CN111954652A - 混合二甲苯和高辛烷值c9+芳族化合物的共同制备方法 - Google Patents
混合二甲苯和高辛烷值c9+芳族化合物的共同制备方法 Download PDFInfo
- Publication number
- CN111954652A CN111954652A CN201980023435.9A CN201980023435A CN111954652A CN 111954652 A CN111954652 A CN 111954652A CN 201980023435 A CN201980023435 A CN 201980023435A CN 111954652 A CN111954652 A CN 111954652A
- Authority
- CN
- China
- Prior art keywords
- stream
- aromatic hydrocarbon
- mixture
- aromatic
- zsm
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000008096 xylene Substances 0.000 title claims abstract description 39
- 150000003738 xylenes Chemical class 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 title description 17
- 150000001491 aromatic compounds Chemical class 0.000 title description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 129
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 121
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 72
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 72
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000002808 molecular sieve Substances 0.000 claims abstract description 46
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 125000003118 aryl group Chemical group 0.000 claims abstract description 43
- 230000029936 alkylation Effects 0.000 claims abstract description 41
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 38
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 28
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000000446 fuel Substances 0.000 claims abstract description 20
- 239000002168 alkylating agent Substances 0.000 claims abstract description 19
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 19
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims description 57
- 239000010457 zeolite Substances 0.000 claims description 28
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 27
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 24
- 229910021536 Zeolite Inorganic materials 0.000 claims description 24
- 239000004215 Carbon black (E152) Substances 0.000 claims description 19
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical class CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 claims description 17
- 150000005199 trimethylbenzenes Chemical class 0.000 claims description 15
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 14
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 12
- -1 1-ethyl Chemical group 0.000 claims description 12
- 229910052680 mordenite Inorganic materials 0.000 claims description 11
- ZLCSFXXPPANWQY-UHFFFAOYSA-N meta-methylethylbenzene Natural products CCC1=CC=CC(C)=C1 ZLCSFXXPPANWQY-UHFFFAOYSA-N 0.000 claims description 7
- 238000006317 isomerization reaction Methods 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 2
- 230000003075 superhydrophobic effect Effects 0.000 claims description 2
- 239000012013 faujasite Substances 0.000 claims 1
