CN109569703B - Catalyst for producing gasoline component from naphtha and methanol, preparation method and application - Google Patents
Catalyst for producing gasoline component from naphtha and methanol, preparation method and application Download PDFInfo
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- CN109569703B CN109569703B CN201710896604.2A CN201710896604A CN109569703B CN 109569703 B CN109569703 B CN 109569703B CN 201710896604 A CN201710896604 A CN 201710896604A CN 109569703 B CN109569703 B CN 109569703B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000003054 catalyst Substances 0.000 title claims abstract description 100
- 239000003502 gasoline Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 27
- 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 23
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 20
- 239000010457 zeolite Substances 0.000 claims abstract description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 18
- 238000005899 aromatization reaction Methods 0.000 claims abstract description 18
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 57
- 239000002994 raw material Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- 150000001875 compounds Chemical class 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910001122 Mischmetal Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical compound [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 description 24
- 239000007789 gas Substances 0.000 description 18
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000011069 regeneration method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 230000008929 regeneration Effects 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 239000001273 butane Substances 0.000 description 4
- 238000004523 catalytic cracking Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- -1 BTX aromatic hydrocarbon Chemical class 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/48—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 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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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
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
一种由石脑油和甲醇芳构化生产汽油组分的催化剂，包括载体和以载体为基准计算的含量如下的活性组分：Ag0.1～5.0质量％，VA族元素氧化物1.0～15.0质量％，稀土元素氧化物0.1～3.0质量％，所述的载体包括40～80质量％的ZSM‑5沸石、3～30质量％的氧化铝和5～30质量％的无定形硅酸铝。该催化剂可促使石脑油和甲醇进行共芳构化反应生成高辛烷值的汽油组分，并可副产优质液化气。A catalyst for producing gasoline components by aromatizing naphtha and methanol, comprising a carrier and active components with the following contents calculated on the basis of the carrier: Ag 0.1-5.0 mass %, VA group element oxides 1.0-15.0 mass %, rare earth element oxide 0.1-3.0 mass %, the carrier comprises 40-80 mass % of ZSM-5 zeolite, 3-30 mass % of alumina and 5-30 mass % of amorphous aluminum silicate. The catalyst can promote the co-aromatization reaction of naphtha and methanol to generate gasoline components with high octane number, and can by-produce high-quality liquefied gas.
Description
Technical Field
The invention relates to a catalyst for producing a gasoline component by utilizing methanol and naphtha aromatization, a preparation method and application thereof.
Background
BTX is an important basic chemical raw material, with the rapid development of the economy of China and the continuous improvement of the living standard of people, the BTX aromatic hydrocarbon industry of China develops rapidly, and the apparent consumption reaches the first place in the world. Light hydrocarbon aromatization is a new petroleum processing technology developed in the last two decades. Under the conditions of certain temperature, pressure and the existence of modified zeolite molecular sieve catalyst, light hydrocarbon is converted into aromatic hydrocarbon or high-octane gasoline blending component rich in aromatic hydrocarbon. Methanol aromatization is a technology for producing BTX from coal and is an important supplement for producing aromatic hydrocarbon from petroleum. Therefore, the development of light hydrocarbon aromatization technology and methanol aromatization technology has important significance for expanding the source of aromatic hydrocarbon raw materials and increasing the yield of aromatic hydrocarbon.
The light hydrocarbon aromatization process taking naphtha as a raw material is accompanied by a series of reactions such as alkane activation, dehydroaromatization or hydrogen transfer aromatization, the temperature is usually higher than 500 ℃, and the process is a strong heat absorption reaction process, so that the energy consumption is large, and the application of a low-carbon alkane aromatization technology is limited. The methanol aromatization is a strong exothermic reaction process, and how to effectively exchange heat and extract heat and control the temperature rise of a reaction bed layer is important content of the research of the methanol aromatization process and is one of key points for determining whether an industrial device can continuously, stably and periodically operate. The prior art discloses treatment catalysts and techniques for co-reacting naphtha with methanol, including:
the ' butane and methanol cofeed aromatization reaction rule ' is reported in the ' 2012 volume-increased journal, and the authors research butane and methanol cofeed aromatization reaction on a modified ZSM-5 molecular sieve catalyst, and find that the addition of methanol inhibits the activation of butane, so that the concentration of a low-carbon olefin intermediate which is generated by butane activation and mainly takes propylene as a main component is relatively low, and the low-carbon olefin intermediate is not beneficial to generating aromatic hydrocarbon through multi-step reaction, and mainly generates propane through hydrogen transfer; when the content of methanol in the raw materials is increased, the concentration of the low-carbon olefin intermediate in the reaction system is increased, the generation of aromatic hydrocarbon is promoted, and the generation amount of propane is relatively reduced.
