CN107759434A - Aromatic hydrocarbons converts the combination bed process of increasing production of xylol - Google Patents
Aromatic hydrocarbons converts the combination bed process of increasing production of xylol Download PDFInfo
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- CN107759434A CN107759434A CN201610710714.0A CN201610710714A CN107759434A CN 107759434 A CN107759434 A CN 107759434A CN 201610710714 A CN201610710714 A CN 201610710714A CN 107759434 A CN107759434 A CN 107759434A
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- Prior art keywords
- aromatic hydrocarbons
- product
- raw material
- catalyst
- increasing production
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 70
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002994 raw material Substances 0.000 claims abstract description 41
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- -1 solve the problems Chemical compound 0.000 claims abstract description 19
- 239000000047 product Substances 0.000 claims abstract description 18
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 239000012263 liquid product Substances 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 4
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000000926 separation method Methods 0.000 claims abstract description 3
- 239000002808 molecular sieve Substances 0.000 claims description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 229930195733 hydrocarbon Natural products 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052702 rhenium Inorganic materials 0.000 claims description 4
- 125000002619 bicyclic group Chemical group 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001833 catalytic reforming Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000007809 chemical reaction catalyst Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 14
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000009466 transformation Effects 0.000 abstract description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 abstract 4
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 20
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 20
- QNLZIZAQLLYXTC-UHFFFAOYSA-N 1,2-dimethylnaphthalene Chemical compound C1=CC=CC2=C(C)C(C)=CC=C21 QNLZIZAQLLYXTC-UHFFFAOYSA-N 0.000 description 20
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 20
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 20
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 20
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 20
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 20
- 206010013786 Dry skin Diseases 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- YQZBFMJOASEONC-UHFFFAOYSA-N 1-Methyl-2-propylbenzene Chemical compound CCCC1=CC=CC=C1C YQZBFMJOASEONC-UHFFFAOYSA-N 0.000 description 10
- 238000007599 discharging Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000002790 naphthalenes Chemical class 0.000 description 4
- 238000010555 transalkylation reaction Methods 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 102220065736 rs543286136 Human genes 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
-
- 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
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—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
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/22—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
-
- 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
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7869—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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
Abstract
The present invention relates to a kind of combination bed process of aromatic hydrocarbons conversion increasing production of xylol, mainly solve the problems, such as effectively handle polycyclic aromatic hydrocarbon in existing aromatic hydrocarbons transformation technology, the present invention converts the combination bed process of increasing yield of p-xylene by using a kind of aromatic hydrocarbons, comprises the following steps：A) after preheating will be mixed with hydrogen containing C9+ aromatic components, it is passed through in paste state bed reactor, contacts and react with the catalyst in slurry bed system, generates product I；B) reaction product I enters the catalyst haptoreaction in fixed bed reactors, with fixed bed after preheating is mixed with benzene and/or toluene, generates product II；C) product II carries out Oil-gas Separation after exchanging heat, cooling down, and obtains gas-phase product III and liquid product V；D) part of gas-phase product III returns to slurry bed system and mixed with the raw material in step a)；The technical scheme that dimethylbenzene produces as product, solve the problem, production paraxylene process is converted available for heavy arene.
Description
Technical field
The present invention relates to a kind of combination bed process of aromatic hydrocarbons conversion increasing production of xylol.
Background technology
Carbon nine and its above heavy aromatics (C9 +A) be oil refining and aromatics production process accessory substance, with oil refining scale expansion
Big and Aromatic Hydrocarbon United Plant maximization, the Heavy Aromatic Hydrocarbons of by-product are more and more, how to be efficiently to carry using this part resource
The important channel of high device benefit.At present, toluene and carbon nine and its above heavy aromatics (C are utilized9 +A) transalkylation reaction volume increase two
Toluene is to be widely used effectively using heavy aromatics come one of method of increasing production of xylol.But in the reaction raw materials carbon ten and
The content of its above heavy arene is higher, and especially naphthalene series substance content is higher, and catalyst activity reduces, and quick coking and deactivation.
Therefore, there is strict limitation to the naphthalene series substance content in reaction raw materials in traditional alkyl transfering process.At present, disproportionation and alkane
Utilization of the group-transfer unit to C9+ heavy aromatics is concentrated mainly on the utilization to C9A and part C10A, and naphthalene series substance and C11+A are obtained
Utilized less than effective.Transalkylation reaction technique uses fixed bed or radial bed more at present, the catalyst change cycle be 4 years with
On.
