the cracking air-flow
5Or heavy component more.It can be called as the lightweight pyrolysis gasoline.
Because the generation of ethene is energy-intensive, many work have been devoted to reclaim heat from the gas that leaves stove.The most of energy that reclaims from reacted gas can be used for making high pressure (approximately 8300kPa) steam.This steam and then can be used for turbine, propylene refrigeration compressor (may be unnecessary in the methods of the invention) and the ethylene refrigeration compressor of drive compression reacted gas.
Described ethene manufacture method also can be implemented in the presence of catalyzer.Advantage is to use much lower temperature and may not have steam.In principle, can realize to alkene than highly selective and may coking less.Although also not commerciality practice in the factory of world scale, the catalytic cracking of ethane is an interested field for a long time always.Being used for the catalyst type of cracking higher hydrocarbon comprises zeolite, clay, aluminosilicate etc.Should be mentioned that this method carried out business practice at several refinerys to high-molecular-weight hydrocarbons, described high-molecular-weight hydrocarbons carries out cracking at zeolite catalyst in the processing unit (plant) that is called FCC (fluid catalytic cracking device).In this method, more generally produce and Propylene recovery as by product, rather than ethene and propylene the two.
One embodiment of the present invention illustrate in the simplification block flow diagram of Fig. 1.In Fig. 1, the stream 10 that is rich in ethane/propane/butane is fed to reactor 12, and described reactor 12 contains suitable catalyzer or catalyst mixture, is used for alkane is converted into benzene.Reactor product stream 14 contains unreacted ethane and thinner (if any), adds hydrogen, methane, a small amount of C
3-C
5Hydrocarbon, benzene,toluene,xylene and heavy arene, and the selectivity of benzene is preferably greater than approximately 20%.This product stream 14 is by suitable separation and extractor 16, and a part of unreacted ethane 18 is fed to ethane cracker 20, is converted at this to be ethene 22.The unreacted ethane 18 of another part is fed to the second aromatization reactor 40, produces aromatic hydrocarbons 42.Randomly (but be not must) utilizes pressure-variable adsorption or membrane process, from the C of tripping device 16
1(methane) stream 24 and/or reclaim H from the similar stream 26 of cracker 20
2, and can be sent to hydro-dealkylation gasifying device as described below.Described aromatic hydrocarbons leaves tripping device 16 by pipeline 17.
For major objective be from contain ethane and the more single mixing raw material 10 of higher hydrocarbon produce the method for ethene and aromatic hydrocarbons, some variations are arranged.In a kind of pattern as shown in Figure 1, only reclaim the benzene that produces in the aromatic hydrocarbons.There is not the hydro-dealkylation gasifying device, common toluene and dimethylbenzene and the C that produces
9+Aromatic hydrocarbons is recovered together.In another kind of pattern, as shown in Figure 2, the two selectivity of toluene and dimethylbenzene is transformed into benzene and methane.Then this extra benzene join in the benzene that produces in main reaction.In another kind of version (not shown), do not attempt separation of benzene, toluene and dimethylbenzene component, their mixture is sent to the hydro-dealkylation gasifying device.
In Fig. 2, benzene also separates with dimethylbenzene with toluene in tripping device 16.Benzene leaves by pipeline 28, and toluene and dimethylbenzene leave and are introduced to hydro-dealkylation gasifying device 32 by pipeline 30 and merges mutually with hydrogen from pipeline 34.Toluene and dimethylbenzene are produced benzene by hydrodealkylation in pipeline 36, then described benzene merge with the benzene of pipeline 28.In addition, C
9+Aromatic hydrocarbons is removed from tripping device 16 by pipeline 38.Aromatic hydrocarbons 42 can be chosen wantonly and be sent to tripping device 16.
Embodiment
Provide following examples only for the illustrative intention, rather than want to limit the scope of the invention.
Embodiment 1
In this embodiment, the scope that shows the product composition that can obtain from flexibly two stage aromatization methods of the present invention with the result of laboratory test.The lower paraffin hydrocarbons raw material of the present embodiment is comprised of 19.9wt% ethane and 80.1wt% propane.The operating temperature in the first and second stages is respectively 540 and 621 ℃.