- 238000011084 recovery Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000001179 sorption measurement Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000002156 adsorbate Substances 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 239000003502 gasoline Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- ODLMAHJVESYWTB-UHFFFAOYSA-N ethylmethylbenzene Natural products CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QUGUFLJIAFISSW-UHFFFAOYSA-N 1,4-difluorobenzene Chemical compound FC1=CC=C(F)C=C1 QUGUFLJIAFISSW-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 241001455273 Tetrapoda Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229940065278 sulfur compound Drugs 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C07C2/865—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 ether
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- 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
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7011—MAZ-type, e.g. Mazzite, Omega, ZSM-4 or LZ-202
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7019—EMT-type, e.g. EMC-2, ECR-30, CSZ-1, ZSM-3 or ZSM-20
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7034—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
-
- 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
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/08—Xylenes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
- C07C5/2729—Changing the branching point of an open chain or the point of substitution on a ring
- C07C5/2732—Catalytic processes
- C07C5/2737—Catalytic processes with crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
-
- 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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/22—Organic compounds not containing metal atoms containing oxygen as the only hetero atom
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
- C10G69/123—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step alkylation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
- C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/10—Use of additives to fuels or fires for particular purposes for improving the octane number
-
- 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
- B01J2029/062—Mixtures of different 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- 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
- C07C2529/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
-
- 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
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/24—Mixing, stirring of fuel components
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
公开了混合二甲苯和C9+烃的制备方法,其中使包含苯和/或甲苯的芳族烃进料与包含甲醇和/或二甲基醚的烷基化剂在烷基化条件下在烷基化催化剂存在下接触以制备包含所述混合二甲苯和C9+烃的烷基化芳族产物料流。随后将所述混合二甲苯转化成对二甲苯,并可以将所述C9+烃和其组分作为车用燃料共混组分供应。所述烷基化催化剂包含具有大于零至大约3的约束指数的分子筛。芳族烃与烷基化剂的摩尔比在大于1:1至小于4:1的范围内。
Description
相关申请的交叉引用
本申请要求于2018年3月30日提交的临时申请号62/650,673和于2018年4月27日提交的欧洲申请号18169815.0的利益,这些文献的公开内容通过参考引入本文。
技术领域
本公开内容涉及如下制备混合二甲苯和C9+烃的方法:用包含甲醇和/或二甲基醚的料流在具有大于零至大约3的约束指数(a Constraint Index)的分子筛,最优选ZSM-12存在下将包含苯和/或甲苯的芳族烃料流烷基化。
背景技术
页岩气的最新发现和增加的生产代表天然气(主要是甲烷)的有意义的新来源。结果,天然气供应已经变得不太昂贵和更加充裕,使得它变成用于升级的有利原料。这已经导致开发将天然气转化成甲醇的方法,甲醇为制备富芳族化合物进料的中间体。
精炼工业当前通过将包括单环芳族化合物和C4-C10饱和支化无环烷烃和烯烃的宽范围烃料流共混来配制车用汽油调合组分总和(gasoline pool)。不管如何获得,这些烃料流含有宽范围的组分并通常已经以单元操作(例如,通过烃转化、蒸馏或溶剂萃取)加工,以获得特定所需组分或组分的组合。这些操作的一个目的是获得高辛烷值汽油组分例如C9和C10+芳族烃。这些操作的另一个目的是从混合二甲苯获得高纯度(通常大于99%)化学原料例如对二甲苯,所述化学原料已经以极大量用于制造苯乙烯、苯酚、聚酰胺单体、对苯二甲酸及其它化学产品。
因此仍需要制备高辛烷值车用汽油共混组分和混合二甲苯的改进方法,例如通过用甲醇和/或二甲基醚将苯和/或甲苯烷基化。本公开内容满足这种及其它需求。
发明内容
在本公开内容的一个方面中,可以经由与烷基化剂料流在烷基化条件下在烷基化催化剂存在下的烷基化反应形成烷基化芳族产物料流而将芳族烃进料转化成烷基化芳族产物料流。通过所述烷基化反应形成的烷基化芳族产物料流包含混合二甲苯和C9+烃。所述芳族烃进料可以包含甲苯和/或苯,并且所述烷基化剂包含甲醇和/或二甲基醚。