The lighting of naphthalene series compound need to be carried out in the case where metal acts synergistically with acidity, be hydrogenated with and be hydrogenated with by part open loop
Cracking process produces light aromatics.The catalyst such as noble metal platinum, palladium and base metal nickel, molybdenum is reported to be hydrogenated with as polycyclic aromatic hydrocarbon
The active principle of cracking.Naphthalene series compound hydrocracking reaction is strongly exothermic process, and bed is easily caused in fixed bed reactors
The temperature runaway of layer.Mononuclear aromatics ties up to same beds with polycyclic aromatic hydrocarbon coexisting body and reacted, and polycyclic aromatic hydrocarbon will suppress single
The conversion of PAH, and deep hydrogenation reaction also occurs for mononuclear aromatics.
CN1122571 discloses a kind of molecular sieve catalyst containing noble metal, and the catalyst is with 10-80% (weight) mercerising
The ZSM-5 of zeolite or β zeolites and 0-70% (weight), 5-90% (weight) γ-Al2O3 are carrier, load 0.001-0.5 weights
Measure part platinum and 0.01-10.0 parts by weight tin or 0.01-7.0 parts by weight lead.The catalyst can handle high C9+A raw materials, and improve
Mixed xylenes yield and catalyst stability.
CN1259930A discloses a kind of heavy aromatics processing method, to contain zeolite of the restricted index as 0.5-3 and hydrogenation
The medium pore zeolite that component is the first catalyst and restricted index is 3-12 is that the second catalyst forms group technology, the technique energy
Effective conversion of heavy arene.
US20080026931A1 disclose it is a kind of containing acidic molecular sieve and rhenium, tin, Chu metal component catalyst, be used for
Heavy aromatics transalkylation, there is greater activity and relatively low ring loss rate.
Above-mentioned patent document is fixed bed reaction technique, and is not directed to handle C9 +Naphthalene series substance component in A.
The content of the invention
The invention aims to overcome existing aromatic hydrocarbons transformation technology effectively to handle polycyclic aromatic hydrocarbon compounds and urge
The shortcomings of agent short life.A kind of combination bed process of new aromatic hydrocarbons conversion increasing production of xylol is provided, the technique turns for aromatic hydrocarbons
Change reaction, can effectively handle polycyclic aromatic hydrocarbon compounds, improve the utilization rate of Heavy Aromatic Hydrocarbons.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：Aromatic hydrocarbons converts the combination of increasing production of xylol
Bed process, comprise the following steps：
A) after the raw material I containing C9+ aromatic components being mixed to preheating with hydrogen, it is passed through in paste state bed reactor, with slurry
Catalyst I contacts in bed react, and generate product I；
B) reaction product I enters in fixed bed reactors, with fixed bed after preheating is mixed with the raw material II of benzene and/or toluene
Catalyst II haptoreactions, generate product II；
C) product II carries out Oil-gas Separation after exchanging heat, cooling down, and obtains gas-phase product III and liquid product V；
D) part of gas-phase product III returns to slurry bed system and mixed with the raw material I in step a)；
E) liquid product V separates through rectifying, and wherein benzene and/or toluene at least partly return to fixed bed and step b) Central Plains
Expect II mixing；C9+A components at least partly return to slurry bed system and mixed with the raw material I in step a)；Dimethylbenzene produces as product.
In such scheme, the bicyclic or polycyclic compound containing 0.1-100% in raw material I C9+ aromatic hydrocarbons.Raw material I C9+
Aromatic hydrocarbons comes from catalytic reforming, pyrolysis gasoline hydrogenation or residual oil/heavy-oil hydrogenation component.The benzene and/or toluene of raw material II are with raw material I's
The part by weight of C9+ aromatic hydrocarbons is 1：9~9：1.Hydrogen hydrocarbon mol ratio in paste state bed reactor is 0.5-6, reaction temperature 100-
400 DEG C, reaction pressure 0.5-5.0MPa, liquid charging stock weight space velocity is 1-10h-1.The hydrogen hydrocarbon mol ratio of fixed bed reactors
For 0.5-4, reaction temperature is 300-500 DEG C, pressure 0.5-5.0MPa, and liquid charging stock weight space velocity is 1-8h-1。
In such scheme, in paste state bed reactor catalyst contain it is at least one selected from ZSM-5, Beta, USY, MCM-44,
Al2O3, amorphous aluminosilicate component.In paste state bed reactor catalyst also containing it is at least one selected from Pt, Pd, Ir, Rh,
Ni, Mo metal component.In above-mentioned technical proposal, it is preferred that contain element Ir and Ni in catalyst.In above-mentioned technical proposal,
Preferably, element Rh and Ni are contained in catalyst I.