Catalyst A is extruded particle manufacturing in diameter 1.6mm cylindrical, and described particle contains the zeolite ZSM-5 CBV 2314 powder (SiO of 80wt%
2/ Al
2O
3Mol ratio is 23: 1, can obtain from Zeolyst International) and the 20wt% alumina adhesive.Described extrudate sample is calcined in air until 650 ℃, to be used for removing residual moisture before the catalyzer preparation.The metal target carrying capacity of catalyst A is 0.025wt%Pt and 0.09wt%Ga.
By at first the storage of four an amount of ammino platinum nitrates and gallium nitrate (III) being merged, dilutes this mixture to the enough volume in the hole of the above-mentioned ZSM-5/ alumina extrudate of filling and flood described extrudate with this solution under room temperature and normal atmosphere just with deionized water with the aqueous solution, thereby restrain metal refining on the described extrudate sample at 25-100.Impregnated sample at room temperature aging 2-3 hour is then 100 ℃ of dried overnight.
Fresh as described below the making a service test of 15-cc catalyst A charging.Performance test 1 is carried out under the condition of the fs of the two stage aromatization methods that can use for the present invention mixing ethane/propane feed.Carry out under the condition of performance test 2 subordinate phase in can be used for two stage aromatization methods of the present invention.
For each performance test, all fresh (in the past not test (N.T.)) catalyst charge " same as before " of 15-cc not being crushed just is loaded in the 316H type stainless steel tube (internal diameter 1.40cm), and puts into the four district's stoves that are connected with air flow system.
Before performance test 1, with the charging of fresh catalyst A barometric point (approximately 0.1MPa absolute pressure) lower following carry out in situ pretreatment:
(a) use the per hour air calcination of about 60 liters (L/hr), during this period, the reactor wall temperature is elevated to 510 ℃ from 25 ℃ in 12hr, keeps 4hr at 510 ℃, then in 1hr, further be elevated to 540 ℃ from 510 ℃, then at 540 ℃ of lower 30min that keep;
(b) under 540 ℃ with the nitrogen purging 20min of about 60L/hr;
(c) under 540 ℃, with the hydrogen reducing 30min of 60L/hr.
When above-mentioned reduction step finishes, stop hydrogen stream, and with catalyst charge under normal atmosphere (approximately 0.1MPa absolute pressure), 540 ℃ of reactor wall temperature and 1000GHSV (every cubic centimetre catalyzer per hour 1000 cubic centimetres of raw materials) input speed, be exposed to the charging that is formed by 19.9wt% ethane and 80.1wt% propane.Introduced after the charging three minutes, and by online gas chromatograph total reactor outlet stream was taken a sample, be used for analyzing.
Performance test 2 is with the same mode of above performance test 1 and carry out under the same conditions, and difference is that the outlet temperature that reaches during the air calcination pre-treatment step is 621 ℃, nitrogen purging and hydrogen reduction step and carries out and 100% ethane feed is introduced at 621 ℃ under 621 ℃ of reactor wall temperature.This has simulated the subordinate phase of dual stage process.
Table 1 has been listed the result that the gross product stream to above-described performance test 1 and 2 carries out online gas chromatographic analysis.According to the composition data that obtain from gas chromatographic analysis, calculate initial ethane and conversion of propane according to formula given below.