在本公开内容中,烷基化催化剂包含分子筛,优选较大孔分子筛,更优选具有大于零至大约3,大于零至大约2的约束指数,最优选,大约2的约束指数的分子筛。在烷基化反应中,芳族烃与烷基化剂的摩尔比选自大约1:1至大约4:1;优选大约2:1至小于大约4:1的范围;更优选,芳族烃与烷基化剂的摩尔比是大约3:1。
烷基化芳族产物料流可以包含至少60wt%,优选至少70wt%的混合二甲苯,并且包含至少17wt%,优选至少21wt%的C9+芳族烃,基于所述烷基化芳族产物料流的重量。
混合二甲苯和C9+烃可以从所述烷基化芳族产物回收。可以将混合二甲苯供给二甲苯异构化单元以制备对二甲苯。可以将C9+烃供给分离单元以至少回收C9芳族烃料流,所述C9芳族烃料流至少包含三甲基苯的混合物和乙基甲基苯的混合物。可以在分离单元中将C9芳族烃料流分离以回收至少包含三甲基苯的混合物的料流和至少包含乙基甲基苯的混合物的料流。可以将这些三甲基苯和乙基甲基苯料流作为车用燃料共混组分(一种或多种)一起或分开地供应,优选具有高的MONC和RONC值。
有利地,烷基化催化剂包含具有MTW、BEA*、FAU骨架结构的分子筛。分子筛可以是沸石和/或这些骨架结构的混合物。优选地,MTW骨架结构的分子筛是ZSM-12。BEA*骨架结构的分子筛优选是沸石β。FAU骨架结构的分子筛优选是沸石Y或超稳Y(USY)。优选地,MOR骨架结构的分子筛是天然丝光沸石或TEA-丝光沸石。在一些方面中,分子筛选自ZSM-3、ZSM-4、ZSM-14、ZSM-18、ZSM-20、ZSM-38和它们的混合物。
适宜地,烷基化条件是较温和的,优选地,反应在小于500℃,优选300℃-450℃的温度的烷基化条件下进行。压力在700kPa-a至7000kPa-a的范围内。基于所述芳族烃进料的重时空速在50hr-1-0.5hr-1的范围内。
在本公开内容的另一个方面中,可以经由与烷基化剂料流在烷基化条件下在烷基化催化剂,优选ZSM-12存在下进行烷基化反应形成烷基化芳族产物料流而将芳族烃进料转化成包含C9芳族烃和C10芳族烃的烷基化芳族产物料流。将所形成的烷基化芳族产物料流分离成C9芳族烃料流和,非必要地,C10芳族烃料流,它们中的每一个可以作为车用燃料共混组分供应。
C9芳族烃料流包含三甲基苯的混合物和/或乙基甲基苯的混合物,它们可以被分离并作为车用燃料共混组分供应。所述三甲基苯是包含并包括1,2,4-三甲基苯、1,3,5-三甲基苯和1,2,3-三甲基苯的异构体。所述乙基甲基苯包含并包括1-乙基,2-甲基苯和1-乙基,3-甲基苯。任何三甲基苯异构体或任何乙基甲基苯也可以被分离并作为具有高辛烷值的车用燃料共混组分供应。
附图说明
图1是在实施例2中描述的用甲醇烷基化甲苯的方法中在ZSM-12上甲苯和甲醇的转化率对运转时间(time on stream)的图解。
图2是在实施例2中描述的用甲醇烷基化甲苯的方法中在ZSM-12上甲苯和甲醇的选择性对运转时间的图解。
发明详述
这里所公开的烷基化方法提供在烷基化催化剂存在下制备混合二甲苯和C9+芳族烃,所述烷基化催化剂包含较大孔分子筛,例如,具有大于零至大约3的约束指数的分子筛。此类分子筛包括,但不限于,具有MTW、BEA*、FAU或MOR骨架结构的分子筛,并在下面进一步进行描述。
定义
这里所使用的术语“α值”是催化剂的裂化活性的量度并且在美国专利号3,354,078和Journal of Catalysis,第4卷,第527页(1965);第6卷,第278页(1966)和第61卷,第395页(1980)中进行了描述,它们中的每一篇通过参考引入本文。
这里所使用的术语“芳族化合物”和“芳族烃”是指含至少一个芳族核的一类烃化合物。
这里所使用的术语“烃”或“烃类”是指含与碳键接的氢的一类化合物,并涵盖(i)饱和烃化合物,(ii)不饱和烃化合物和(iii)烃化合物(饱和和/或不饱和)的混合物,包括具有不同的n值的烃化合物的混合物。
本文所使用的术语“Cn”烃(其中n是正整数,例如1、2、3、4、5等)是指每分子具有n数量碳原子(一个或多个)的烃。
这里所使用的术语“Cn+”烃(其中n是正整数,例如1、2、3、4、5等)是指每分子具有至少n数量碳原子(一个或多个)的烃。因此,术语“C9+烃”是指含9个或更多个碳原子的烃,并包括“C10+烃”。
这里所使用的术语“Cn-”烃(其中n是正整数,例如1、2、3、4、5等)是指每分子具有至多n数量碳原子(一个或多个)的烃。
这里所使用的术语“约束指数”是硅铝酸盐或分子筛提供受控进入各种尺寸的分子到其内部结构中的程度的适宜量度。例如,提供高度受限的进入和从其内部结构外出的硅铝酸盐具有高的约束指数值,并且此类硅铝酸盐通常具有小尺寸,例如小于5埃的孔隙。另一方面,提供较自由进入内部硅铝酸盐结构的硅铝酸盐具有低的约束指数值,并且通常具有大尺寸的孔隙。可以测定约束指数的方法在美国专利号4,016,218中进行了完全描述。
这里所使用的术语“混合二甲苯”是指邻二甲苯、间二甲苯和对二甲苯的平衡混合物。
这里所使用的术语“分子筛”和“沸石”可互换地使用。
这里所使用的术语“MON”是指马达法辛烷值(Motor Octane Number)。
这里所使用的术语“MONC”是指不含铅的马达法辛烷值。
这里所使用的术语“RON”是指研究法辛烷值(Research Octane Number)。
这里所使用的术语“RONC”是指不含铅的研究法辛烷值。
这里所使用的术语“车用燃料共混组分”是指用于共混到成品车用燃料或汽油调合组分总和中的具有108-119的RONC值和/或98-111的MONC值的烃。
方法
本公开内容的一个方面是一种方法,其中可以经由在烷基化条件下在下面论述的烷基化催化剂存在下与烷基化剂发生烷基化反应而将芳族烃进料转化成烷基化芳族产物料流,所述烷基化催化剂布置在至少一个烷基化反应区(一个或多个)中。所述烷基化芳族产物料流被回收并可以分离为C8烃料流和C9+芳族烃料流。所述C8烃料流包括,例如,混合二甲苯。所述C9+烃料流包括,例如,C9芳族烃,例如三-甲基苯,和C10芳族烃。可以将所回收的混合二甲苯料流异构化成对二甲苯。可以将C9+芳族烃料流供给分离单元以至少回收C9芳族烃料流和C10烃料流。下面论述的C9芳族烃料流,和,非必要地,C10烃料流可以作为车用燃料共混组分供应。
芳族烃进料优选包含甲苯,或在其它方面中,至少90wt%甲苯,基于所述芳族烃进料的重量,或仅仅是甲苯。非必要地,此种甲苯进料可以与苯共进料。或者,进料可以仅仅是苯。烷基化剂优选包含甲醇或作为甲醇和甲苯和/或苯的混合物。非必要地,烷基化剂包含甲醇和/或二甲基醚或作为甲醇和/或二甲基醚和甲苯和/或苯的混合物。
所述方法有效地将苯和/或甲苯以基本上100%甲醇转化率和实质上无轻质气体产出的情况下转化成混合二甲苯和C9+芳族烃。这种高甲醇利用率鉴于现有技术甲苯和/或苯甲基化方法中的甲醇利用率是令人意外的,并实现了更少焦炭形成的显著优点,这增加了催化剂寿命。另外,在现有技术方法中,优选将蒸汽与甲醇一起共进料到反应器中以使甲醇副反应最小化,并且蒸汽负面地影响催化剂寿命。由于在本发明方法中几乎100%的甲醇与芳族环反应以产生芳族化合物,所以无需共进料蒸汽,从而降低所述方法的能量需要并提高催化剂寿命。
在这里所公开的方面中对混合二甲苯的选择性典型地约为混合二甲苯的至少60wt%,优选至少70wt%,最优选至少75wt%,基于烷基化芳族产物料流的重量。副产物是苯和C9+芳族烃,例如C9和C10芳族烃。C9+芳族烃占至少21wt%,或至少17wt%,或至少15wt%,基于烷基化芳族产物料流的重量。C9芳族烃占至少10wt%,或优选至少13wt%,或更优选至少15wt%,或最优选至少17wt%,基于烷基化芳族产物料流的重量。C10芳族烃占至少4wt%,或至少3wt%,或至少1wt%,基于烷基化芳族产物料流的重量。