Catalyst contains at least one acidity selected from ZSM-5, MOR, Beta, ZSM-12, NU-87 in fixed bed reactors
Molecular sieve component.Catalyst contains at least one metal component selected from Pt, Re, Mo, Zn, Fe in fixed bed reactors.It is above-mentioned
In technical scheme, it is preferred that contain Re and Zn in catalyst II；In above-mentioned technical proposal, it is preferred that contain Pt in catalyst II
And Fe.
The present invention mainly realizes the conversion to bicyclic and polycyclic heavy aromatics, the light aromatics of generation by paste state bed reactor
Disproportionation and transalkylation reaction occurs on fixed bed catalyst with benzene or/and toluene again.The present invention realizes at a lower temperature
Polycyclic aromatic hydrocarbon hydrocracking, be advantageous to improve heavy aromatics conversion ratio.And it is disproportionated at relatively high temperatures by fixed bed and alkane
Group-transfer is reacted.The present invention by two reactor handles different material, can each course of reaction of efficient hardening, while suppress benzene
Ring is hydrogenated with, and reduces aromatic ring loss.
Embodiment
【Embodiment 1】
By 70 grams of ZSM-5 molecular sieves and 50 grams of boehmites and be well mixed, carrier is made in roller forming, roasting, will
A certain amount of chloroplatinic acid is impregnated in carrier surface, and 120 DEG C of dryings are calcined 3 hours and gone back by hydrogen at 400 DEG C for 4 hours, 500 DEG C
Catalyst A1 is made after former 3 hours.
By 70 grams of MOR molecular sieves and 50 grams of boehmites and it is well mixed, carrier is made in extruded moulding, roasting, by one
Quantitative ammonium perrhenate is impregnated in carrier surface, and 120 DEG C of dryings are calcined 3 hours and gone back by hydrogen at 400 DEG C for 4 hours, 500 DEG C
Catalyst B1 is made after former 3 hours.
10 grams of catalyst A 1 are filled in paste state bed reactor, fill 10 grams of catalyst B1 in fixed bed reactors, and be passed through hydrogen
Gas, C9+ heavy aromatics raw material is passed through paste state bed reactor, reaction pressure 2.0MPa, reaction temperature with the flow of 20 Grams Per Hours
300 DEG C, hydrogen hydrocarbon molecule ratio is 3.0, and paste state bed reactor discharging enters fixed bed reactors after being mixed with 20 Grams Per Hour toluene,
380 DEG C of fixed bed reaction temperature.C9A raw material weights composition is in heavy aromatics：Propyl benzene 5.70%, the first and second benzene 31.51%, trimethylbenzene
62.79%, C10 +A weight forms：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene
28.84%th, naphthalene 11.80%, methyl naphthalene 10.49%, dimethylnaphthalene 8.16%, other components 8.10%.Catalyst composition such as table
1st, shown in table 2, evaluation result is as shown in table 3.
【Embodiment 2】
By 30 grams of ZSM-5 molecular sieves, 40 grams of USY molecular sieves and 50 grams of boehmites and be well mixed, roller forming, roasting
Carrier is fired into, a certain amount of chloroplatinic acid is carried on carrier surface, 120 DEG C of dryings are calcined 3 hours and passed through for 4 hours, 500 DEG C
Catalyst A2 is made after being reduced 3 hours at 400 DEG C in hydrogen.
By 70 grams of Beta molecular sieves and 50 grams of boehmites and it is well mixed, carrier is made in extruded moulding, roasting, by one
Quantitative ammonium perrhenate is impregnated in carrier surface, and 120 DEG C of dryings are calcined 3 hours and gone back by hydrogen at 400 DEG C for 4 hours, 500 DEG C
Catalyst B2 is made after former 3 hours.