Ethane conversion, %=100x (ethane wt% during ethane wt%-outlet is flowed in the charging)/(ethane wt% in the charging)
Conversion of propane, %=100x (propane wt% during propane wt%-outlet is flowed in the charging)/(propane wt% in the charging)
For performance test 1, in the reactor outlet stream except ethane each component calculate according to following formula based on the normalization method wt% yield that is converted charging:
The normalization method wt% yield of component C=10,000x (wt% of component C in the reactor outlet stream)/(propane wt%x transformation of propane % in the charging)
For performance test 1, calculate according to following formula based on the clean ethane recovery of normalization method wt% that is converted charging:
The clean ethane recovery of normalization method wt%=10,000x (in the reactor outlet stream in the ethane wt%-charging ethane wt%)/(propane wt%x transformation of propane % in the charging)
For performance test 2, in the reactor outlet stream except ethane each component calculate according to following formula based on the normalization method wt% yield that is converted charging:
Normalization method wt% yield=100x of component C (wt% of component C in the reactor outlet stream)/(ethane transforms wt%)
For performance test 1, based on all clean ethane that transform from performance test 1 under the condition of using in the performance test 2, total normalization method wt% yield of each component (except ethane) calculates according to following formula in the reactor outlet stream:
In subordinate phase, has the normalization method wt% yield of the component C that clean ethane transforms=from the normalization method wt% yield of the component C of performance test 1+(from the normalization method wt% yield of the clean ethane recovery x of the normalization method wt% of performance test 1 from the component C of performance test 2)/100.
Table 1
| Performance test | 1 | 2 |
| The reactor wall temperature, ℃ | 540 | 621 |
| Pressure, MPa | 0.1 | 0.1 |
| Feed composition | ? | ? |
| Ethane, wt% | 19.9 | 100 |
| Propane, wt% | 80.1 | 0 |
| Total feed rate, GHSV | 1000 | 1000 |
| Total feed rate, WHSV | 2.16 | 1.61 |
| Ethane conversion, % | -154.54 | 48.34 |
| Conversion of propane, % | 95.26 | -- |
| ? | ? | ? |
| Reactor outlet forms, wt% | ? | ? |
| Hydrogen | 2.67 | 4.56 |
| Methane | 9.05 | 7.94 |
| Ethene | 0.8 | 4.37 |
| Ethane | 50.58 | 51.66 |
| Propylene | 0.68 | 0.57 |
| Propane | 3.8 | 0.63 |
| C4 | 0.2 | 0.11 |
| C5 | 0 | 0 |
| Benzene | 11.1 | 14.61 |
| Toluene | 12.33 | 6.94 |
| C8 aromatic hydrocarbons | 3.63 | 1.19 |
| C9+ aromatic hydrocarbons | 5.16 | 7.41 |
| Total aromatic hydrocarbons | 32.22 | 30.15 |
| Based on the normalization method wt% yield that is converted charging | ? | ? |
| Hydrogen | 3.50 | 9.43 |
| Clean ethane | 40.21 | -- |
| Benzene | 14.55 | 30.22 |
| Toluene | 16.16 | 14.36 |
| C8 aromatic hydrocarbons | 4.76 | 2.46 |
| C9+ aromatic hydrocarbons | 6.76 | 15.33 |
| Total aromatic hydrocarbons | 42.23 | 62.37 |
| Total aromatic hydrocarbons+clean ethane | 82.43 | 62.37 |
| Total normalization method wt% yield, the clean ethane that in the stage 2, transforms | ? | ? |
| Hydrogen | 7.29 | ? |
| Benzene | 26.70 | ? |
| Toluene | 21.93 | ? |
| C8 aromatic hydrocarbons | 5.75 | ? |
| C9+ aromatic hydrocarbons | 12.92 | ? |
| Total aromatic hydrocarbons | 67.30 | ? |
Can find out from table 1, can can change to the 67.30wt% at 42.23wt% from the normalization method total arenes yield (based on the wt% of charging) that dual stage process of the present invention obtains, depending on has what to be passed to subordinate phase from the clean ethane of fs.Similarly, can be from 14.55wt% to 26.70wt% from the scope of the total benzene yield of the normalization method that the method obtains (based on the wt% of charging), depending on has what to be passed to subordinate phase from the clean ethane of fs.If the ethene of making is favourable economically more than aromatic hydrocarbons, the operator can select and will be sent to steam cracker to produce ethene from a part or all clean ethane of fs of lower paraffin hydrocarbons aromatization method so.If benzene or other aromatic hydrocarbons made are favourable economically more than ethene, the operator can select to be sent to from the most of clean ethane of fs the subordinate phase of lower paraffin hydrocarbons aromatization method so.Therefore, two stage lower paraffin hydrocarbons aromatization methods of the present invention can provide refining with suitable flexibility of operation/petrochemical industry machinery, according to demand or the variation of economic environment and change its product composition.