将所制备的烷基化芳族产物料流至少回收为包含混合二甲苯的料流,和至少回收为包含C9+芳族烃的料流。此种烷基化芳族产物料流还包含苯和/或甲苯(既有残留的又有方法中共产生的)连同共同产生的水、含氧化合物(oxygenate)副产物和在一些情形下,未反应的甲醇。然而,通常优选操作所述方法以致所有甲醇与芳族烃进料反应并且烷基化芳族产物料流一般不含残留甲醇。烷基化芳族产物料流也通常不含由甲醇分解成乙烯及其它烯烃而产生的轻质气体。在一些实施方案中,烷基化芳族产物料流可以含有高达至少75wt%混合二甲苯,基于所述烷基化芳族产物料流的重量,并且对二甲苯可以占至少35wt%,基于所述混合二甲苯级分的重量。
在分离水后,可以将烷基化芳族产物料流供给分离单元或部分,例如一个或多个蒸馏柱,以通过常规蒸馏技术回收混合二甲苯并将苯和甲苯与C9+芳族烃副产物分离。将混合二甲苯料流供给二甲苯异构化单元以制备对二甲苯。
C9+芳族烃可以分离为共混到车用燃料中的组分;优选,此种C9+芳族化合物具有高辛烷值,例如超过108的RONC值和超过98的MONC值。或者,可以用附加的苯和/或甲苯使C9+芳族烃发生烷基转移以制备附加的混合二甲苯。可以使苯从烷基化芳族产物料流中分离并循环回到烷基化反应区(一个或多个)。
与现有的方法相比较,烷基化催化剂的寿命得到提高,因为在更低反应温度下甲醇分解少得多。此外,使用更大孔隙分子筛使扩散限制最小化并允许烷基化在商业上可行的WHSV下进行。此外,当使用甲苯进料(含至少90wt%甲苯的进料,基于所述芳族烃进料的重量)时,与现有的方法相比,相对于其它分子例如烷基化剂或反应的副产物,更多烷基化剂与甲苯反应,而产生混合二甲苯。
含氧化合物副产物可以通过本领域中已知的任何手段从烷基化芳族产物料流中除去,例如美国专利号9,012,711、9,434,661和9,205,401中所述的吸附;美国专利号9,294,962中所述的苛性碱洗涤;8,252,967、8,507,744和8,981,171中所公开的结晶;和美国专利公开号2016/0115094和2016/0115103中所述的向酮转化。
可以将从烷基化芳族产物料流和任何下游的C9+烷基转移方法回收的混合二甲苯送到对二甲苯生产回路。后者包括对二甲苯分离区,其中常规上通过吸附或结晶或这两种的组合分离对二甲苯并回收。当通过吸附分离对二甲苯时,所使用的吸附剂优选含有沸石。所使用的典型吸附剂包括天然或合成的结晶硅铝酸盐沸石,例如沸石X,或Y,或它们的混合物。这些沸石优选通过阳离子例如碱或碱土金属或稀土阳离子进行交换。吸附柱优选是模拟移动床柱(SMB)并且使用解吸剂,例如对二乙基苯、对二氟代苯、二乙基苯或甲苯或它们的混合物回收选择性吸附的对二甲苯。适合用于本发明方法的商业SMB单元是PAREXTM或ELUXYLTM。
在本公开内容的一个或多个方面中,下面论述的烷基化催化剂包含分子筛,优选较大孔分子筛,更优选具有大于零至大约3的约束指数的分子筛。
本公开内容的另一个方面是C9芳族烃料流和C10芳族烃料流的制备方法,其包括许多步骤。使包含苯和/或甲苯的芳族烃进料与包含甲醇和/或二甲基醚的进料在包含ZSM-12的烷基化催化剂存在下在烷基化条件下接触或反应以制备烷基化芳族产物料流。或者,可以将包含苯和/或甲苯和/或二甲基醚的混合物的混合进料供给所述方法。
使芳族烃进料和甲醇进料反应而产生包含C9芳族烃和C10芳族烃连同未反应的苯及其它副产物一起的烷基化芳族产物料流。非必要地,可以将甲醇进料与二甲基醚共进料或二甲基醚可以是仅有的进料。在反应中,芳族烃与甲醇进料的摩尔比在大于大约1:1至小于大约4:1,优选大约2:1至大约4:1,更优选大约2.5:1至大约3.5:1,最优选大约3:1的范围内。
所述烷基化条件包括大约500℃或更低,或大约300℃-大约450℃的温度、700kPa-a至7000kPa-a的压力和50hr-1-0.5hr-1的基于所述芳族烃进料的重时空速。在方法的第二步骤中,使包含C9芳族烃和C10芳族烃的料流从所述烷基化芳族产物料流中分离。然后可以将这些料流作为车用燃料共混组分供应。优选地,此种C9芳族烃和/或C10芳族烃共混组分具有高辛烷值,例如108-111的RONC值,和98-111的MONC值。
C9芳族烃料流可以包含三甲基苯的混合物和乙基甲基苯的混合物。可以将这些混合物供给分离单元或部分,例如一个或多个蒸馏柱,以通过常规蒸馏技术回收包含三甲基苯的所述混合物的料流和/或包含乙基甲基苯的混合物的料流。可以将这些料流作为具有在如上文所述范围中的高辛烷值的车用燃料共混组分供应。
三甲基苯的混合物可以包含三甲基苯异构体的混合物。此类异构体包含1,2,4-三甲基苯、1,3,5-三甲基苯和1,2,3-三甲基苯。这种异构体混合物可以作为车用燃料共混组分供应。或者,可以将此种混合物供给分离单元或部分,例如一个或多个蒸馏柱,以通过常规蒸馏技术回收包含1,2,4-三甲基苯、1,3,5-三甲基苯和1,2,3-三甲基苯的一个或多个独立料流。也可以将这些料流作为具有在如上文所述范围中的高辛烷值的车用燃料共混组分供应。
乙基甲基苯的混合物可以包含1-乙基,2-甲基苯和1-乙基,3-甲基苯。这种混合物可以作为车用燃料共混组分供应。或者,可以将此种混合物供给分离单元或部分,例如一个或多个蒸馏柱,以通过常规蒸馏技术回收包含1-乙基,2-甲基苯和1-乙基,3-甲基苯的一个或多个独立料流。也可以将这些料流作为具有在如上文所述范围中的高辛烷值的车用燃料共混组分供应。
烷基化催化剂
烷基化催化剂包含具有大于零至大约3,优选大于零至大约2的约束指数,最优选大约2的约束指数的分子筛。
用于本发明方法的具有大于零至大约3的约束指数的适合的分子筛的实例包括沸石β、沸石Y、超稳Y(USY)、超疏水性Y(UHP-Y)、脱铝Y(Deal Y)、丝光沸石、ZSM-3、ZSM-4、ZSM-12、ZSM-14、ZSM-18、ZSM-20、ZSM-38和它们的混合物。
沸石β描述在美国专利号3,308,069和Re.号28,341中。低钠超稳Y分子筛(USY)描述在美国专利号3,293,192和3,449,070中。超疏水Y(UHP-Y)描述在美国专利号4,401,556中。脱铝Y沸石(DealY)可以通过美国专利号3,442,795中提出的方法制备。沸石Y和丝光沸石为天然存在的材料但也可以合成形式获得,如TEA-丝光沸石(即,由包括四乙基铵导向剂的反应混合物制备的合成丝光沸石)。TEA-丝光沸石在美国专利号3,766,093和3,894,104中进行了公开。
沸石ZSM-3描述在美国专利号3,415,736中。沸石ZSM-4描述在美国专利号4,021,947中。沸石ZSM-12描述在美国专利号3,832,449中。沸石ZSM-14描述在美国专利号3,923,636中。沸石ZSM-18描述在美国专利号3,950,496中。沸石ZSM-20描述在美国专利号3,972,983中。ZSM-38描述在US 4,046,859中,并具有如US 3,960,705中所规定的为2的约束指数。
分子筛可以具有MTW、BEA*、FAU的骨架结构。分子筛可以是沸石和/或这些骨架结构的混合物。优选地,MTW骨架结构的分子筛是ZSM-12。BEA*骨架结构的分子筛是沸石β。FAU骨架结构的分子筛优选是沸石Y或超稳Y(USY)。MOR骨架结构的分子筛是天然丝光沸石或TEA-丝光沸石。