10 grams of catalyst A2 are filled in paste state bed reactor, 10 grams of catalyst B2 are filled in fixed bed reactors, and are passed through hydrogen,
C9+ heavy aromatics raw material is passed through paste state bed reactor, reaction pressure 2.0MPa, reaction temperature 300 with the flow of 20 Grams Per Hours
DEG C, hydrogen hydrocarbon molecule ratio is 3.0, and paste state bed reactor discharging enters fixed bed reactors after being mixed with 20 Grams Per Hour toluene, fixed
380 DEG C of reaction temperature of bed.C9A raw material weights composition is in heavy aromatics：Propyl benzene 5.70%, the first and second benzene 31.51%, trimethylbenzene
62.79%, C10 +A weight forms：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene
28.84%th, naphthalene 11.80%, methyl naphthalene 10.49%, dimethylnaphthalene 8.16%, other components 8.10%.Catalyst composition such as table
1st, shown in table 2, evaluation result is as shown in table 3.
【Embodiment 3】
By 70 grams of USY molecular sieves and 50 grams of amorphous aluminosilicates and be well mixed, carrier is made in roller forming, roasting,
A certain amount of chloroplatinic acid is carried on carrier surface, 120 DEG C of dryings are calcined 3 hours and by hydrogen at 400 DEG C for 4 hours, 500 DEG C
Catalyst A3 is made after 3 hours in reduction.
By 70 grams of ZSM-12 molecular sieves and 50 grams of boehmites and it is well mixed, carrier is made in extruded moulding, roasting, will
A certain amount of ammonium perrhenate is impregnated in carrier surface, and 120 DEG C of dryings are calcined 3 hours and by hydrogen at 400 DEG C for 4 hours, 500 DEG C
Catalyst B3 is made after 3 hours in reduction.
10 grams of catalyst A3 are filled in paste state bed reactor, 10 grams of catalyst B3 are filled in fixed bed reactors, and are passed through hydrogen,
C9+ heavy aromatics raw material is passed through paste state bed reactor, reaction pressure 2.0MPa, reaction temperature 300 with the flow of 20 Grams Per Hours
DEG C, hydrogen hydrocarbon molecule ratio is 3.0, and paste state bed reactor discharging enters fixed bed reactors after being mixed with 20 Grams Per Hour toluene, fixed
380 DEG C of reaction temperature of bed.C9A raw material weights composition is in heavy aromatics：Propyl benzene 5.70%, the first and second benzene 31.51%, trimethylbenzene
62.79%, C10 +A weight forms：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene
28.84%th, naphthalene 11.80%, methyl naphthalene 10.49%, dimethylnaphthalene 8.16%, other components 8.10%.Catalyst composition such as table
1st, shown in table 2, evaluation result is as shown in table 3.
【Embodiment 4】
By 70 grams of USY molecular sieves and 50 grams of amorphous aluminosilicates and be well mixed, carrier is made in roller forming, roasting,
A certain amount of chlorine palladium acid is carried on carrier surface, 120 DEG C of dryings are calcined 3 hours and by hydrogen at 400 DEG C for 4 hours, 500 DEG C
Catalyst A4 is made after 3 hours in reduction.
By 70 grams of MOR molecular sieves and 50 grams of boehmites and it is well mixed, carrier is made in extruded moulding, roasting, by one
Quantitative chloroplatinic acid is impregnated in carrier surface, and 120 DEG C of dryings are calcined 3 hours and by hydrogen in 400 DEG C of reduction for 4 hours, 500 DEG C
Catalyst B4 is made after 3 hours.
10 grams of catalyst A4 are filled in paste state bed reactor, 10 grams of catalyst B4 are filled in fixed bed reactors, and are passed through hydrogen,
C9+ heavy aromatics raw material is passed through paste state bed reactor, reaction pressure 2.0MPa, reaction temperature 300 with the flow of 20 Grams Per Hours
DEG C, hydrogen hydrocarbon molecule ratio is 3.0, and paste state bed reactor discharging enters fixed bed reactors after being mixed with 20 Grams Per Hour toluene, fixed
380 DEG C of reaction temperature of bed.C9A raw material weights composition is in heavy aromatics：Propyl benzene 5.70%, the first and second benzene 31.51%, trimethylbenzene
62.79%, C10 +A weight forms：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene
28.84%th, naphthalene 11.80%, methyl naphthalene 10.49%, dimethylnaphthalene 8.16%, other components 8.10%.Catalyst composition such as table
1st, shown in table 2, evaluation result is as shown in table 3.