Embodiment 2
In this embodiment, show the scope of the product composition that can obtain from flexibly two stage aromatization methods of the present invention with the result of laboratory test.The lower paraffin hydrocarbons raw material of the present embodiment is comprised of 19.9wt% ethane and 80.1wt% propane.The operating temperature in the first and second stages is respectively 580 and 621 ℃.
Fresh 15-cc catalyst A charging such as preparation among the above-mentioned embodiment 1 is made a service test 3, performance test 3 according to top embodiment 1 in performance test 1 the same manner of describing carry out, except the outlet temperature that reaches during the air calcination pre-treatment step be 580 ℃, nitrogen purging and hydrogen reduction step carry out under 580 ℃ and the reactor wall temperature of ethane/propane feed at 580 ℃ under introduce.
Table 2 listed performance test 3 and as top embodiment 1 described in the online gas chromatographic analysis result of gross output logistics of the performance test 2 of carrying out.Performance test 3 is carried out under the condition of the fs of the two stage aromatization methods that are used for use mixing ethane/propane feed of the present invention.Described in top embodiment 1, performance test 2 is carried out under the condition of the subordinate phase that can be used for two stage aromatization methods of the present invention.
According to the composition data that obtain from gas chromatographic analysis, calculate initial ethane and conversion of propane according to the top formula that in embodiment 1, provides.The normalization method wt% yield of reactor outlet stream component calculates according to the formula that these amounts of calculating in the top performance test 1 provide in the performance test 3.Described in the normalization method wt% yield of the reactor outlet of performance test 2 stream component such as top embodiment 1, calculate.
Table 2
| Performance test | 3 | 2 |
| The reactor wall temperature, ℃ | 580 | 621 |
| Pressure, MPa | 0.1 | 0.1 |
| Feed composition | ? | ? |
| Ethane, wt% | 19.9 | 100 |
| Propane, wt% | 80.1 | 0 |
| Total feed rate, GHSV | 1000 | 1000 |
| Total feed rate, WHSV | 2.13 | 1.61 |
| ? | ? | ? |
| Ethane conversion, % | -120.09 | 48.34 |
| Conversion of propane, % | 98.80 | -- |
| ? | ? | ? |
| Reactor outlet forms, wt% | ? | ? |
| Hydrogen | 3.55 | 4.56 |
| Methane | 10.87 | 7.94 |
| Ethene | 1.85 | 4.37 |
| Ethane | 43.74 | 51.66 |
| Propylene | 0.43 | 0.57 |
| Propane | 0.96 | 0.63 |
| C4 | 0.07 | 0.11 |
| C5 | 0 | 0 |
| Benzene | 15.98 | 14.61 |
| Toluene | 12.95 | 6.94 |
| C8 aromatic hydrocarbons | 3.04 | 1.19 |
| C9+ aromatic hydrocarbons | 6.56 | 7.41 |
| Total aromatic hydrocarbons | 38.53 | 30.15 |
| Based on the normalization method wt% yield that is converted charging | ? | ? |
| Hydrogen | 4.49 | 9.43 |
| Clean ethane | 30.12 | -- |
| Benzene | 20.19 | 30.22 |
| Toluene | 16.36 | 14.36 |
| C8 aromatic hydrocarbons | 3.84 | 2.46 |
| C9+ aromatic hydrocarbons | 8.29 | 15.33 |
| Total aromatic hydrocarbons | 48.69 | 62.37 |
| Total aromatic hydrocarbons+clean ethane | 78.81 | 62.37 |
| Total normalization method wt% yield, the clean ethane that in the stage 2, transforms | ? | ? |
| Hydrogen | 7.33 | ? |
| Benzene | 29.29 | ? |
| Toluene | 20.68 | ? |
| C8 aromatic hydrocarbons | 4.58 | ? |
| C9+ aromatic hydrocarbons | 12.91 | ? |
| Total aromatic hydrocarbons | 67.46 | ? |
Can find out from table 2, can can change to the 67.46wt% at 48.69wt% from the normalization method total arenes yield (based on the wt% of charging) that dual stage process of the present invention obtains, depending on has what to be passed to subordinate phase from the clean ethane of fs.Similarly, can be for from 20.19wt% to 29.29wt% from the total benzene yield of the normalization method that this method obtains (based on the wt% of charging), depending on has what to be passed to subordinate phase from the clean ethane of fs.If the ethene of making is favourable economically more than aromatic hydrocarbons, the operator can select and will be sent to steam cracker to produce ethene from a part or all clean ethane of fs of lower paraffin hydrocarbons aromatization method so.If benzene or other aromatic hydrocarbons made are favourable economically more than ethene, the operator can select to be sent to from the most of clean ethane of fs the subordinate phase of lower paraffin hydrocarbons aromatization method so.Therefore, two stage lower paraffin hydrocarbons aromatization methods of the present invention can provide refining with suitable flexibility of operation/petrochemical industry machinery, according to demand or the variation of economic environment and change its product composition.