另外或备选地,这里有用的分子筛可以是由硅与铝的摩尔比表征的沸石。在本公开内容的特定方面中,这里适合的分子筛包括具有大约5-100,优选大约10-大约80摩尔比,最优选大约15-大约50摩尔比的Si/Al2摩尔比的那些。
烷基化催化剂具有100-800,优选150-600,最优选200-500的α值。
烷基化催化剂的分子筛晶体具有大于0.05微米至大约0.2微米或大于0.05微米至0.5微米的对于主晶体的晶体尺寸。
上述分子筛可以在没有任何粘结剂或基体的情况下用作这里采用的烷基化催化剂。或者,可以将分子筛与耐受烷基化反应中使用的温度及其它条件的其它材料复合。此类材料包括活性和非活性材料和合成或天然存在的沸石以及无机材料例如粘土和/或氧化物例如氧化铝、二氧化硅、二氧化硅-氧化铝、氧化锆、氧化钛、氧化镁或这些及其它氧化物的混合物。后者可以是天然存在的或呈包括二氧化硅和金属氧化物的混合物的凝胶状沉淀或凝胶形式。除了此类金属氧化物,烷基化催化剂不含有添加的金属,例如稀土金属或碱土金属。
还可以与氧化物类型粘结剂一起包括粘土以改进催化剂的机械性能或帮助其制造。材料连同本身是催化活性的分子筛(即,与其结合或在其合成期间存在)一起的使用可以改变催化剂的转化率和/或选择性。非活性材料合适地充当稀释剂来控制转化率的数量以致产物可以经济和顺序地获得,而无需采用控制反应速率的其它手段。可以将这些材料结合到天然存在的粘土,例如膨润土和高岭土中,以改进催化剂在商业操作条件下的抗压强度和充当催化剂的粘结剂或基体。分子筛和无机氧化物基体的相对比例可以广泛地改变,其中分子筛含量为复合材料的大约1-大约90wt%和更通常,尤其是当复合材料呈珠粒形式制备时,为复合材料的大约2-大约80wt%。
烷基化条件
本发明烷基化方法在较低温度,即小于500℃,例如小于475℃,或小于450℃,或小于425℃,或小于400℃下进行。为了提供商业上可行的反应速率,所述方法可以在至少250℃,例如至少275℃,例如至少300℃的温度下进行。在范围方面,所述方法可以在250至小于500℃,例如275-475℃,例如300-450℃的温度下进行。操作压力将随温度而变化,但是一般是至少700kPa-a,例如至少1000kPa-a,例如至少1500kPa-a,或至少2000kPa-a,最高大约7000kPa-a,例如最高大约6000kPa-a,最高大约5000kPa-a。在范围方面,操作压力可以为700kPa-a至7000kPa-a,例如1000kPa-a至6000kPa-a,例如2000kPa-a至5000kPa-a。基于总芳族化合物和烷基化剂进料的适合的WHSV值在50hr-1-0.5hr-1,例如10hr-1-1hr-1的范围内。在本公开内容的一些方面中,芳族化合物进料、甲醇烷基化剂和/或烷基化排出物的至少一部分可以在液相中存在于烷基化反应区(一个或多个)中。
反应器
烷基化反应可以在任何已知的反应器***中进行,包括但不限于固定床反应器、移动床反应器、流化床反应器和反应性蒸馏单元。另外,反应器可以包括单个反应区或位于相同或不同的反应容器中的多个反应区。另外,甲醇和/或二甲基醚烷基化剂的注射可以在反应器中的单个位置或沿着反应器间隔的多个位置进行。
进料
本发明方法的进料包含芳族烃进料(包含苯和/或甲苯)和包含甲醇,非必要地,和/或二甲基醚的烷基化剂。任何精炼厂芳族进料可以用作苯和/或甲苯的来源,但是在本公开内容的一些方面中,使用包含至少90wt%甲苯的芳族烃进料可能是合乎需要的,基于所述芳族烃进料的重量。另外,在一些方面中,预处理芳族烃进料以除去催化剂毒物,例如氮-和硫-化合物可能是合乎需要的。在其它方面中,进料可以还包括非芳族化合物,例如没有从其中提取非芳族化合物的精炼厂芳族进料。
现将参照以下非限制性实施例和附图更具体地描述本公开内容。
实施例
X射线衍射图案
用具有多路检测器的Bruker D4 Endeavor衍射***使用铜K-α-辐射收集X射线衍射数据(粉末XRD或XRD)。通过具有0.018度2θ的扫描模式并对于每一步骤使用大约30秒的有效计数时间记录衍射数据,其中θ是布拉格角。
通过BET测量总表面积和中孔(Mesoporous)表面积
在350℃下将锻烧沸石粉末脱气4小时后,用Micromeritics Tristar II 3020仪器通过氮吸附/解吸测量总BET和t-绘图微孔表面积。通过从总BET表面积扣除t-绘图微孔获得中孔表面积。中孔体积源自于相同数据组。关于所述方法的更多信息可以参见例如,“Characterization of Porous Solids and Powders:Surface Area,Pore Size andDensity“,S.Lowell等,Springer,2004。
α值
本文所使用的试验的实验条件包括538℃的恒温,和如Journal of Catalysis,第61卷,第395页(1980)中详细描述的可变流速。
吸附数据
正己烷吸附的吸附数据是如下测定的平衡吸附值:使用经锻烧吸附剂的称重样品,与所需纯的被吸附物蒸气在吸附室中接触,抽空至小于1mm Hg并与40托蒸气压(小于相应的被吸附物的气-液平衡压力)的正己烷在90℃接触。在吸附期通过添加由稳压器控制的被吸附物蒸气保持压力恒定(在大约±0.5mm Hg内),所述吸附期不超过大约8小时。随着被吸附物被结晶材料吸附,压力降低引起稳压器打开阀门,从而容许更多被吸附物蒸气到腔室以恢复上述控制压力。当压力变化不足以激活稳压器时,吸附完成。重量增加计算为样品的吸附容量,以g/100g经锻烧吸附剂为单位。
实施例1:ZSM-12催化剂的制备
根据美国专利8,202,506(通过参考引入本文)中的公开内容合成ZSM-12小晶体。按合成时原样的材料的X射线衍射(XRD)图案显示ZSM-12拓扑结构的典型的纯相。按合成时原样的材料的SEM显示所述材料由小晶体(具有<0.05微米的平均晶体尺寸)的附聚物构成。所得的ZSM-12晶体具有大约43的SiO2/Al2O3摩尔比。如下形成氧化铝粘结的催化剂:使用大约80wt%ZSM-12按合成时原样的晶体和大约20wt%氧化铝(VersalTM300,可从HoneywellUOP获得)挤出而制备1/20”四叶体挤出物。将所得的干燥挤出物在氮气中锻烧(在大约538℃(1000°F)下大约3小时),与大约1N硝酸铵溶液铵交换,并在空气中锻烧(在538℃(1000°F)下大约6小时)以形成酸性成品,命名为H-ZSM-12,为呈四叶体形状并具有540的α值、44.5mg/g的己烷吸附和334m2/g的通过BET测量的表面积的挤出物。
实施例2:性能评价
进行实验研究通过用甲醇在350℃的温度、600psig(4238kPa-a)的压力和3.5hr-1的基于总进料的WHSV下烷基化甲苯以制备混合二甲苯和C9+芳族化合物。所使用的进料由甲醇和甲苯按3:1摩尔比的混合物组成。所使用的催化剂是H-ZSM-12(80%沸石/20%氧化铝粘结剂),如上所述,其具有大约1-大约3的约束指数。反应在下降流固定床反应器中进行。收集液体产物并通过6890Agilent GC分析。通过差值计算气体产率。将结果归纳在图1和图2中。
甲醇和甲苯转化率
图1示出了在十五(15)天试验中在H-ZSM-12催化剂上的甲苯和甲醇转化率。如可以从图1看出那样,甲醇转化率基本上是100%。在整个试验期间在产物中没有检测到甲醇。甲苯转化率在十五天试验内稳定。平均甲苯转化率超过31%,符合进料组成。
选择性
图2示出了在十五(15)天试验中混合二甲苯、C9、C10+、苯和C4气体的选择性。如可以从图2看出的那样,平均混合二甲苯选择性起始于65%,然后在催化剂达到稳态后增加到75%。平均C9选择性是17%。平均C10+选择性是4%。平均苯选择性是4wt%。气体产出基本上是零。