【Embodiment 5】
By 70 grams of USY molecular sieves and 50 grams of amorphous aluminosilicates and be well mixed, carrier is made in roller forming, roasting,
A certain amount of iridium chloride and nickel nitrate are carried on carrier surface, 120 DEG C of dryings are calcined 3 hours and pass through hydrogen for 4 hours, 500 DEG C
Catalyst A5 is made after being reduced 3 hours at 400 DEG C in gas.
By 70 grams of MOR molecular sieves and 50 grams of boehmites and it is well mixed, carrier is made in extruded moulding, roasting, by one
Quantitative chloroplatinic acid and iron chloride is impregnated in carrier surface, and 120 DEG C of dryings are calcined 3 hours and existed by hydrogen for 4 hours, 500 DEG C
Catalyst B5 is made after 3 hours in 400 DEG C of reduction.
10 grams of catalyst A5 are filled in paste state bed reactor, 10 grams of catalyst B5 are filled in fixed bed reactors, and are passed through hydrogen,
C9+ heavy aromatics raw material is passed through paste state bed reactor, reaction pressure 2.0MPa, reaction temperature 300 with the flow of 20 Grams Per Hours
DEG C, hydrogen hydrocarbon molecule ratio is 3.0, and paste state bed reactor discharging enters fixed bed reactors after being mixed with 20 Grams Per Hour toluene, fixed
380 DEG C of reaction temperature of bed.C9A raw material weights composition is in heavy aromatics：Propyl benzene 5.70%, the first and second benzene 31.51%, trimethylbenzene
62.79%, C10+A weight form：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene
28.84%th, naphthalene 11.80%, methyl naphthalene 10.49%, dimethylnaphthalene 8.16%, other components 8.10%.Catalyst composition such as table
1st, shown in table 2, evaluation result is as shown in table 3.
【Embodiment 6】
By 30 grams of USY molecular sieves and 90 grams of amorphous aluminosilicates and be well mixed, carrier is made in roller forming, roasting,
A certain amount of radium chloride and nickel nitrate are loaded in carrier surface, 120 DEG C of dryings are calcined 3 hours and pass through hydrogen for 4 hours, 500 DEG C
Catalyst A6 is made after being reduced 3 hours at 400 DEG C.
By 70 grams of NU-87 molecular sieves and 50 grams of boehmites and it is well mixed, carrier is made in extruded moulding, roasting, will
A certain amount of perrhenic acid and zinc chloride are impregnated in carrier surface, and 120 DEG C of dryings are calcined 3 hours and pass through hydrogen for 4 hours, 500 DEG C
Catalyst B6 is made after being reduced 3 hours at 400 DEG C.
10 grams of catalyst A6 are filled in paste state bed reactor, 10 grams of catalyst B6 are filled in fixed bed reactors, and are passed through hydrogen,
C9+ heavy aromatics raw material is passed through paste state bed reactor, reaction pressure 2.0MPa, reaction temperature 300 with the flow of 20 Grams Per Hours
DEG C, hydrogen hydrocarbon molecule ratio is 3.0, and paste state bed reactor discharging enters fixed bed reactors after being mixed with 20 Grams Per Hour toluene, fixed
380 DEG C of reaction temperature of bed.C9A raw material weights composition is in heavy aromatics：Propyl benzene 5.70%, the first and second benzene 31.51%, trimethylbenzene
62.79%, C10+A weight form：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene
28.84%th, naphthalene 11.80%, methyl naphthalene 10.49%, dimethylnaphthalene 8.16%, other components 8.10%.Catalyst composition such as table
1st, shown in table 2, evaluation result is as shown in table 3.
【Embodiment 7】
10 grams of catalyst A3 are filled in paste state bed reactor, 10 grams of catalyst B4 are filled in fixed bed reactors, and are passed through hydrogen,
C9+ heavy aromatics raw material is passed through paste state bed reactor, reaction pressure 2.0MPa, reaction temperature 300 with the flow of 20 Grams Per Hours
DEG C, hydrogen hydrocarbon molecule ratio is 3.0, and paste state bed reactor discharging enters fixed bed reactors after being mixed with 20 Grams Per Hour toluene, fixed
380 DEG C of reaction temperature of bed.C9A raw material weights composition is in heavy aromatics：Propyl benzene 5.70%, the first and second benzene 31.51%, trimethylbenzene
62.79%, C10+A weight form：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene
28.84%th, naphthalene 11.80%, methyl naphthalene 10.49%, dimethylnaphthalene 8.16%, other components 8.10%.Catalyst composition such as table
1st, shown in table 2, evaluation result is as shown in table 3.