Embodiment 3
In this embodiment, show the scope of the product composition that can obtain from flexibly two stage aromatization methods of the present invention with the result of laboratory test.The lower paraffin hydrocarbons raw material of the present embodiment is comprised of 19.9wt% ethane and 80.1wt% propane.The operating temperature in the first and second stages is respectively 600 and 621 ℃.
To make a service test 4 according to the fresh 15-cc catalyst A charging of preparation described in the top embodiment 1, performance test 4 according to top embodiment 1 in the same mode of the performance test 1 described carry out, except the outlet temperature that reaches during the air calcination pre-treatment step be 600 ℃, nitrogen purging and hydrogen reduction step 600 ℃ carry out and the reactor wall temperature of ethane/propane feed at 600 ℃ under introduce.
Table 3 has been listed from performance test 4 with as describing the online gas chromatographic analysis result of the gross output logistics of the performance test 2 of carrying out among the top embodiment 1.Performance test 4 is carried out under the condition of the fs of the two stage aromatization methods that can be used for use mixing ethane/propane feed of the present invention.Described in top embodiment 1, performance test 2 is carried out under the condition of the subordinate phase that can be used for two stage aromatization methods of the present invention.
According to the composition data that obtain from gas chromatographic analysis, calculate initial ethane and conversion of propane according to the top formula that in embodiment 1, provides.The normalization method wt% yield of reactor outlet stream component is according to the formula calculating that provides for calculating this tittle in the top performance test 1 in the performance test 4.Reactor outlet from performance test 2 flows the normalization method wt% yield of component according to the description calculating of top embodiment 1.
Table 3
| Performance test | 4 | 2 |
| The reactor wall temperature, ℃ | 600 | 621 |
| Pressure, MPa | 0.1 | 0.1 |
| Feed composition | ? | ? |
| Ethane, wt% | 19.9 | 100 |
| Propane, wt% | 80.1 | 0 |
| Total feed rate, GHSV | 1000 | 1000 |
| Total feed rate, WHSV | 2.13 | 1.61 |
| ? | ? | ? |
| Ethane conversion, % | -99.81 | 48.34 |
| Conversion of propane, % | 99.25 | -- |
| ? | ? | ? |
| Reactor outlet forms, wt% | ? | ? |
| Hydrogen | 3.79 | 4.56 |
| Methane | 12.64 | 7.94 |
| Ethene | 2.27 | 4.37 |
| Ethane | 39.71 | 51.66 |
| Propylene | 0.37 | 0.57 |
| Propane | 0.60 | 0.63 |
| C4 | 0.06 | 0.11 |
| C5 | 0 | 0 |
| Benzene | 18.68 | 14.61 |
| Toluene | 12.47 | 6.94 |
| C8 aromatic hydrocarbons | 2.55 | 1.19 |
| C9+ aromatic hydrocarbons | 6.85 | 7.41 |
| Total aromatic hydrocarbons | 40.55 | 30.15 |
| Based on the normalization method wt% yield that is converted charging | ? | ? |
| Hydrogen | 4.77 | 9.43 |
| Clean ethane | 24.92 | -- |
| Benzene | 23.5 | 30.22 |
| Toluene | 15.69 | 14.36 |
| C8 aromatic hydrocarbons | 3.21 | 2.46 |
| C9+ aromatic hydrocarbons | 8.62 | 15.33 |
| Total aromatic hydrocarbons | 51.01 | 62.37 |
| Total aromatic hydrocarbons+clean ethane | 75.93 | 62.37 |
| Total normalization method wt% yield, the clean ethane that in the stage 2, transforms | ? | ? |
| Hydrogen | 7.12 | ? |
| Benzene | 31.03 | ? |
| Toluene | 19.27 | ? |
| C8 aromatic hydrocarbons | 3.82 | ? |
| C9+ aromatic hydrocarbons | 12.44 | ? |
| Total aromatic hydrocarbons | 66.56 | ? |