C9+芳族化合物分布
所述表显示:用甲醇在ZSM-12催化剂上烷基化甲苯产生的C9+芳族化合物的组成。如从所述表可以看出那样,C9芳族化合物由64%的1,2,4-三甲基苯构成,其具有110的RONC值和102的MONC。
C9芳族化合物还含有28%1,3,5三-甲苯,其具有119的RONC值和111的MONC。因此,三甲基苯具有108-119的RONC值和98-111的MONC值。
由甲醇与甲苯的烷基化产生的C9芳族化合物预期是用于车用燃料(车用汽油)池的优异共混组分。当用甲醇在ZSM-12上烷基化甲苯时,还产生一些C10+芳族化合物。所述C10+芳族化合物也预期是用于车用汽油的优异共混组分。
表
C9+芳族化合物组成和辛烷值
组分 | 浓度% | RONC | MONC |
1,2,4-三甲基苯 | 63.5 | 110 | 102 |
1,3,5-三甲基苯 | 27.5 | 119 | 111 |
1,2,3-三甲基苯 | 8.3 | 108 | 98 |
1-乙基,2-甲基苯 | 0.5 | 114 | 102 |
1-乙基,3-甲基苯 | 0.2 | 113 | 102 |
本文引用的所有专利、试验程序和其它文件(包括优先权文件)在此公开物与本发明一致并且针对允许这种引入的所有权限的程度上充分引入供参考。
尽管已经详细描述了本文公开的示例性形式,但是应当理解在不脱离本公开内容精神和范围的各种其它修改对本领域技术人员来说是显而易见且可容易达到的。相应地,不希望在此所附的权利要求的范围受到在这里列出的实施例和描述所限制,而是认为权利要求涵盖属于本发明专利新颖性的所有特征,包括本公开内容所属领域普通技术人员认为是它们的等同物的所有特征。
当多个下限和多个上限在此列出时,从任一下限到任一上限的范围应被考虑。
在本文详细描述和权利要求内的所有数值通过"大约"或"大致"指示值进行修饰,并且考虑本领域中普通技术人员将预计的实验误差和偏差。
Claims (17)
1.混合二甲苯料流和C9+芳族烃料流的制备方法,所述方法包括以下步骤:
(a)使芳族烃进料与烷基化剂进料在烷基化催化剂存在下在烷基化条件下接触以制备包含所述混合二甲苯和所述C9+芳族烃的烷基化芳族产物料流,
其中所述芳族烃包含苯和/或甲苯,所述烷基化剂包含甲醇和/或二甲基醚,所述烷基化催化剂包含具有大于零至大约3的约束指数的分子筛和烷基化条件包括小于500℃的温度,和
其中芳族烃进料与烷基化剂进料的摩尔比在大于1:1至小于4:1的范围内;
(b)从所述烷基化芳族产物料流回收包含所述混合二甲苯和所述C9+芳族烃的料流;
(c)将所述混合二甲苯料流供应给二甲苯异构化单元以制备对二甲苯;和
(d)将所述C9+芳族烃料流供应给分离单元以至少回收C9芳族烃料流,其中所述C9芳族烃料流包含三甲基苯的混合物和乙基甲基苯的混合物;
(e)将所述C9芳族烃料流供应给分离单元以回收包含三甲基苯的所述混合物的料流和/或包含乙基甲基苯的混合物的所述料流;和
(f)将包含三甲基苯的所述混合物的所述料流和/或包含乙基甲基苯的混合物的所述料流作为一种或多种车用燃料共混组分供应。
2.权利要求1的方法,其中所述分子筛具有MTW、BEA*、FAU或MOR骨架结构。
3.权利要求2的方法,其中具有所述MTW骨架结构的所述分子筛是ZSM-12。
4.上述权利要求中任一项的方法,其中所述烷基化芳族产物料流包含至少大约75wt%的所述混合二甲苯和/或至少大约21wt%的所述C9+芳族烃,每个wt%基于所述烷基化芳族产物料流的重量。
5.权利要求2的方法,其中具有所述BEA*骨架结构的所述分子筛是沸石β。
6.权利要求2的方法,其中具有所述FAU骨架结构的所述分子筛选自八面沸石、沸石Y、超稳Y(USY)、脱铝Y(Deal Y)、稀土Y(REY)、超疏水性Y和它们的混合物。
7.权利要求2的方法,其中具有所述MOR骨架结构的所述分子筛选自天然丝光沸石、TEA-丝光沸石和它们的混合物。
8.权利要求1的方法,其中所述分子筛选自ZSM-3、ZSM-4、ZSM-14、ZSM-18、ZSM-20、ZSM-38和它们的混合物。
9.上述权利要求中任一项的方法,其中所述烷基化条件包括300℃-450℃的温度、700kPa-a至7000kPa-a的压力和50hr-1-0.5hr-1的基于所述芳族烃进料的重时空速。
10.C9芳族烃料流和C10芳族烃料流的制备方法,所述方法包括以下步骤:
(a)使包含苯和/或甲苯的芳族烃进料与包含甲醇和/或二甲基醚的进料在包含ZSM-12的烷基化催化剂存在下在烷基化条件下接触以制备包含所述C9芳族烃和C10芳族烃的烷基化芳族产物料流;
其中芳族烃进料与包含甲醇的进料的摩尔比在大于大约1:1至大约4:1的范围内,和所述烷基化条件包括300℃-450℃的温度、700kPa-a至7000kPa-a的压力和50hr-1-0.5hr-1的基于所述芳族烃进料的重时空速;
(b)将所述烷基化芳族产物料流分离以回收所述C9芳族烃料流和所述C10芳族烃料流,其中所述C9芳族烃料流包含三甲基苯的混合物和乙基甲基苯的混合物;
(c)将所述C9芳族烃料流供应给分离单元以回收包含三甲基苯的所述混合物的料流和/或包含乙基甲基苯的混合物的所述料流;和
(d)将包含三甲基苯的所述混合物的所述料流和/或包含乙基甲基苯的混合物的所述料流作为一种或多种车用燃料共混组分供应。
11.权利要求10的方法,还包括以下步骤:
(e)将所述C10芳族烃料流作为一种或多种车用燃料共混组分供应。
12.权利要求10或权利要求11的方法,其中三甲基苯的所述混合物包含1,2,4-三甲基苯、1,3,5-三甲基苯和1,2,3-三甲基苯。
13.权利要求10-12中任一项的方法,还包括以下步骤:
(e)将所述包含三甲基苯的所述混合物的料流供应给所述分离单元以回收包含1,2,4-三甲基苯、1,3,5-三甲基苯和1,2,3-三甲基苯的独立料流。
14.权利要求13的方法,还包括以下步骤:
(f)将所述独立的三甲基苯料流中的每一个作为车用燃料共混组分供应。
15.权利要求10-14中任一项的方法,其中乙基甲基苯的所述混合物包含1-乙基,2-甲基苯和1-乙基,3-甲基苯。
16.权利要求15的方法,还包括以下步骤:
(e)将包含乙基甲基苯的所述混合物的所述料流供应给所述分离单元以回收包含1-乙基,2-甲基苯和1-乙基,3-甲基苯的独立料流。
17.权利要求16的方法,还包括以下步骤:
(f)将包含1-乙基,2-甲基苯和1-乙基,3-甲基苯的所述独立料流中的每一个作为车用燃料共混组分供应。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201862650673P | 2018-03-30 | 2018-03-30 | |
US62/650,673 | 2018-03-30 | ||
EP18169815.0 | 2018-04-27 | ||
EP18169815 | 2018-04-27 | ||
PCT/US2019/022387 WO2019190774A1 (en) | 2018-03-30 | 2019-03-15 | Process for co-production of mixed xylenes and high octane c9+ aromatics |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111954652A true CN111954652A (zh) | 2020-11-17 |
CN111954652B CN111954652B (zh) | 2022-11-08 |
Family