【Embodiment 8】
10 grams of catalyst A3 are filled in paste state bed reactor, 10 grams of catalyst B1 are filled in fixed bed reactors, and are passed through hydrogen,
C9+ heavy aromatics raw material is passed through paste state bed reactor, reaction pressure 2.0MPa, reaction temperature 300 with the flow of 20 Grams Per Hours
DEG C, hydrogen hydrocarbon molecule ratio is 3.0, and paste state bed reactor discharging enters fixed bed reactors after being mixed with the toluene of 20 Grams Per Hours, Gu
380 DEG C of fixed bed reaction temperature.C9A raw material weights composition is in heavy aromatics：Propyl benzene 5.70%, the first and second benzene 31.51%, trimethylbenzene
62.79%, C10 +A weight forms：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene
28.84%th, naphthalene 11.80%, methyl naphthalene 10.49%, dimethylnaphthalene 8.16%, other components 8.10%.Catalyst composition such as table
1st, shown in table 2, evaluation result is as shown in table 3.
【Embodiment 9】
10 grams of catalyst A3 are filled in paste state bed reactor, 10 grams of catalyst B1 are filled in fixed bed reactors, and are passed through hydrogen,
C9+ heavy aromatics raw material is passed through paste state bed reactor, reaction pressure 2.0MPa, reaction temperature 300 with the flow of 10 Grams Per Hours
DEG C, hydrogen hydrocarbon molecule ratio is 3.0, and paste state bed reactor discharging enters fixed bed reactors after being mixed with 30 Grams Per Hour toluene, fixed
380 DEG C of reaction temperature of bed.C9A raw material weights composition is in heavy aromatics：Propyl benzene 5.70%, the first and second benzene 31.51%, trimethylbenzene
62.79%, C10 +A weight forms：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene
28.84%th, naphthalene 11.80%, methyl naphthalene 10.49%, dimethylnaphthalene 8.16%, other components 8.10%.Catalyst composition such as table
1st, shown in table 2, evaluation result is as shown in table 3.
【Embodiment 10】
10 grams of catalyst A3 are filled in paste state bed reactor, 10 grams of catalyst B1 are filled in fixed bed reactors, and are passed through hydrogen,
C9+ heavy aromatics raw material is passed through paste state bed reactor, reaction pressure 2.0MPa, reaction temperature 300 with the flow of 20 Grams Per Hours
DEG C, hydrogen hydrocarbon molecule ratio is 3.0, and paste state bed reactor discharging enters fixed bed reactors after being mixed with 10 Grams Per Hour toluene, fixed
380 DEG C of reaction temperature of bed.C9A raw material weights composition is in heavy aromatics：Propyl benzene 5.70%, the first and second benzene 31.51%, trimethylbenzene
62.79%, C10 +A weight forms：Diethylbenzene 3.33%, dimethyl ethylbenzene 26.96%, methyl propyl benzene 2.32%, durene
28.84%th, naphthalene 11.80%, methyl naphthalene 10.49%, dimethylnaphthalene 8.16%, other components 8.10%.Catalyst composition such as table
1st, shown in table 2, evaluation result is as shown in table 3.
Table 1
Table 2
| Fixed bed catalyst II | Catalyst carrier | Metal promoter/wt% |
| B1 | MOR | Re/0.2 |
| B2 | Beta | Re/0.2 |
| B3 | ZSM-12 | Re/0.2 |
| B4 | MOR | Pt/0.1 |
| B5 | MOR | Pt/0.1-Fe/0.1 |
| B6 | NU-87 | Re/0.1-Zn/0.1 |
Table 3
Claims (10)
1. aromatic hydrocarbons converts the combination bed process of increasing production of xylol, comprise the following steps：
A) after the raw material I containing C9+ aromatic hydrocarbons being mixed to preheating with hydrogen, it is passed through in paste state bed reactor, with urging in slurry bed system
Agent I contacts react, and generate product I；
B) reaction product I enters urging in fixed bed reactors, with fixed bed after preheating is mixed with the raw material II of benzene and/or toluene
Agent II haptoreactions, generate product II；
C) product II carries out Oil-gas Separation after exchanging heat, cooling down, and obtains gas-phase product III and liquid product V；
D) part of gas-phase product III returns to slurry bed system and mixed with the raw material I in step a)；
E) liquid product V separates through rectifying, and wherein benzene and/or toluene at least partly return to fixed bed and raw material II in step b)
Mixing；C9+ aromatic components at least partly return to slurry bed system and mixed with the raw material I in step a)；Dimethylbenzene produces as product.