Can find out from table 3, can can change to the 66.56wt% at 51.01wt% from the normalization method total arenes yield (based on the wt% of charging) that dual stage process of the present invention obtains, depending on has what to be passed to subordinate phase from the clean ethane of fs.Similarly, can be for from 23.50wt% to 31.03wt% from the total benzene yield of the normalization method that the method obtains (based on the wt% of charging), depending on has what to be passed to subordinate phase from the clean ethane of fs.If the ethene of making is favourable economically more than aromatic hydrocarbons, the operator can select and will be sent to steam cracker to produce ethene from a part or all clean ethane of fs of lower paraffin hydrocarbons aromatization method so.If benzene or other aromatic hydrocarbons made are favourable economically more than ethene, the operator can select to be sent to from the most of clean ethane of fs the subordinate phase of lower paraffin hydrocarbons aromatization method so.Therefore, two stage lower paraffin hydrocarbons aromatization methods of the present invention can provide refining with suitable flexibility of operation/petrochemical industry machinery, according to demand or the variation of economic environment and change its product composition.
Embodiment 4
In this embodiment, show the scope of the product composition that can obtain from flexibly two stage aromatization methods of the present invention with the result of laboratory test.The lower paraffin hydrocarbons raw material of the present embodiment is comprised of 33.2wt% ethane, 46.8wt% propane and 20.0wt% normal butane.The operating temperature in the first and second stages is respectively 600 and 621 ℃.
To make a service test 5 according to the fresh 15-cc catalyst A charging of preparation described in the top embodiment 1, performance test 5 according to top embodiment 1 in the same mode of the performance test 1 described carry out, carry out and added by 33.2wt% ethane introducing under the reactor wall temperature of lower paraffin hydrocarbons charging at 600 ℃ that 46.8wt% propane adds that the 20.0wt% normal butane forms at 600 ℃ except the outlet temperature that reaches during the air calcination pre-treatment step is 600 ℃, nitrogen purging and hydrogen reduction step.
Table 4 listed from performance test 5 and as top embodiment 1 in the result of online gas chromatographic analysis of the gross output logistics of the performance test 2 carry out is described.Carry out under the condition of performance test 5 fs in can be used for two stage aromatization process of use mixing ethane/propane feed of the present invention.Described in top embodiment 1, performance test 2 is carried out under the condition of the subordinate phase that can be used for two stage aromatization methods of the present invention.
According to the composition data that obtain from gas chromatographic analysis, calculate initial ethane and conversion of propane according to the top formula that in embodiment 1, provides.Initial n-butane conversion is calculated according to following formula
Butanes conversion, %=100x (butane wt% during butane wt%-outlet is flowed in the charging)/(butane wt% in the charging)
The normalization method wt% yield of reactor outlet stream component is according to the formula calculating that provides for calculating this tittle in the top performance test 1 in the performance test 5.Reactor outlet from performance test 2 flows the normalization method wt% yield of component according to the description calculating of top embodiment 1.