ID=65895065
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201980023435.9A Active CN111954652B (zh) | 2018-03-30 | 2019-03-15 | 混合二甲苯和高辛烷值c9+芳族化合物的共同制备方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US11053176B2 (zh) |
JP (1) | JP7109571B2 (zh) |
KR (1) | KR102433148B1 (zh) |
CN (1) | CN111954652B (zh) |
SA (1) | SA520420241B1 (zh) |
WO (1) | WO2019190774A1 (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115872828A (zh) * | 2022-12-12 | 2023-03-31 | 黄河三角洲京博化工研究院有限公司 | 一种共熔溶剂从重整c9芳烃中分离提纯均三甲苯的方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1403329A (en) * | 1972-04-28 | 1975-08-28 | Mobil Oil Corp | Vapour-phase alkylation in presence of crystalline alumino silicate catalyst |
CN104445262A (zh) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | 具有特定晶体取向的zsm-12分子筛及其制备方法 |
CN105722808A (zh) * | 2013-11-19 | 2016-06-29 | 环球油品公司 | 制备烷基化芳族化合物的方法 |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL6503410A (zh) | 1963-02-21 | 1965-09-20 | ||
US3442795A (en) | 1963-02-27 | 1969-05-06 | Mobil Oil Corp | Method for preparing highly siliceous zeolite-type materials and materials resulting therefrom |
US3308069A (en) | 1964-05-01 | 1967-03-07 | Mobil Oil Corp | Catalytic composition of a crystalline zeolite |
US3354078A (en) | 1965-02-04 | 1967-11-21 | Mobil Oil Corp | Catalytic conversion with a crystalline aluminosilicate activated with a metallic halide |
US3293192A (en) | 1965-08-23 | 1966-12-20 | Grace W R & Co | Zeolite z-14us and method of preparation thereof |
US3415736A (en) | 1965-09-20 | 1968-12-10 | Mobil Oil Corp | Lithium-containing crystalline aluminosilicate |
US3832449A (en) | 1971-03-18 | 1974-08-27 | Mobil Oil Corp | Crystalline zeolite zsm{14 12 |
US3766093A (en) | 1972-01-07 | 1973-10-16 | Mobil Oil Corp | Treatment of organic cationcontaining zeolites |
US3950496A (en) | 1973-05-29 | 1976-04-13 | Mobil Oil Corporation | Synthetic zeolite ZSM-18 |
US3894104A (en) | 1973-08-09 | 1975-07-08 | Mobil Oil Corp | Aromatization of hetero-atom substituted hydrocarbons |
US3960705A (en) | 1974-03-21 | 1976-06-01 | Mobil Oil Corporation | Conversion of foots oil to lube base stocks |
US3923636A (en) | 1974-06-03 | 1975-12-02 | Texaco Inc | Production of lubricating oils |
US3972983A (en) | 1974-11-25 | 1976-08-03 | Mobil Oil Corporation | Crystalline zeolite ZSM-20 and method of preparing same |
US4046859A (en) | 1974-11-29 | 1977-09-06 | Mobil Oil Corporation | Crystalline zeolite and method of preparing same |
US4021947A (en) | 1975-10-30 | 1977-05-10 | Shneider Aaron H | Rotary display stands |
US4016218A (en) | 1975-05-29 | 1977-04-05 | Mobil Oil Corporation | Alkylation in presence of thermally modified crystalline aluminosilicate catalyst |
US4211886A (en) * | 1978-09-25 | 1980-07-08 | Mobil Oil Corporation | Manufacture of benzene, toluene and xylene |
US4401556A (en) | 1979-11-13 | 1983-08-30 | Union Carbide Corporation | Midbarrel hydrocracking |
AU2003247572A1 (en) | 2002-06-19 | 2004-01-06 | Exxonmobil Chemical Patents Inc. | Manufacture of xylenes from reformate |
US8252967B2 (en) | 2009-04-14 | 2012-08-28 | Exxonmobil Chemical Patents Inc. | Process for the purification of paraxylene |
US8558046B2 (en) | 2009-05-28 | 2013-10-15 | Saudi Basic Industries Corporation | Aromatic alkylation process |