2. the combination bed process of aromatic hydrocarbons conversion increasing production of xylol according to claim 1, it is characterised in that raw material I C9+
Bicyclic or polycyclic compound containing 0.1-100% in aromatic hydrocarbons.
3. the combination bed process of aromatic hydrocarbons conversion increasing production of xylol according to claim 1, it is characterised in that raw material I C9+
Aromatic hydrocarbons comes from catalytic reforming, pyrolysis gasoline hydrogenation or residual oil/heavy-oil hydrogenation component.
4. the combination bed process of aromatic hydrocarbons conversion increasing production of xylol according to claim 1, it is characterised in that the benzene of raw material II
And/or the part by weight of toluene and raw material I C9+ aromatic hydrocarbons is 1：9~9：1.
5. the combination bed process of aromatic hydrocarbons conversion increasing production of xylol according to claim 1, it is characterised in that slurry reactor
Hydrogen hydrocarbon mol ratio in device is 0.5-6, and reaction temperature is 100-400 DEG C, reaction pressure 0.5-5.0MPa, liquid charging stock weight
Air speed is 1-10h-1。
6. the combination bed process of aromatic hydrocarbons conversion increasing production of xylol according to claim 1, it is characterised in that fixed bed reaction
The hydrogen hydrocarbon mol ratio of device is 0.5-4, and reaction temperature is 300-500 DEG C, pressure 0.5-5.0MPa, and liquid charging stock weight space velocity is
1-8h-1。
7. the combination bed process of aromatic hydrocarbons conversion increasing production of xylol according to claim 1, it is characterised in that slurry reactor
Catalyst I contains at least one selected from ZSM-5, Beta, USY, MCM-44, Al2O3, the component of amorphous aluminosilicate in device.
8. the combination bed process of aromatic hydrocarbons conversion increasing production of xylol according to claim 7, it is characterised in that slurry reactor
Catalyst I also contains at least one metal component selected from Pt, Pd, Ir, Rh, Ni, Mo in device.
9. the combination bed process of aromatic hydrocarbons conversion increasing production of xylol according to claim 1, it is characterised in that fixed bed reaction
Catalyst II contains at least one acidic molecular sieve component selected from ZSM-5, MOR, Beta, ZSM-12, NU-87 in device.
10. the combination bed process of the aromatic hydrocarbons conversion increasing production of xylol described in claim 9, it is characterised in that in fixed bed reactors
Catalyst contains at least one metal component selected from Pt, Re, Mo, Zn, Fe.
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| CN103540349A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Low-quality heavy oil and residual oil hydrotreatment combined process capable of prolonging service life of catalyst |
| CN104357084A (en) * | 2014-11-11 | 2015-02-18 | 中国海洋石油总公司 | Combined process for conversion of C10+ heavy aromatics to light aromatics |
| CN105272803A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Method for disproportionation and transalkylation of toluene and heavy aromatic hydrocarbon |
| EP3015445A1 (en) * | 2014-10-30 | 2016-05-04 | China Petroleum & Chemical Corporation | A method for producing an aromatic hydrocarbon with an oxygenate as raw material |
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- 2016-08-23 CN CN201610710714.0A patent/CN107759434A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103540349A (en) * | 2012-07-12 | 2014-01-29 | 中国石油天然气股份有限公司 | Low-quality heavy oil and residual oil hydrotreatment combined process capable of prolonging service life of catalyst |
| CN105272803A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Method for disproportionation and transalkylation of toluene and heavy aromatic hydrocarbon |
| EP3015445A1 (en) * | 2014-10-30 | 2016-05-04 | China Petroleum & Chemical Corporation | A method for producing an aromatic hydrocarbon with an oxygenate as raw material |
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Application publication date: 20180306 |