Table 4
| Performance test | 5 | 2 |
| The reactor wall temperature, ℃ | 600 | 621 |
| Pressure, MPa | 0.1 | 0.1 |
| Feed composition | ? | ? |
| Ethane, wt% | 33.2 | 100 |
| Propane, wt% | 46.8 | 0 |
| Normal butane, wt% | 20.0 | ? |
| Total feed rate, GHSV | 1000 | 1000 |
| Total feed rate, WHSV | 2.13 | 1.61 |
| Ethane conversion, % | -27.64 | 48.34 |
| Conversion of propane, % | 98.57 | -- |
| N-butane conversion, % | 99.62 | -- |
| Reactor outlet forms, wt% | ? | ? |
| Hydrogen | 3.59 | 4.56 |
| Methane | 11.96 | 7.94 |
| Ethene | 2.47 | 4.37 |
| Ethane | 42.38 | 51.66 |
| Propylene | 0.43 | 0.57 |
| Propane | 0.67 | 0.63 |
| C4 | 0.08 | 0.11 |
| C5 | 0 | 0 |
| Benzene | 17.29 | 14.61 |
| Toluene | 11.59 | 6.94 |
| C8 aromatic hydrocarbons | 2.49 | 1.19 |
| C9+ aromatic hydrocarbons | 7.05 | 7.41 |
| Total aromatic hydrocarbons | 38.42 | 30.15 |
| Based on the normalization method wt% yield that is converted charging | ? | ? |
| Hydrogen | 5.43 | 9.43 |
| Clean ethane | 13.90 | -- |
| Benzene | 26.18 | 30.22 |
| Toluene | 17.55 | 14.36 |
| C8 aromatic hydrocarbons | 3.77 | 2.46 |
| C9+ aromatic hydrocarbons | 10.67 | 15.33 |
| Total aromatic hydrocarbons | 58.16 | 62.37 |
| Total aromatic hydrocarbons+clean ethane | 72.06 | 62.37 |
| Total normalization method wt% yield, the clean ethane that in the stage 2, transforms | ? | ? |
| Hydrogen | 6.74 | ? |
| Benzene | 30.38 | ? |
| Toluene | 19.55 | ? |
| C8 aromatic hydrocarbons | 4.11 | ? |
| C9+ aromatic hydrocarbons | 12.80 | ? |
| Total aromatic hydrocarbons | 66.84 | ? |
Can find out from table 4, can can change to the 66.84wt% at 58.16wt% from the normalization method total arenes yield (based on the wt% of charging) that dual stage process of the present invention obtains, depending on has what to be passed to subordinate phase from the clean ethane of fs.Similarly, can be for from 26.18wt% to 30.38wt% from the total benzene yield of the normalization method that this method obtains (based on the wt% of charging), depending on has what to be passed to subordinate phase from the clean ethane of fs.If the ethene of making is favourable economically more than aromatic hydrocarbons, the operator can select and will be sent to steam cracker to produce ethene from a part or all clean ethane of fs of lower paraffin hydrocarbons aromatization method so.If benzene or other aromatic hydrocarbons made are favourable economically more than ethene, the operator can select to be sent to from the most of clean ethane of fs the subordinate phase of lower paraffin hydrocarbons aromatization method so.Therefore, two stage lower paraffin hydrocarbons aromatization methods of the present invention can provide refining with suitable flexibility of operation/petrochemical industry machinery, according to demand or the variation of economic environment and change its product composition.
Claims (12)
1. method, described method comprises:
A. in the fs, the lower paraffin hydrocarbons charging is contacted under the fs reaction conditions with aromatized catalyst, produce the fs product stream that comprises ethane and aromatic hydrocarbons;
B. from described fs product stream aromatics separation, form aromatic product stream and non-aromatics product stream;
C. first part's non-aromatics product stream is introduced the alkane cracker; With
D. second section non-aromatics product stream is contacted under the subordinate phase reaction conditions in subordinate phase with aromatized catalyst, produce the subordinate phase product stream that comprises aromatic hydrocarbons.
2. method claimed in claim 1, wherein said alkane cracker is thermally splitting device or cat cracker.
3. each described method of claim 1-2, the major part of wherein said lower paraffin hydrocarbons charging comprises ethane and propane.
4. each described method of claim 1-3, wherein said fs reaction conditions comprises that temperature is from 400 to 700 ℃.
5. each described method of claim 1-4, wherein said fs reaction conditions comprises that temperature is from 480 to 600 ℃.
6. each described method of claim 1-5, wherein said subordinate phase reaction conditions comprises that temperature is from 400 to 700 ℃.
7. each described method of claim 1-6, wherein said subordinate phase reaction conditions comprises that temperature is from 575 to 675 ℃.
8. each described method of claim 1-7, wherein said fs product stream produces at least two reactors that are arranged in parallel.
9. each described method of claim 1-8, wherein said subordinate phase product stream produces at least two reactors that are arranged in parallel.
10. each described method of claim 1-9, wherein the non-aromatics except ethane and propane produced in the fs.
11. each described method of claim 1-10, wherein said first part non-aromatics product stream comprises the ethane of 10-90% in the described non-aromatics product stream.
12. each described method of claim 1-11, wherein said first part non-aromatics product stream comprises the ethane of 20-70% in the described non-aromatics product stream.
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| US42010410P | 2010-12-06 | 2010-12-06 | |
| US61/420,104 | 2010-12-06 | ||
| PCT/US2011/063279 WO2012078506A2 (en) | 2010-12-06 | 2011-12-05 | Process for the conversion of lower alkanes to aromatic hydrocarbons and ethylene |
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| CN (1) | CN103328417A (en) |
| BR (1) | BR112013013575A2 (en) |
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| CN102851063B (en) * | 2012-09-19 | 2014-10-22 | 北京惠尔三吉绿色化学科技有限公司 | Method for producing high-octane rating clean gasoline by dry gas and liquefied gas aromatization |
| US20170057888A1 (en) * | 2015-08-27 | 2017-03-02 | Shell Oil Company | Separation of catalyst and hydrogen acceptor after aromatization of a methane containing gas stream |
| US9988325B2 (en) | 2015-09-25 | 2018-06-05 | Exxonmobil Chemical Patents Inc. | Hydrocarbon conversion |
| EP3689843A1 (en) | 2019-02-01 | 2020-08-05 | Basf Se | A method for producing an aromatic hydrocarbon or a mixture of aromatic hydrocarbons from a low molecular hydrocarbon or a mixture of low molecular hydrocarbons |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267275A (en) * | 1997-07-23 | 2000-09-20 | 菲利浦石油公司 | Hydrocarbon conversion process |
| US20090156870A1 (en) * | 2007-12-12 | 2009-06-18 | Ann Marie Lauritzen | Process for the conversion of ethane to mixed lower alkanes to aromatic hydrocarbons |
| US20100048968A1 (en) * | 2008-08-19 | 2010-02-25 | Ann Marie Lauritzen | Process for the conversion of lower alkanes to aromatic hydrocarbons and ethylene |
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| US5030782A (en) * | 1989-05-04 | 1991-07-09 | Mobil Oil Corporation | Light alkane conversion |
| EA022457B1 (en) * | 2009-11-02 | 2016-01-29 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Process for the conversion of mixed lower alkanes to aromatic hydrocarbons |
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- 2011-12-05 CN CN2011800652974A patent/CN103328417A/en active Pending
- 2011-12-05 WO PCT/US2011/063279 patent/WO2012078506A2/en active Application Filing
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1267275A (en) * | 1997-07-23 | 2000-09-20 | 菲利浦石油公司 | Hydrocarbon conversion process |
| US20090156870A1 (en) * | 2007-12-12 | 2009-06-18 | Ann Marie Lauritzen | Process for the conversion of ethane to mixed lower alkanes to aromatic hydrocarbons |
| US20100048968A1 (en) * | 2008-08-19 | 2010-02-25 | Ann Marie Lauritzen | Process for the conversion of lower alkanes to aromatic hydrocarbons and ethylene |
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| BR112013013575A2 (en) | 2016-10-11 |
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