US8202506B2 (en) | 2009-11-17 | 2012-06-19 | Exxonmobil Research And Engineering Company | High activity small crystal ZSM-12 |
WO2011098655A1 (en) | 2010-02-11 | 2011-08-18 | Nokia Corporation | Apparatus and method to allocate communication resources in a communication system |
KR101632529B1 (ko) | 2012-05-31 | 2016-06-21 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 파라크실렌 회수 공정에서의 페놀 제거 |
US10011538B2 (en) | 2014-10-27 | 2018-07-03 | Exxonmobil Chemical Patents Inc. | Method of making aromatic hydrocarbons |
WO2018067282A1 (en) | 2016-10-06 | 2018-04-12 | Exxonmobil Chemical Patents Inc. | Process for selectivating catalyst for producing paraxylene by methylation of benzene and/or toluene |
WO2018067281A1 (en) * | 2016-10-06 | 2018-04-12 | Exxonmobil Chemical Patents Inc. | Process for methylating aromatic hydrocarbons |
-
2019
- 2019-03-15 US US16/979,751 patent/US11053176B2/en active Active
- 2019-03-15 WO PCT/US2019/022387 patent/WO2019190774A1/en active Application Filing
- 2019-03-15 CN CN201980023435.9A patent/CN111954652B/zh active Active
- 2019-03-15 JP JP2020552708A patent/JP7109571B2/ja active Active
- 2019-03-15 KR KR1020207028184A patent/KR102433148B1/ko active IP Right Grant
-
2020
- 2020-09-29 SA SA520420241A patent/SA520420241B1/ar unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1403329A (en) * | 1972-04-28 | 1975-08-28 | Mobil Oil Corp | Vapour-phase alkylation in presence of crystalline alumino silicate catalyst |
CN104445262A (zh) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | 具有特定晶体取向的zsm-12分子筛及其制备方法 |
CN105722808A (zh) * | 2013-11-19 | 2016-06-29 | 环球油品公司 | 制备烷基化芳族化合物的方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115872828A (zh) * | 2022-12-12 | 2023-03-31 | 黄河三角洲京博化工研究院有限公司 | 一种共熔溶剂从重整c9芳烃中分离提纯均三甲苯的方法 |
CN115872828B (zh) * | 2022-12-12 | 2024-05-31 | 黄河三角洲京博化工研究院有限公司 | 一种共熔溶剂从重整c9芳烃中分离提纯均三甲苯的方法 |
Also Published As
Publication number | Publication date |
---|---|
JP2021519767A (ja) | 2021-08-12 |
WO2019190774A1 (en) | 2019-10-03 |
KR102433148B1 (ko) | 2022-08-17 |
US20210040016A1 (en) | 2021-02-11 |
SA520420241B1 (ar) | 2022-11-29 |
CN111954652B (zh) | 2022-11-08 |
KR20200128422A (ko) | 2020-11-12 |
JP7109571B2 (ja) | 2022-07-29 |
US11053176B2 (en) | 2021-07-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110035987B (zh) | 通过苯和/或甲苯的甲基化生产对二甲苯的方法 | |
US10696608B2 (en) | Process for methylating aromatic hydrocarbons | |
TWI567049B (zh) | 對二甲苯之製法 | |
US10246387B2 (en) | Process for selectivating catalyst for producing paraxylene by methylation of benzene and/or toluene | |
WO2007120951A2 (en) | Processes for producing xylenes using isomerization and transalkylation reactions and apparatus therefor | |
AU2006285236A1 (en) | Methods of making xylene isomers | |
US20190241485A1 (en) | Catalysts for Producing Paraxylene by Methylation of Benzene and/or Toluene | |
CN111954652B (zh) | 混合二甲苯和高辛烷值c9+芳族化合物的共同制备方法 | |
US20210040013A1 (en) | Multistage alkylation via byproduct removal | |
US11673849B2 (en) | Process for selectivating catalyst for producing paraxylene by methylation of benzene and/or toluene | |
US11643375B2 (en) | Processes for converting benzene and/or toluene via methylation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |