CN104395436A - 由c5-c12烃混合物生产btx的方法 - Google Patents
由c5-c12烃混合物生产btx的方法 Download PDFInfo
- Publication number
- CN104395436A CN104395436A CN201380029411.7A CN201380029411A CN104395436A CN 104395436 A CN104395436 A CN 104395436A CN 201380029411 A CN201380029411 A CN 201380029411A CN 104395436 A CN104395436 A CN 104395436A
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- Prior art keywords
- hydrocarbon
- hydrocracking
- btx
- hydrodealkylation
- catalyst
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 89
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 87
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 81
- 239000000203 mixture Substances 0.000 title claims description 40
- 230000008569 process Effects 0.000 title abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 54
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000010457 zeolite Substances 0.000 claims abstract description 51
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 105
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 74
- 150000002430 hydrocarbons Chemical class 0.000 claims description 73
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 41
- 125000003118 aryl group Chemical group 0.000 claims description 37
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- 229960001866 silicon dioxide Drugs 0.000 claims description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims description 11
- 238000004821 distillation Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 10
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 239000003502 gasoline Substances 0.000 claims description 9
- 239000002737 fuel gas Substances 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 238000004939 coking Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000011148 porous material Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 21
- 239000003915 liquefied petroleum gas Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 17
- 239000011230 binding agent Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 8
- 230000023556 desulfurization Effects 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- -1 compound aromatic hydrocarbon Chemical class 0.000 description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 229910052797 bismuth Inorganic materials 0.000 description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- PFEOZHBOMNWTJB-UHFFFAOYSA-N 3-methylpentane Chemical compound CCC(C)CC PFEOZHBOMNWTJB-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002361 compost Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 125000003454 indenyl group Chemical class C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010555 transalkylation reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Chemical group 0.000 description 1
Classifications
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- 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
- C07C4/06—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- C10G45/60—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 characterised by the catalyst used
- C10G45/64—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 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J21/12—Silica and alumina
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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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
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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
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- 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
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- B01J35/615—100-500 m2/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- 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
- C07C4/08—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule
- C07C4/12—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene
- C07C4/14—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by splitting-off an aliphatic or cycloaliphatic part from the molecule from hydrocarbons containing a six-membered aromatic ring, e.g. propyltoluene to vinyltoluene splitting taking place at an aromatic-aliphatic bond
-
- 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
- C10G45/60—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 characterised by the catalyst used
- C10G45/62—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 characterised by the catalyst used containing platinum group metals or compounds thereof
-
- 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
- C10G45/68—Aromatisation of hydrocarbon oil fractions
- C10G45/70—Aromatisation of hydrocarbon oil fractions with catalysts containing platinum group metals or compounds thereof
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Abstract
本发明涉及一种由包含C5-C12烃的混合的供料流如下来生产化学级BTX的方法:在氢的存在下使所述供料流与具有加氢裂化/加氢脱硫活性的催化剂接触。具体地,提供了一种由包含C5-C12烃的供料流来生产BTX的方法,其包括步骤:(a)在氢的存在下将所述供料流与组合的加氢裂化/加氢脱硫催化剂接触,来生产包含BTX的加氢裂化产物流;和(b)将该BTX从加氢裂化产物流分离。该加氢裂化/加氢脱硫催化剂包含相对于总催化剂重量0.1-1wt%的加氢金属。该加氢裂化/加氢脱硫催化剂进一步包含沸石,其孔径是并且二氧化硅(SiO2)与氧化铝(Al2O3)摩尔比是5-200。该加氢裂化/加氢脱硫条件包括温度450-580℃,表压300-5000kPa和重时空速0.1-10h-1。
Description
本发明涉及一种由包含C5-C12烃的混合的供料流如下来生产化学级BTX的方法:在氢的存在下将所述供料流与具有加氢裂化/加氢脱硫活性的催化剂接触。
以前在WO02/44306A1和WO2007/055488A1中已经描述了芳族烃化合物和LPG可以由沸点为30-250℃的混合烃给料来生产。所以将沸点为30-250℃的烃给料和氢引入到反应区,其中将所述烃给料在催化剂存在下,通过加氢脱烷基化和/或烷基转移作用转化成富含BTX的芳族烃化合物和通过加氢裂化转化成富含LPG的非芳族烃化合物,并且通过气-液分离和蒸馏分别回收该芳族烃化合物和LPG。WO02/44306A1的方法中所用的催化剂包含铂/锡或铂/铅和混合物载体,该载体由10-95wt%的沸石(其二氧化硅/氧化铝摩尔比是200或更低)和5-90wt%的无机粘结剂组成,所述沸石选自发光沸石、β类型沸石、ZSM-5类型沸石及其混合物,在其中所述铂的存在量是0.01-0.5重量份,并且所述锡的存在量是0.01-5.0重量份或者所述铅的存在量是0.02-5.0份,基于100重量份的所述混合物载体计。WO2007/055488A1的方法所用的催化剂是通过将0.01~0.5重量份的铂(Pt)和0.01~3.0重量份的铋(Bi)负载于100重量份的混合物载体上来制备的,该混合物载体包括10~95wt%的二氧化硅/氧化铝摩尔比为200或更低的沸石,其选自发光沸石、β沸石、ZSM-5沸石及其组合,和5~90wt%的无机粘结剂。WO02/44306 A1和WO2007/055488的方法的特征在于催化剂所含的加氢金属铂的加氢活性必须通过次级金属例如锡、铅或者铋来抑制。作为其结果,该催化剂变得非常易于被污染物和杂原子(其经常包含在烃给料中)例如硫减活。此外,WO02/44306A1和WO2007/055488的方法生产了包含相对高量的非芳族烃的产物流,其与BTX共沸(co-boil)而导致在不使用溶剂萃取方法和相对大量的燃料气,以所生产的LPG为代价的情况下,不可能生产化学级BTX。
本发明的一个目标是提供一种方法,用于将混合的C5-C12烃供料流(其相对富含BTX和BTX的共沸物,例如第一级的加氢处理的热解汽油或者直馏石脑油)转化成化学级BTX,而无需溶剂萃取来从共沸的非BTX烃物质中分离BTX。本发明的另一目标是提供一种方法,用于将混合的C5-C12烃供料流转化成BTX和LPG,其不易于由供料中的含硫化合物导致催化剂减活和其无需在供料到所述方法之前对给料进行脱硫。本发明的另一目标是提供一种方法,用于将混合的C5-C12烃供料流转化成BTX和LPG,其中与常规方法相比甲烷的产生减少。本发明的另一目标是提供一种方法,用于将混合的C5-C12烃供料流转化成BTX和LPG,其中当与常规方法相比时,供料流中所含的苯向其他烃化合物例如萘化合物、甲苯或二甲苯的转化减少。
上述问题的解决方案是通过提供此下所述和权利要求中所表现的实施方案来实现的。因此,本发明提供一种生产BTX的方法,其包含:
(a)在包含温度450-580℃,表压300-5000kPa和重时空速0.1-10h-1的工艺条件下,在氢的存在下将包含C5-C12烃的供料流与组合的加氢裂化/加氢脱硫催化剂接触,来生产包含BTX的加氢裂化产物流,所述催化剂包含相对于总催化剂重量为0.1-1wt%的加氢金属,和沸石,该沸石的孔径是并且二氧化硅(SiO2)与氧化铝(Al2O3)摩尔比是5-200;和
(b)将BTX从该加氢裂化产物流分离。
在本发明的上下文中,令人惊讶地发现通过本发明的方法,C5-C12烃混合物可以有效的转化成基本上不含BTX的共沸物的混合物。作为其结果,化学级是通过将加氢裂化产物流进行相对简单的分离方法例如气-液分离或者蒸馏来获得的。此外,已经发现在由包含C5-C12烃的供料流来生产BTX的方法中所产生的甲烷的量可以通过本发明的方法显著降低。甲烷是一种不期望的副产物,因为它仅仅具有燃料气价值,其低于BTX和LPG的价值。本发明的另一优点是氢的消耗减少。
在本文上下文中,要注意的是WO02/44306A1和WO2007/055488A1所述方法中所用的催化剂不使用加氢裂化/加氢脱硫催化剂,因为加氢抑制性次级金属锡、铅或铋的存在导致这些催化剂不适于加氢脱硫。
如此处使用的术语“C#烃”(其中“#”是正整数)意思是描述了具有#个碳原子的全部烃。此外,术语“C#+烃”意思是描述了具有#个或者更多个碳原子的全部烃分子。因此,术语“C5+烃”意思是描述具有5个或者更多个碳原子的烃的混合物。
通过本发明方法的加氢裂化/加氢脱硫步骤所生产的产物(加氢裂化产物流)包含LPG、BTX和甲烷。如此处使用的术语“LPG”指的是公知的用于术语“液化石油气”的首字母缩写词。LPG通常由C2-C4烃的共混物组成,即C2、C3和C4烃的混合物,其中C3烃是主要成分。如此处使用的术语“BTX”是本领域公知的,并且涉及苯、甲苯和二甲苯的混合物。如此处使用的术语“化学级BTX”涉及一种烃混合物,其包含小于5wt%的除苯、甲苯和二甲苯的烃,优选小于4wt%的除苯、甲苯和二甲苯的烃,更优选小于3wt%的除苯、甲苯和二甲苯的烃,和最优选小于2.5wt%的除苯、甲苯和二甲苯的烃。此外,通过本发明方法中所生产的“化学级BTX”包含小于1wt%的非芳族C6+烃,优选小于0.7wt%的非芳族C6+烃,更优选小于0.6wt%的非芳族C6+烃和最优选小于0.5wt%的非芳族C6+烃。大部分关键的污染物是沸点接近于苯的非芳族物质,包括但不限于环己烷,甲基环戊烷,正己烷,2-甲基戊烷和3-甲基戊烷。
因此,该加氢裂化产物流基本上没有非芳族C6+烃。如此处意味的,术语“加氢裂化产物流基本上没有非芳族C6+烃”意为所述加氢裂化产物流包含小于1wt%的非芳族C6+烃,优选小于0.7wt%的非芳族C6+烃,更优选小于0.6wt%的非芳族C6+烃和最优选小于0.5wt%的非芳族C6+烃。
术语“芳族烃”是本领域非常公知的。因此,术语“芳族烃”涉及成环共轭烃,其稳定性(归因于离位)明显大于假定的定域结构(例如Kekulé结构)。用于确定给定的烃的芳香度的最常用的方法是观察1HNMR光谱中的抗磁性,例如对于苯环质子,7.2-7.3ppm的化学位移的存在。
在本发明的方法中所生产的加氢裂化产物流优选包含小于5wt%的甲烷。优选本发明方法中所生产的加氢裂化产物流包含小于4wt%的甲烷,更优选小于3wt%的甲烷,甚至更优选小于2wt%的甲烷,特别优选小于1.5wt%的甲烷和最优选小于1wt%的甲烷。
在一个实施方案中,本发明方法中所生产的加氢裂化产物流包含小于10wt%的乙烷,优选小于8wt%的乙烷,最优选小于7wt%的乙烷。
在另一实施方案中,本发明方法中所生产的加氢裂化产物流包含小于10wt%的甲烷和乙烷,优选小于8wt%的甲烷和乙烷,最优选小于7.5wt%的甲烷和乙烷。
优选该加氢裂化产物流还基本上没有C5烃。如此处意味的,术语“加氢裂化产物流基本上没有C5烃”意为所述加氢裂化产物流包含小于1wt%的C5烃,优选小于0.7wt%的C5烃,更优选小于0.6wt%的C5烃和最优选小于0.5wt%的C5烃。
本发明方法的一个特别的优点是所述加氢裂化产物流基本上没有非芳族C6+烃,因为这些烃的沸点通常接近于C6+芳族烃的沸点。因此,可能难以将非芳族C6+烃通过蒸馏与加氢裂化产物流中所含的芳族C6+烃分离。
本发明方法的有利效果是通过有策略地选择加氢裂化/加氢脱硫催化剂和相组合的加氢裂化/加氢脱硫条件来获得的。在本发明的上下文中,令人惊讶地发现通过将具有相对强的酸功能(例如通过选择这样的催化剂,其包含孔径为并且二氧化硅(SiO2)与氧化铝(Al2O3)摩尔比为5-200的沸石)和相对强的加氢活性(例如通过选择包含0.1-1wt%的加氢金属的催化剂)的加氢裂化/加氢脱硫催化剂与包含相对高的工艺温度(例如选择450-580℃的温度)的工艺条件相组合,可以由混合的C5-C12烃供料流来生产化学级BTX和LPG,而无需事先对给料进行脱硫,其中减少了甲烷的产生并且其中减少了供料流中所含的苯向其他烃化合物例如环烷化合物、甲苯或者二甲苯的转化。
因此,该加氢裂化/加氢脱硫催化剂包含孔径二氧化硅(SiO2)与氧化铝(Al2O3)摩尔比为5-200的沸石和0.1-1wt%的加氢金属(相对于总催化剂)并且该加氢裂化/加氢脱硫条件包括温度450-580℃,表压300-5000kPa和重时空速0.1-10h-1。
该工艺条件(在其下进行供料流的加氢裂化/加氢脱硫)是加氢裂化产物流组成的重要决定因素。优选该加氢裂化/加氢脱硫条件包括温度450-580℃,更优选470-550℃。必须避免较低的温度,因为芳族环的加氢变成有利的。这与现有技术的教导是完全相反的,在现有技术中高到430℃的相对低的工艺温度是优选的。在反应温度过高的情况中,LPG的收率(特别是丙烷和丁烷)降低,甲烷收率增加。因为催化剂活性可能在催化剂寿命期间降低,因此有利的是在催化剂寿命期间逐渐增加反应器温度,来保持加氢裂化转化率。这意味着在运行周期开始时的最佳温度优选处于加氢裂化温度范围的下端,而最佳反应器温度将随着催化剂减活而增加,以使得所述周期的终点(在催化剂被替换或者再生之前不久)优选选择在该加氢裂化温度范围的高端。
优选该供料流的加氢裂化/加氢脱硫是在表压300-5000kPa,更优选表压600-3000kPa,特别优选表压1000-2000kPa和最优选表压1200-1600kPa进行的。通过增加反应器压力,可以增加C5+非芳族烃的转化率,但是也增加了甲烷的收率和芳族环向环己烷物质(其可裂解成LPG物质)的加氢。这导致芳族化合物收率随着压力增加而降低,并且因为一些环己烷和它的异构体甲基环戊烷没有完全加氢裂化,因此在1200-1600kPa的压力所得的苯的纯度存在着一个最佳值。
优选该供料流的加氢裂化/加氢脱硫是在重时空速(WHSV)为0.1-10h-1,更优选重时空速为0.2-6h-1和最优选重时空速为0.4-2h-1下进行的。当该空速过高时,并非全部的BTX共沸链烷烃组分都加氢裂化,因此将不可能通过反应器产物的简单蒸馏实现BTX规格。在过低的空速下,甲烷的收率以丙烷和丁烷为代价而升高。通过选择最佳的重时空速,令人惊讶地发现实现了苯共沸物足够完全的反应来生产规格BTX,无需液体再循环。
因此,优选的加氢裂化/加氢脱硫条件因此包括温度450-580℃,表压300-5000kPa和重时空速0.1-10h-1。更优选的加氢裂化/加氢脱硫条件包括温度470-550℃,表压600-3000kPa和重时空速0.2-6h-1。特别优选的加氢裂化/加氢脱硫条件包括温度470-550℃,表压1000-2000kPa和重时空速0.4-2h-1。
具有加氢裂化/加氢脱硫活性的催化剂(“加氢裂化/加氢脱硫催化剂”)描述在Hydrocracking Science and Technology(1996)Ed.JuliusScherzer,A.J.Gruia,Pub.Taylor and Francis的第13-14和174页中。加氢裂化和加氢脱硫反应通过双功能机理来进行,其需要相当强的酸功能,其提供裂化和异构化和其提供了供料中所含的有机硫化合物中所含的硫-碳键的断裂,和金属功能,其提供烯烃加氢和硫化氢的形成。用于加氢裂化/加氢脱硫方法的许多催化剂是通过将各种过渡金属用固体载体例如氧化铝,二氧化硅,氧化铝-二氧化硅,氧化镁和沸石混合(compost)来形成的。
特别适于本发明方法的加氢裂化/加氢脱硫催化剂包含分子筛,优选沸石,其的孔径是
沸石是具有公知孔径的公知的分子筛。如此处使用的术语“沸石”或者“铝硅酸盐沸石”涉及到铝硅酸盐分子筛。关于它们特性的概述例如提供在Kirk-Othmer Encyclopedia of Chemical Technology,第16卷第811-853页关于Molecular Sieves的章节中;Atlas of ZeoliteFramework Types,第5版,(Elsevier,2001)中。优选该加氢裂化/加氢脱硫催化剂包含中孔径的铝硅酸盐沸石或者大孔径铝硅酸盐沸石。合适的沸石包括但不限于ZSM-5,MCM-22,ZSM-11,β沸石,EU-1沸石,沸石Y,faujastite和发光沸石。术语“中孔沸石”通常用于沸石催化剂领域。因此,中孔径沸石是孔径为大约的沸石。合适的中孔径沸石是10环沸石,即,所述孔是通过由10个SiO4四面体组成的环形成的。合适的大孔径沸石的孔径是大约并且是12环结构类型。8环结构类型的沸石被称作小孔径沸石。在上述的Atlas of Zeolite Framework Types中,基于环结构列出各种沸石。最优选的沸石是ZSM-5沸石,其是具有MFI结构的公知沸石。
该沸石优选是脱铝酸盐的。优选ZSM-5沸石的二氧化硅(SiO2)与氧化铝(Al2O3)摩尔比是5-200,更优选10-100。用于获得脱铝酸盐沸石的手段和方法是本领域公知的,并且包括但不限于酸沥滤技术;参见例如Post-synthesis Modification I;Molecular Sieves,第3卷;Eds.H.G.Karge,J.Weitkamp;Year(2002);第204-255页。在本发明的上下文中,发现使用SiO2:Al2O3摩尔比为10-200的脱铝酸盐沸石改进了该催化剂的性能/稳定性。用于量化脱铝酸盐沸石的SiO2:Al2O3摩尔比的手段和方法是本领域公知的,并且包括但不限于AAS(原子吸收光谱仪)或者ICP(感应耦合等离子体光谱法)分析。
所述沸石是氢形式的:即,至少一部分的与其关联的初始阳离子被氢替换。将铝硅酸盐沸石转化成氢形式的方法是本领域公知的。第一方法包括使用酸直接离子交换。第二方法包括使用铵盐来碱交换,随后煅烧。
此外,该催化剂组合物包含了足量的加氢金属来确保该催化剂具有相对强的加氢活性。加氢金属是石化催化剂领域公知的。因此,优选的是该催化剂不包含次级金属例如锡、铅或者铋,其抑制了加氢金属的加氢活性。优选本发明方法所用的加氢裂化/加氢脱硫催化剂因此包含小于0.01份的锡和小于0.02份的铅和小于0.01份的铋(基于100重量份的总催化剂),优选小于0.005份的锡和小于0.01份的铅和小于0.005份的铋(基于100重量份的总催化剂)。该催化剂组合物优选包含0.1-1wt%的加氢金属,更优选0.2-07wt%的加氢金属。在本发明的上下文中,术语“wt%”当涉及催化剂组合物中所含的金属含量时,其涉及到所述金属相对于总催化剂重量的wt%(或者“wt-%”),所述总催化剂包括催化剂粘结剂、填料、稀释剂等。优选该加氢金属是选自元素周期表第10族的至少一种元素。优选的第10族元素是铂。因此,本发明方法所用的加氢裂化/加氢脱硫催化剂包含沸石,其孔径是二氧化硅(SiO2)与氧化铝(Al2O3)摩尔比是5-200,和0.1-1wt%的铂(相对于总催化剂)。
该加氢裂化/加氢脱硫催化剂组合物可以进一步包含粘结剂。氧化铝(Al2O3)是优选的粘结剂。本发明的催化剂组合物优选包含至少10wt%,最优选至少20wt%的粘结剂和优选包含高到40wt%的粘结剂。在一个实施方案中,该加氢金属沉积在粘结剂(其优选是Al2O3)上。
在一个实施方案中,该加氢裂化/加氢脱硫催化剂包含ZSM-5和Pt改性的氧化铝(Pt/Al2O3)的混合物,其中ZSM-5:Pt/Al2O3重量比是5:1-1:5,优选3:1-1:3和最优选2:1-1:2。在本发明上下文中,令人惊讶地发现通过选择包含ZSM-5和Pt改性的氧化铝混合物的加氢裂化/加氢脱硫催化剂,与其中铂沉积在ZSM-5沸石上的加氢裂化/加氢脱硫催化剂相比时,可以增加加氢裂化产物流的BTX含量。
本发明方法所用的供料流是包含C5-C12烃的混合物,优选的沸点是30-195℃。优选该供料流主要包含C6-C8烃。合适的供料流包括但不限于第一级加氢处理的热解汽油,直馏石脑油,加氢裂化的汽油,轻质焦化石脑油和焦化炉轻质油,FCC汽油,重整油或者其混合物。本发明的方法特别适于加工具有相对高的硫含量的烃供料流,例如热解汽油(重质裂解汽油,pygas),直馏石脑油,轻质焦化石脑油和焦化炉轻质油及其混合物。此外,优选的是烃供料中所含的非芳族物质是饱和的(例如通过事先加氢)来降低本发明方法中所用的催化剂床内的放热。
例如第一级加氢处理的热解汽油典型的组成可以包含10-15wt%的C5烯烃,2-4wt%的C5链烷烃和环链烷烃,3-6wt%的C6烯烃,1-3wt%的C6的链烷烃和环烷烃,25-30wt%的苯,15-20wt%的甲苯,2-5wt%的乙基苯,3-6wt%的二甲苯,1-3wt%的三甲基苯,4-8wt%的二环戊二烯和10-15wt%的C9+芳族化合物,烷基苯乙烯和茚;参见例如Applied Heterogeneous Catalysis:Design,Manufacture,and Useof Solid Catalysts(1987)J.F.Le Page中的表E3.1。但是,同样可以有利的用作本发明方法的供料流的是这样的烃混合物,其进行了脱戊烷和调节,以使得全部的C6-C9烃物质的浓度与典型的以上数据相比是相对高的。
在一个实施方案中,处理本发明方法所用的烃供料流,以使得它富含单芳族化合物。如此处使用的术语“单芳族化合物”涉及具有仅仅一个芳族环的烃化合物。适于使单芳族化合物内容物富含在混合的烃流中的手段和方法是本领域公知的,例如Maxene方法;参见Bhirud(2002)Proceedings of the DGMK-conference 115-122。
本发明方法所用的烃供料流可以包含高到300wppm的硫(即,任何化合物中所存在的硫原子的重量,相对于供料的总重量)。本发明方法的一个优点是它在将所述烃供料流进行加氢裂化处理之前,不必将烃供料流进行脱硫处理。优选该供料流包含10-300wppm的硫,其中该加氢脱烷基化产物流包含0.1-5wppm的硫。测量烃流中硫含量的方法是公知的。优选硫含量是使用IP490标准来测量的;也参见ISO20846:2011。因此,将样品引入到热解炉中,在这里该样品在高温下在氧气气氛中氧化。该样品中全部的硫被氧化成SO2。该SO2曝露于紫外线,导致它发荧光。该荧光所发射的光是通过光电倍增管来检测的,并且所形成的信号与样品的硫含量成比例。
该加氢裂化/加氢脱硫步骤是在反应混合物中过量的氢存在下进行的。这意味着大于化学计量量的氢存在于该进行加氢裂化的反应混合物中。优选反应器供料中氢与烃物质的摩尔比(H2/HC摩尔比)是1:1-4:1,优选1:1-3:1和最优选1:1-2:1。在本发明上下文中,令人惊讶地发现通过选择相对低的H2/HC摩尔比,可以获得产物流中更高的苯纯度。在本文上下文中,术语“烃物质”表示了反应器供料中所存在的全部烃分子,例如苯,甲苯,己烷,环己烷等。需要要知道供料的组成,然后计算这个料流的平均分子量,以便能够计算正确的氢供料率。反应混合物中过量的氢抑制了焦炭的形成,据信其导致了催化剂减活。
该加氢裂化产物流通过常规手段和方法进行分离,所述常规手段和方法适于分离包含在作为第一分离流的加氢裂化产物流中的甲烷和未反应的氢,包含在作为第二分离流的加氢裂化产物流中的LPG和作为第三分离流的BTX。优选该BTX是通过气-液分离或者蒸馏从加氢裂化产物流分离的。这样的分离方法的一个非限定性例子包括一系列的蒸馏步骤。在适度温度下的第一蒸馏步骤是使大部分的芳族物质(液体产物)与氢,H2S,甲烷和LPG物质分离。来自这个蒸馏的气态流进一步冷却(到大约-30℃)并且再次蒸馏来分离其余的芳族物质和大部分的丙烷和丁烷。该气态产物(主要是氢,H2S,甲烷和乙烷)然后进一步冷却(到大约-100℃)来分离乙烷并且在气态流中留下氢,H2S和甲烷,所述气态流将再循环到反应器。为了控制反应器供料中的H2S和甲烷的水平,将一定比例的再循环气流从所述系统中作为扫气除去。所吹扫的材料的量取决于再循环流中甲烷和H2S的水平,其进而取决于供料组成。该吹扫流将具有与再循环流相同的组成。因为该扫气主要将包含氢和甲烷,因此它适于用作燃料气或者可以进一步处理(例如经由变压吸附单元)来分离地回收高纯氢流和甲烷/H2S流(其可以用作燃料气)。
在另一实施方案中,本发明涉及一种由包含C5-C12烃的供料流来生产苯的方法,其中所述方法包括本发明的生产BTX的方法,进一步包括将BTX(或者仅仅所生产的所述BTX的甲苯和二甲苯部分)与氢在适合于生产包含苯和燃料气的加氢脱烷基化产物流的条件下接触的步骤。
早先已经描述了非常高纯度的苯可以通过包含脂肪族烃和芳族烃的供料流的加氢脱烷基化来制备。制备苯的加氢脱烷基化方法是商业使用的,例如用于将蒸汽裂化器中所获得的热解产物的C6-C9部分转化成苯;参见例如Handbook of Commercial Catalysts:Heterogeneous Catalysts ed.Howard F.Rase(2000)CRC Press第211-212页和Handbook of Petroleum Refining Processes ed.RobertA.Meyers(1986)Mcgraw-Hill第2-3-2-7页。
常规的加氢脱烷基化方法的一个主要缺点是主要部分的烃供料降级到主要由甲烷组成的燃料气。在本发明的上下文中,令人惊讶地发现通过本发明的生产苯的方法所生产的燃料气(甲烷)的量可以通过使用多步方法而显著降低,其中首先生产BTX,随后将该BTX(或者与所述BTX分离的甲苯和二甲苯)进行加氢脱烷基化。
现有技术公开了加氢脱烷基化方法,其中降低了甲烷的形成。这样的方法描述在WO2008/015027中,其提供一种催化加氢脱烷基化方法,使用由ZSM-5催化剂(Si/Al摩尔比为5-100),铂和钼组成的催化剂。在根据WO2008/015027A1的加氢脱烷基化方法中,选择工艺条件来减少甲烷的形成。相对温和的加氢脱烷基化条件(需要其来抑制甲烷形成)具有缺点,即,产物流富含甲苯,其具有远低于苯的市场价值。
WO2010/102712A2描述了一种通过加氢脱烷基化来获得基本纯的苯的方法,其中通过萃取性蒸馏从供给到加氢脱烷基化反应器中的料流中除去非芳族烃。这种方法的一个缺点是获得了非芳族烃的非均相混合物,其需要进一步分离和/或处理。
在该生产苯的方法中,分离步骤(b)可以包括这样的步骤,其中包含在加氢裂化产物流中的苯是在加氢脱烷基化之前,与甲苯和二甲苯分离的。这种分离步骤的优点是增加了加氢脱烷基化反应器的能力。所述苯可以通过常规的蒸馏来与中间芳族流分离。通过这种方法,苯能够容易地与其他芳族物质分离。这种方法因为所述供料流包含多种沸点接近于苯的物质,不能用于从本发明方法的包含C5+烃的供料流中回收苯。这些物质在反应器区中几乎完全反应,以使得它们在加氢裂化产物流中的浓度足够低,来允许通过蒸馏加氢脱烷基化产物流来生产足够纯的苯。
加氢脱烷基化包含C6-C9芳族烃的烃混合物的方法是本领域公知的,并且包括热加氢脱烷基化和催化加氢脱烷基化;参见例如WO2010/102712A2。催化加氢脱烷基化在本发明上下文中是优选的,因为相比于热加氢脱烷基化,这种加氢脱烷基化方法通常具有朝着苯的更高的选择性。优选使用催化加氢脱烷基化,其中该加氢脱烷基化催化剂选自负载的氧化铬催化剂,负载的氧化钼催化剂,在二氧化硅或者氧化铝上的铂和在二氧化硅或者氧化铝上的氧化铂。
可用于加氢脱烷基化的工艺条件(在此也描述为“加氢烷基化条件”)可以由本领域技术人员容易地确定。用于热加氢脱烷基化的工艺条件例如描述在DE1668719A1中并且包括温度600-800℃,表压3-10MPa和反应时间15-45秒。描述了用于优选的催化加氢脱烷基化的工艺条件,并且所述工艺条件优选包括温度500-650℃,表压3.5-7MPa和重时空速0.5-2h-1;也参见Handbook of CommercialCatalysts:Heterogeneous Catalysts ed.Howard F.Rase(2000)Loc.cit。
该加氢脱烷基化产物流典型地通过冷却和蒸馏的组合而分离成液体流(包含苯和其他芳族物质)和气体流(包含氢,H2S,甲烷和其他低沸点烃)。该液体流可以通过蒸馏进一步分离成苯流,C7-C9芳族流和重质芳族流。C7-C9芳族流可以作为再循环供给回反应器区,来增加整体转化率和苯收率。该重质芳族流(其包含多芳族物质例如联苯(byphenyl))优选不循环到反应器,而可以输出作为分离的产物流。该气体流包含大量的氢,其可以经由再循环气体压缩机再循环回到反应器区。再循环气体吹扫可以用于控制反应器供料中的甲烷和H2S的浓度。
虽然本发明已经出于说明的目的而进行了详细描述,但是应当理解这样的细节仅仅是用于所述目的,并且可以由本领域技术人员在其中进行改变,而不脱离权利要求中所定义的本发明的主旨和范围。
另外要注意的是本发明涉及这里所述特征全部可能的组合,优选的特别是权利要求中所提出的特征的那些组合。
要注意的是术语“包含”不排除其他要素的存在。但是,还要理解的是对于包含某些组分的产物的描述也公开了由这些组分所组成的产物。类似的,还应当理解对于包含某些步骤的方法的描述也公开由这些步骤组成的方法。
具体实施方式
本发明现在将通过下面的非限定性实施例来说明。
实施例1制备加氢裂化/加氢脱硫催化剂
加氢裂化/加氢脱硫催化剂已经如下来制备。
将氢形式的市售MFI类型沸石(Si:Al摩尔比是大约100:1)与氧化铝粘结剂以沸石与粘结剂重量比为大约9:1进行混合。随后的混合物形成大约1.6mm直径的球形粒子,来提供结合的沸石粒子。
获得了市售的铂改性的γ-氧化铝粒子(直径大约1.6mm的球),其包含0.75wt%的铂。该铂改性的γ-氧化铝粒子的总表面积是大约200m2/g(通过常规的氮BET方法来测量),孔体积是大约0.7cc/g和平均孔直径是大约20nm。
随后,将该结合的沸石粒子和铂改性的γ-氧化铝粒子以1:1的重量比均匀混合,来提供加氢裂化/加氢脱硫催化剂组合物。
实施例2热解汽油的加氢裂化/加氢脱硫
反应测试是使用含有催化剂床的12mm(内径)不锈钢反应器管来进行的,所述催化剂床含有实施例1中所制备的4g的加氢裂化/加氢脱硫催化剂组合物。在该实验开始时,将该混合的催化剂床在所述测试反应器中,在140℃和在流动氢下(100ml/min,在40-60psig运行压力下)原位干燥最小2小时(来除去任何所吸收的水)。此后,保持氢流量和压力,同时将反应器温度升高到期望的测试温度(典型的~500℃),并且在引入烃供料之前在这个温度保持最少2小时。在这些调节阶段期间,煅烧的催化剂中所存在的任何Pt氧化物据信被还原成Pt金属。该反应器是在450-550℃的温度,100-400psig(690-2760kPa)的压力和2-4h-1的重时空速运行的。(WHSV定义为供给到反应器的液烃的时间质量/反应器中催化剂的质量)。
在每种情况中,反应器供料中氢与烃的摩尔比保持在摩尔比是大约4:1。用于这些测试的热解汽油典型的组成显示在下文提供的表1中:
表1
组分 | wt%(通过GC) |
总C6-C8烷烃 | 16.54 |
C6烷烃 | 13.17 |
C7烷烃 | 3.25 |
C8烷烃 | 0.12 |
总芳族化合物 | 75.36 |
BTX | 74.85 |
C9+芳族化合物 | 0.51 |
三甲基苯 | 0.03 |
EMBzs | 0.21 |
C10+芳族化合物 | 0.08 |
次要量物质(未识别) | 8.10 |
在该测试期间,反应器产物流(加氢裂化产物流)是经由在线气相色谱仪来分析的,其安装有火焰离子化检测仪,并且校正来允许识别和量化烃物质。(使用Shimadzu GC-2014来测量,其安装有60m长;0.32mm内径和5.00μm膜厚的DB1柱。分析测试方法条件:-烘箱50℃保持3min,以5℃/min升温到250℃,保持5min。氦载气柱流量3.37ml/min;总流量107.4ml/min;分离比30:1;线速度40.0cm/s;入口压力25.8psi)。
下文的表2中显示了用于在每组运行条件下进行的实验的加氢裂化产物流。
因此,已经发现包含C5+烃的高度复杂混合物的供料流可以使用本发明的加氢裂化/加氢脱硫方法转化成包含LPG的加氢裂化产物流,中间体芳族流和小于5wt%的甲烷。
实施例3H2/烃摩尔比对苯纯度的影响
反应测试是使用与实施例2所述相同的催化剂和相同的实验装置来进行的。该加氢裂化/加氢脱硫方法是在整个实验中,在495℃的温度,大约1380kPa表压(200psig)和1h-1的WHSV(基于液体供料的重量),使用植物来源的热解汽油(具有下表3所示的组成)来进行的。
表3:
组分 | wt%(通过GC) |
总C6-C8烷烃 | 13.14 |
C6烷烃 | 12.25 |
C7烷烃 | 0.81 |
C8烷烃 | 0.08 |
总芳族化合物 | 72.89 |
BTX | 71.78 |
C9+芳族化合物 | 0.98 |
三甲基苯 | 0.07 |
EMBzs | 0.48 |
C10+芳族化合物 | 0.13 |
次要量物质(未识别) | 13.97 |
因此,已经发现产物流中较高的苯纯度可以通过选择相对低的H2/HC摩尔比来获得;参见表4。
表4
Claims (14)
1.一种生产BTX的方法,其包含:
(a)在包括450-580℃的温度,300-5000kPa的表压和0.1-10h-1的重时空速的工艺条件下,在氢的存在下使包含C5-C12烃的供料流与加氢裂化/加氢脱硫催化剂接触,来生产包含BTX的加氢裂化产物流,所述催化剂包含相对于总催化剂重量的0.1-1wt%的加氢金属,和沸石,所述沸石的孔径是并且二氧化硅(SiO2)与氧化铝(Al2O3)摩尔比是5-200;和
(b)使BTX从该加氢裂化产物流分离。
2.根据权利要求1的方法,其中该加氢裂化产物流进一步包含小于5wt%的甲烷,优选小于4wt%的甲烷,更优选小于3wt%的甲烷,特别优选小于2wt%的甲烷和最优选小于1wt%的甲烷。
3.根据权利要求1或2的方法,其中该加氢裂化产物流进一步包含小于1wt%的非芳族C6+烃和优选小于0.5wt%的非芳族C6+烃。
4.根据权利要求1-3任一项的方法,其中该加氢裂化/加氢脱硫条件包括470-550℃的温度,600-3000kPa的表压和0.2-6h-1的重时空速,并且优选470-550℃的温度,1000-2000kPa的表压和0.4-2h-1的重时空速。
5.根据权利要求1-4任一项的方法,其中该加氢金属是选自元素周期表第10族的至少一种元素。
6.根据权利要求1-5任一项的方法,其中该沸石是ZSM-5。
7.根据权利要求1-6任一项的方法,其中该加氢金属是铂。
8.根据权利要求1-7任一项的方法,其中该加氢裂化/加氢脱硫催化剂包含ZSM-5和Pt改性的氧化铝(Pt/Al2O3)的混合物,其中ZSM-5:Pt/Al2O3的重量比是5:1-1:5,优选3:1-1:3。
9.根据权利要求1-8任一项的方法,其中该供料流进一步包含10-300wppm的硫并且该加氢裂化产物流包含小于5wppm的硫。
10.根据权利要求1-9任一项的方法,其中在反应器供料中,氢与烃物质的摩尔比(H2/HC摩尔比)是至少1:1-4:1,优选至少1:1-3:1和最优选1:1-2:1。
11.根据权利要求1-10任一项的方法,其中该供料流包含热解汽油、直馏石脑油、轻质焦化石脑油和焦化炉轻质油或其混合物。
12.根据权利要求1-11任一项的方法,其中该BTX通过气-液分离或者蒸馏从加氢裂化产物流分离。
13.根据权利要求1-12任一项的方法,其进一步包括在适合于生产包含苯和燃料气的加氢脱烷基化产物流的条件下,使所述BTX与氢接触的步骤。
14.根据权利要求13的方法,其中该加氢脱烷基化在加氢脱烷基化条件下,在不存在加氢脱烷基化催化剂的情况下进行,所述加氢脱烷基化条件包括600-800℃的温度,3-10MPa的表压和15-45秒的反应时间;或者其中该加氢脱烷基化在选自以下的加氢脱烷基化催化剂的存在下,在包括500-650℃的温度,3.5-7MPa的表压和0.5-2h-1的重时空速的加氢脱烷基化条件下进行:负载的氧化铬催化剂、负载的氧化钼催化剂、在二氧化硅或氧化铝上的铂和在二氧化硅或氧化铝上的氧化铂。
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KR20150021558A (ko) | 2015-03-02 |
US9926240B2 (en) | 2018-03-27 |
EP2855636A1 (en) | 2015-04-08 |
CN104395436B (zh) | 2016-10-05 |
EA028843B1 (ru) | 2018-01-31 |
EA201401334A1 (ru) | 2015-04-30 |
US20150166434A1 (en) | 2015-06-18 |
WO2013182534A1 (en) | 2013-12-12 |
EP2855636B1 (en) | 2022-02-16 |
SG11201407321SA (en) | 2014-12-30 |
JP2015523345A (ja) | 2015-08-13 |
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