The journal of fuel chemistry, vol.12, No. 4 of 1995, reports a research paper on the study on the process of coupling and converting methanol/propane on a ZSM-5 molecular sieve, and the authors investigated the reaction process of coupling and converting methanol/lower alkanes on a ZSM-5 molecular sieve into aromatic hydrocarbons and lower olefins, and found that there is an optimal raw material ratio for a specific catalytic system, so that the thermal effect of the reaction is approximately zero. The methanol is completely converted during coupling conversion, and the conversion rate of the low-carbon alkane is low; the coupling conversion products on different catalysts have great distribution difference, and compared with ZSM-5, the Ga modified product can obtain higher yield of aromatic hydrocarbon and low-carbon olefin.
CN201010607910.8 discloses a method for catalyzing methanol coupled naphtha catalytic cracking reaction with a modified ZSM-5 molecular sieve catalyst, in which method the modified ZSM-5 molecular sieve catalyst contains 25-80 wt% of ZSM-5, 15-70 wt% of a binder and 2.2-6.0 wt% of lanthanum and 1.0-2.8 wt% of phosphorus supported on the ZSM-5 molecular sieve. The reaction is carried out at the high temperature of more than 580 ℃ and 670 ℃ to produce the low-carbon olefin and the aromatic hydrocarbon.
Disclosure of Invention
The invention aims to provide a catalyst for producing gasoline components by aromatization of naphtha and methanol, and preparation and application thereof.
The catalyst for producing gasoline components from naphtha and methanol provided by the invention comprises a carrier and active components with the following contents calculated by taking the carrier as a reference:
0.1 to 5.0 mass% of Ag,
1.0 to 15.0 mass% of a VA group element oxide,
0.1 to 3.0 mass% of rare earth element oxide,
the carrier comprises 40-80 mass% of ZSM-5 zeolite, 3-30 mass% of alumina and 3-30 mass% of amorphous aluminum silicate.
The catalyst is prepared by loading a proper amount of Ag, VA group elements and rare earth elements on a carrier prepared from ZSM-5 zeolite, alumina and amorphous silica-alumina. The catalyst is used for the reaction of producing high-octane gasoline components by the co-aromatization of naphtha and methanol, can obtain higher gasoline yield, and has long one-way service life and less carbon deposition.
Drawings
FIG. 1 is a schematic flow chart of the method of the present invention.
Figure 2 is an XRD pattern of the catalyst prepared by the present invention.
Detailed Description
The catalyst carrier provided by the invention takes ZSM-5 as a main component, the alumina and amorphous aluminum silicate contained in the catalyst carrier not only increase the strength of the carrier, but also modulate the distribution of B acid and L acid, the Ag element contained in the catalyst can further modulate the acidity of the carrier, the VA group element and the rare earth element are added to obviously improve the stability of the catalyst, and the three components have synergistic effects, so that the yield of gasoline in a reaction product and the yield of aromatic hydrocarbon in gasoline are improved, the one-way service life of the catalyst can be prolonged, and the catalyst has good regeneration performance.
The method takes naphtha and methanol as raw materials, leads the naphtha and the methanol to be in contact with the catalyst provided by the invention under the non-hydrogen reaction condition, and carries out a series of reactions such as superposition, hydrogen transfer, aromatization, alkylation and the like, thus producing high-octane gasoline components and producing high-quality liquefied gas as a byproduct. The produced gasoline component contains less than 5% of olefin, more than or equal to 90% of Research Octane Number (RON), lower benzene content and higher xylene content, is high-quality blended gasoline, and can greatly reduce the olefin content of the catalytic cracking gasoline under the condition that the finished gasoline octane number RON is more than or equal to 93 after being blended with the catalytic cracking gasoline with higher olefin content according to a certain proportion, so that the catalytic cracking factory gasoline reaches the clean motor gasoline standard specified by national environmental protection.
The carrier preferably comprises 45-80 mass% of ZSM-5 zeolite, 6-28 mass% of alumina and 6-28 mass% of amorphous aluminum silicate.
In the carrier, SiO of ZSM-5 zeolite2/Al2O3The molar ratio of (b) is preferably 30 to 100, more preferably 40 to 80. The alumina is preferably gamma-Al2O3. The carrier can be in the shape of a strip, a pellet, a sheet, a particle or a microsphere, so as to be suitable for fixed bed, moving bed or fluidized bed reaction.
Preferably, the active component content of the catalyst of the invention is as follows:
0.5 to 3.0 mass% of Ag,
2.0 to 10.0 mass% of a VA group element oxide,
0.1 to 3.0 mass% of a rare earth element oxide.
In the catalyst, the Ag element exists in a free state, and the VA group element is phosphorus, antimony or bismuth. The rare earth element oxide can be at least one of lanthanum, cerium, praseodymium and neodymium, and is preferably a mixed rare earth oxide. The content of each metal in the mixed rare earth oxide is calculated by the oxide: 20-60% by mass of lanthanum oxide, 40-80% by mass of cerium oxide, 0-10% by mass of praseodymium oxide and 0-10% by mass of neodymium oxide, wherein the mixed rare earth oxide may contain no praseodymium oxide and no neodymium oxide, and if all four elements are contained, the contents thereof may be 20-40% by mass of lanthanum oxide, 40-60% by mass of cerium oxide, 10-18% by mass of praseodymium oxide and 2-10% by mass of neodymium oxide.
The preparation method of the catalyst comprises the following steps:
(1) mixing hydrogen type ZSM-5 zeolite, alumina and silica sol, adding peptizing agent, forming, drying, roasting to obtain a carrier,
(2) carrying out water vapor treatment on the carrier at 450-700 ℃,
(3) and (3) impregnating the carrier treated by the water vapor with a solution containing an Ag compound, a VA group element compound and a rare earth element compound, and then drying and roasting.
In the method, the step (1) is carrier forming, and the hydrogen type ZSM-5 zeolite, the alumina and the silica sol are mixed and then formed. SiO in the silica sol2The content is 20-30% by mass, and the molding can be extrusion molding, dropping ball molding, rolling ball molding or tabletting molding. Preferably, the extrusion molding is carried out, and during the extrusion molding, a proper amount of peptizing agent is preferably added into the mixture for kneading and extrusion molding, wherein the peptizing agent is preferably nitric acid or hydrochloric acid, the peptizing agent is preferably diluted with water to prepare a dilute solution, and the concentration of the solution is preferably 0.5-1.0 mass%. And drying and roasting the formed solid to obtain the carrier. The roasting temperature is 500-650 ℃, preferably 530-600 ℃, and the roasting time is preferably 1-10 hours, more preferably 3-5 hours.
(2) And (2) carrying out steam treatment on the carrier prepared in the step (1), wherein the steam treatment is to carry out aging treatment on the catalyst by using 100% of steam so as to improve the stability and the regeneration performance of the catalyst. The steam treatment temperature is preferably 500-600 ℃, and the steam treatment time is 0.5-8 hours, preferably 2-6 hours. The alpha value of the carrier after the water vapor treatment is 10-100, preferably 20-60. (the method of measuring the alpha value is described in "analytical methods for petrochemical industry (RIPP methods of experiments)" published by scientific Press, "published by Yangchini et al," P255 "measuring the alpha value of an acidic catalyst by a constant temperature method").
The water vapor treatment can also be carried out on the hydrogen type ZSM-5 zeolite before the catalyst is formed, then the hydrogen type ZSM-5 zeolite after the water vapor treatment, alumina and silica sol are mixed, and the carrier is prepared after forming, drying and roasting, wherein the drying and roasting temperatures are the same as those in the step (1). And (3) loading the formed carrier with an active component according to the method in the step (3) to obtain the catalyst.
In the method, the Ag and VA group elements and rare earth elements are introduced into the carrier in a dipping way in the step (3), the Ag-containing compound is preferably silver nitrate, the VA group element-containing compound is preferably phosphoric acid, antimony nitrate or bismuth acetate, and the mixed rare earth element-containing compound is preferably chloride or nitrate of mixed rare earth. The impregnation can be co-impregnation, namely, the carrier is impregnated after a compound solution containing the VA group element and a compound solution mixed with the rare earth element are mixed, or the carrier is impregnated by the compound solution containing the VA group element, the impregnated solid is dried, then the Ag compound and the compound solution containing the rare earth element are co-impregnated, and then the impregnated solid is dried and roasted. The dipping temperature is preferably 20-90 ℃.
In the method, the drying temperature of the carrier and the impregnated catalyst is preferably 80-140 ℃, more preferably 90-120 ℃, and the drying time is preferably 5-30 hours, more preferably 8-24 hours. (3) The roasting temperature of the catalyst obtained after the impregnation in the step (A) is preferably 500-650 ℃, more preferably 530-600 ℃, and the roasting time is preferably 1-10 hours, more preferably 3-5 hours.
The catalyst of the invention can be repeatedly used by regeneration after being deactivated. The catalyst regeneration method comprises the following steps: and treating the catalyst by using an oxygen-containing inert gas, wherein the oxygen content in the inert gas is 0.5-5.0 volume percent, and the inert gas is preferably nitrogen. The regeneration temperature is 350-500 ℃, the pressure is 0.1-3.0 MPa, and the gas/agent volume ratio is 250-1000.
The method for producing the gasoline component from naphtha and methanol comprises the steps of taking naphtha and methanol as reaction raw materials, enabling the reaction raw materials to be in a non-hydrogen state at 0.1-2.0 MPa and 200-500 ℃, and enabling the mass airspeed of raw material feeding to be 0.1-10.0 h-1And then the catalyst is contacted and reacted with the catalyst of the invention under the condition of (1), and the liquid component in the product is collected. The reaction temperature is preferably 300-450 ℃, the reaction pressure is preferably 0.2-1.5 MPa, and the feeding mass space velocity of the raw materials is preferably 0.1-3.0 h-1。
Preferably, the reaction raw material contains 10 to 90 mass% of naphtha and 10 to 90 mass% of methanol.
The reactor used for the reaction of the process of the present invention may be a fixed bed, a moving bed or a fluidized bed.
The invention is described below with reference to the accompanying drawings.
In the figure 1, raw materials are output through a metering pump 1, heat exchange is carried out on the raw materials and reaction products flowing out of a reactor 3 after heat exchange through a heat exchanger 4, the raw materials enter a heating furnace 2 and are heated to the reaction temperature, the raw materials enter the reactor 3 from the top end and are contacted with a catalyst, the reaction raw materials generate high-octane gasoline under the action of the catalyst, meanwhile, a part of liquefied gas and water are generated as byproducts, the reaction products flowing out of the bottom of the reactor 3 enter the heat exchanger 4, the reaction products enter a flash tank 5 after heat exchange and cooling with the raw materials and are separated into three phases of gas, liquid and water, rich gas discharged from the top of the tank enters an absorption and desorption tower 6 after being compressed through a compressor, and fuel gas (H) is generated (H) after the rich gas is compressed through the compressor2And C1、C2Hydrocarbon) is discharged from a tower top pipeline 9, the liquid separated from the bottom of the flash tank 5 is dehydrated and then mixed with the material discharged from the bottom of the absorption and desorption tower 6, and the mixture enters the middle part of a stabilizing tower 7, and liquefied gas (C) is added into the stabilizing tower 73、C4Hydrocarbon) and high octane number gasoline components, liquefied gas is discharged from a pipeline 10 and introduced into a gas separation tower (not shown in the figure), propane is discharged from the top end, the gasoline components discharged from the bottom of a stabilizer 7 are pumped into an absorption and desorption tower 6 as an absorbent, and the rest are discharged from a pipeline 8 as finished gasoline and sent out of the device.
The present invention is further illustrated by the following examples, but the present invention is not limited thereto.
Comparative example 1
The catalyst was prepared according to prior art methods.
(1) Preparation of the support
Taking 130 g of SiO2/Al2O3HZSM-5 zeolite powder (produced by Jianchang molecular sieve factory) with a molar ratio of 56, 70 g of pseudo-boehmite powder (produced by Sasol company of Germany and with an alumina content of 75 mass percent) are mixed, 100g of nitric acid aqueous solution with a concentration of 1.0 mass percent is added for peptization, kneaded and extruded into strips with a diameter of 2 mm, dried at 110 ℃ for 4 hours, cut into particles with a length of 2-3 mm, and roasted at 550 ℃ for 4 hours to prepare the carrier, wherein the alumina is gamma-Al2O3。
(2) Steam treatment
And (2) loading the carrier prepared in the step (1) into a tubular reactor, heating to 550 ℃ in air flow under 0.1MPa, and introducing steam for treatment for 4 hours at the temperature to obtain a catalyst G, wherein the alpha value of the catalyst is 31, and the composition of the catalyst is shown in Table 1. The XRD diffraction pattern is shown in figure 2, and it can be seen that characteristic diffraction peaks of the ZSM-5 molecular sieve appear near 8 degrees, 9 degrees, 23 degrees and 24 degrees of 2 theta respectively.
Comparative example 2
100G of the catalyst G prepared in step 1 and 2 was used as a carrier, and the catalyst was immersed in 50ml of a 100mg/ml phosphoric acid solution at 80 ℃ for 1 hour, dried at 120 ℃ for 2 hours, and then immersed in a mixture of 100ml of a 10mg/ml aqueous solution of a chlorinated mixed rare earth (containing 40% by mass of lanthanum oxide and 60% by mass of cerium oxide) and 20ml of a 100mg/ml aqueous solution of silver nitrate at 80 ℃ for 2 hours, and the immersed solid was dried at 120 ℃ for 8 hours and calcined at 550 ℃ for 4 hours to obtain a catalyst H having a catalyst α value of 32, the composition of which is shown in Table 1.
Example 1
The catalyst of the present invention is prepared.
(1) Preparation of the support
Taking 130 g of SiO2/Al2O3HZSM-5 zeolite powder with a molar ratio of 56, 35 g of pseudo-boehmite powder, 35 g of silica Sol (SiO)2Content of 30% by mass), addingPeptizing 100g of 1.0 m% nitric acid aqueous solution, kneading and extruding into strips with the diameter of 2 mm, drying at 110 ℃ for hours, cutting into particles with the length of 2-3 mm, roasting at 550 ℃ for 4 hours to obtain the carrier, wherein the alumina is gamma-Al2O3。
(2) Steam treatment
And (3) loading the carrier prepared in the step (1) into a tubular reactor, heating to 550 ℃ in air flow under 0.1MPa, and introducing water vapor for treatment for 4 hours.
(3) Preparation of the catalyst
And (3) taking 100g of the carrier treated by the water vapor in the step (2), soaking the carrier at 80 ℃ for 1 hour by using 50ml of phosphoric acid solution with the concentration of 100mg/ml, taking the soaked solid, drying the solid at 120 ℃ for 2 hours, soaking a mixture of 100ml of chlorinated mixed rare earth (containing 40 mass percent of lanthanum oxide and 60 mass percent of cerium oxide) aqueous solution with the concentration of 10mg/ml and 20ml of silver nitrate aqueous solution with the concentration of 100mg/ml at 80 ℃ for 2 hours, taking the soaked solid, drying the solid at 120 ℃ for 8 hours, and roasting the solid at 550 ℃ for 4 hours to obtain the catalyst A, wherein the alpha value of the catalyst A is 30, and the composition is shown in Table 1.
The XRD diffractogram of catalyst a is shown in fig. 2, and it can be seen that a new diffraction peak, which is a diffraction peak of amorphous alumino-silicate having an alumina content of 36.2 mass% in 2 θ of 20 ° (the same applies hereinafter) appears.
Example 2
A catalyst was prepared as in example 1, except that (1) 130 g of SiO were taken2/Al2O3HZSM-5 zeolite powder with a molar ratio of 56, 20 g of pseudo-boehmite powder and 50 g of silica sol are added into 100g of 1.0m percent nitric acid aqueous solution for peptization, and the alpha value of the prepared catalyst B is 32, and the composition is shown in Table 1.
The XRD diffractogram of catalyst B is shown in FIG. 2, and it can be seen that a new diffraction peak, which is an amorphous aluminosilicate, appears around 20 ℃ 2. theta.
Example 3
A catalyst was prepared as in example 1, except that (1) 130 g of SiO were taken2/Al2O3HZSM-5 zeolite powder with a molar ratio of 56, 50 g of pseudo-boehmite powder, 20 g of silica sol, 100g of nitric acid with a concentration of 1.0 m%The aqueous solution was peptized to obtain catalyst C having an α value of 34 and the composition shown in Table 1.
The XRD diffractogram of catalyst C is shown in FIG. 2, and it can be seen that a new diffraction peak, which is a diffraction peak of amorphous aluminosilicate, appears around 20 ° 2 θ.
Example 4
The catalyst was prepared as in example 1, except that in step (1) 90 g of SiO were taken2/Al2O3HZSM-5 zeolite powder with a molar ratio of 56, 55 g of pseudo-boehmite powder and 55 g of silica sol are added into 100g of 1.0 m% nitric acid aqueous solution for peptization, and the alpha value of the prepared catalyst D is 31, and the composition is shown in Table 1.
The XRD diffractogram of catalyst D is shown in FIG. 2, and it can be seen that a new diffraction peak, which is a diffraction peak of amorphous aluminosilicate, appears around 20 ° 2 θ.
As can be seen from FIG. 2, when the carrier is prepared by introducing the silica sol into the alumina, amorphous aluminum silicate is generated in the carrier obtained after the calcination, and the peak area of the amorphous aluminum silicate increases with the increase of the introduced amount of the silica sol, which indicates that the amount of the formed amorphous aluminum silicate increases with the increase of the introduced amount of the silica sol.
Example 5
A catalyst was prepared as in example 1 except that (3) the catalyst E obtained by impregnating 50ml of a phosphoric acid solution having a concentration of 100mg/ml at 80 ℃ for 1 hour, taking the impregnated solid, drying at 120 ℃ for 2 hours, impregnating a mixture of 100ml of a mixed rare earth aqueous solution having a concentration of 20mg/ml and 20ml of a silver nitrate aqueous solution having a concentration of 100mg/ml at 80 ℃ for 2 hours, drying and calcining the impregnated solid was used to obtain a catalyst E having an α value of 34, the composition of which is shown in Table 1.
Example 6
A catalyst was prepared by following the procedure of example 1 except that (3) the catalyst F having an α value of 34 was prepared by impregnating 50ml of a phosphoric acid solution having a concentration of 200mg/ml at 80 ℃ for 1 hour, taking the impregnated solid, drying at 120 ℃ for 2 hours, impregnating 100ml of a mixture of a mischmetal aqueous solution having a concentration of 10mg/ml and 20ml of a silver nitrate aqueous solution having a concentration of 100mg/ml at 80 ℃ for 2 hours, drying and calcining the impregnated solid, and the composition was as shown in Table 1.
Examples 7 to 8
In two identical 10 ml reactors, 7 g of catalyst A were charged each. Under the same conditions, naphtha and methanol are respectively fed into two reactors for reaction, wherein the composition of the naphtha is shown in the table 2, and the methanol is chemically pure methanol. Reaction conditions are as follows: the mass airspeed of the raw material feeding is 0.5h-1The temperature is 360 ℃ and the pressure is 0.3MPa, the reaction product is sent into a water cooler to be separated into a gas phase and a liquid phase, the gas phase and the liquid phase are respectively measured and subjected to composition analysis, and the reaction result is shown in Table 3.
As can be seen from Table 3, both feedstocks produced a portion of the gasoline component, but had a lower octane number and a gasoline component (C)5+) The medium benzene content is higher, and the gasoline is not an excellent high-octane gasoline blending component.
Examples 9 to 11
In three identical 10 ml reactors, 7 g of catalyst A were charged each. Naphtha and methanol with different proportions are mixed to prepare three batches of mixed raw materials with the methanol contents of 20 mass percent, 50 mass percent and 80 mass percent respectively, and the three mixed raw materials are respectively sent into three reactors for reaction. Reaction conditions are as follows: the mass airspeed of the raw material feeding is 0.5h-1The temperature is 360 ℃ and the pressure is 0.3MPa, the reaction product is sent into a water cooler to be separated into a gas phase and a liquid phase, the gas phase and the liquid phase are respectively measured and subjected to composition analysis, and the reaction result is shown in Table 4.
As can be seen from Table 4, three mixed feedstocks with different methanol contents can produce gasoline components with high octane number, and the xylene and aromatic hydrocarbon contents in the gasoline are increased with the increase of the methanol addition amount.
TABLE 1
Calculated on carrier basis.
TABLE 2
TABLE 3
C5+A hydrocarbon component having a carbon number of not less than five.
TABLE 4
Examples 12 to 14
In three identical 10 ml reactors, each of which was charged with 7 g of catalyst A, the reaction feed was a mixture of 70% by mass naphtha and 30% by mass methanol, at a feed mass space velocity of 0.5h-1The effect of different reaction temperatures on the reaction was examined under a pressure of 0.3MPa, and the results are shown in Table 5.
TABLE 5
As can be seen from Table 5, as the reaction temperature increased, the gasoline yield decreased, the benzene content in the gasoline did not increase substantially, but the gasoline octane number, the xylene content and the aromatic hydrocarbon content in the gasoline increased. It is shown that the proper increase of the reaction temperature is beneficial to the increase of the quality of the gasoline product.
Examples 15 to 17
In three identical 10 ml reactors, each of which was charged with 7 g of catalyst A and the reaction feed was a mixture of 70% by mass naphtha and 30% by mass methanol, at a feed mass space velocity of 0.5h-1The effect of different pressures on the reaction was examined at 360 ℃ and the results are shown in Table 6.
TABLE 6
From the results in Table 6, it is clear that the gasoline yield and gasoline octane number slightly increase with increasing reaction pressure, but the changes are not great. The naphtha and methanol are subjected to a co-aromatization reaction, the production of macromolecular gasoline and micromolecular dry gas is accompanied, and the molecular number is not changed greatly. Therefore, the reaction pressure has less influence on the reaction result.
Examples 18 to 20
In three identical 10 ml reactors, each of which was charged with 7 g of catalyst A and the reaction feed was a mixture of 70% by mass naphtha and 30% by mass methanol, the effect of the mass space velocity of the different feeds on the reaction was examined at a temperature of 360 ℃ and a pressure of 0.3MPa, the results being shown in Table 7.
TABLE 7
As can be seen from Table 7, the yield of gasoline increases with the increase of the mass airspeed of the feedstock, and the octane number of gasoline, the xylene content of gasoline and the aromatic hydrocarbon content are slightly reduced, which indicates that the reaction airspeed can be properly increased on the premise of meeting the product properties.
Examples 21 to 28
In a 10 ml reactor, 7 g of catalyst is filled, the reaction raw material is a mixture of naphtha with the mass percent of 70% and methanol with the mass space velocity of the raw material feeding is 0.5h at the temperature of 360 DEG C-1The reaction performance of the catalyst of the present invention and the comparative catalyst was examined under a pressure of 0.3MPa, and the results are shown in Table 8.
TABLE 8
As can be seen from Table 8, the catalyst of the present invention is compared with the comparative catalyst G, H, C5+The yield is obviously improved, which shows that the reaction selectivity is improved, the amorphous aluminum silicate contained in the carrier modulates the acidity distribution of the catalyst, the modulated medium and low acidity is more favorable for alkylation reaction, and C is increased5+The liquid yield and the content of dimethylbenzene in the gasoline, thereby improving the octane number of the gasoline.
Example 29
This example demonstrates the good stability of the catalyst of the invention.
A reactor of a small fixed bed reaction device is filled with a catalyst A, the reaction raw material is a mixture of naphtha with the mass percent of 70% and methanol with the mass space velocity of the raw material feeding of 0.5h at the reaction temperature of 360 DEG C-1The reaction was continued for 800 hours under a pressure of 0.3MPa, and the reaction results are shown in Table 9.
TABLE 9
Example 30
This example examines the regeneration performance of the catalyst of the invention.
A reactor of a small fixed bed reaction device is filled with a catalyst A, the reaction raw material is a mixture of naphtha with the mass percent of 70% and methanol with the mass space velocity of the raw material feeding of 0.5h at the reaction temperature of 360 DEG C-1And continuously reacting for 100 hours under the condition of 0.3MPa, and regenerating the catalyst after continuously reacting for 100 hours.
The regeneration method comprises the following steps: introducing nitrogen with the oxygen content of 0.5-2.0 vol% into a catalyst bed layer, and regenerating the catalyst at the conditions of 400 ℃, 0.8MPa and the gas/agent volume ratio of 500. After regeneration, the catalyst is reacted again according to the above conditions for 100 hours. The catalyst was regenerated several times and reacted for 100 hours after each regeneration, the results are shown in Table 10, in which liquefied gas (C)3+C4) The compositions are shown in Table 11.
As can be seen from Table 10, the catalyst of the present invention was regenerated 10 times and 20 times, and C5+The yield of the liquid product is still very close to that before regeneration, which shows that the catalyst of the invention has good regeneration performance.
As can be seen from Table 11, the catalyst of the present invention, after being regenerated 10 times and 20 times, reacts, and the liquefied gas product has a low olefin content, and belongs to high-quality liquefied gas for vehicles.
| Number of times of catalyst regeneration | 0 | 10 | 20 |
| (H2+C1+C2) Yield, mass% | 1.0 | 0.9 | 0.8 |
| (C3+C4) Yield, mass% | 31.7 | 31.5 | 31.3 |
| C5+Yield, mass% | 55.9 | 56.2 | 56.5 |
| The olefin content in the gasoline component is percent by mass | 0.5 | 0.5 | 0.6 |
| The content of benzene in the gasoline component is percent by mass | 0.9 | 0.8 | 0.8 |
| The content of dimethylbenzene in the gasoline component is percent by mass | 18.8 | 18.4 | 18.2 |
| The aromatic hydrocarbon content in the gasoline component is percent by mass | 33.5 | 33.0 | 32.5 |
| C5+RON | 92.8 | 92.5 | 92.1 |
TABLE 11
Claims (17)
1. A catalyst for producing gasoline components by aromatization of naphtha and methanol, which comprises a carrier and the following active components in an amount calculated by taking the carrier as a reference:
0.1 to 5.0 mass% of Ag,
1.0 to 15.0 mass% of a VA group element oxide,
0.1 to 3.0 mass% of rare earth element oxide,
the carrier comprises 40-80 mass% of ZSM-5 zeolite, 3-30 mass% of alumina and 3-30 mass% of amorphous aluminum silicate.
2. The catalyst according to claim 1, characterized in that the active component content of the catalyst is as follows:
0.5 to 3.0 mass% of Ag,
2.0 to 10.0 mass% of a VA group element oxide,
0.1 to 3.0 mass% of a rare earth element oxide.
3. The catalyst according to claim 1 or 2, wherein the carrier comprises 45 to 80 mass% of ZSM-5 zeolite, 6 to 28 mass% of alumina, and 6 to 28 mass% of amorphous alumina.
4. The catalyst according to claim 1 or 2, characterized in that the SiO of the ZSM-5 zeolite2/Al2O3The molar ratio is 30-100.
5. The catalyst of claim 1 or 2 wherein the group VA element is phosphorus, antimony or bismuth.
6. The catalyst according to claim 1 or 2, characterized in that the rare earth oxide is selected from at least one of lanthanum, cerium, praseodymium and neodymium oxide.
7. The catalyst of claim 6 wherein the rare earth oxide is a mixed rare earth oxide.
8. A catalyst according to claim 1 or 2, characterised in that the alumina is γ -Al2O3。
9. A method of preparing the catalyst of claim 1, comprising the steps of:
(1) mixing hydrogen type ZSM-5 zeolite, alumina and silica sol, adding peptizing agent, forming, drying, roasting to obtain a carrier,
(2) carrying out water vapor treatment on the carrier at 450-700 ℃,
(3) and (3) impregnating the carrier treated by the water vapor with a solution containing an Ag compound, a VA group element compound and a rare earth element compound, and then drying and roasting.
10. The method according to claim 9, wherein step (1) comprises SiO in the silica sol2The content is 20-30 mass%, the roasting temperature is 500-650 ℃, and the peptizing agent is selected from nitric acid or hydrochloric acid.
11. The method according to claim 9, wherein the carrier after the steam treatment in the step (2) has an α value of 10 to 100.
12. The method according to claim 9, wherein the water vapor treatment in step (2) is carried out on the hydrogen type ZSM-5 zeolite before the catalyst is formed, and then the hydrogen type ZSM-5 zeolite after the water vapor treatment, the alumina and the silica sol are mixed, formed, dried and calcined to obtain the carrier.
13. The method according to claim 9, wherein the carrier is impregnated with the solution of the compound containing the group VA element in step (3), and then impregnated with the solution of the compound containing the Ag compound and the compound containing the rare earth element, followed by drying and calcining.
14. The method according to claim 9, wherein the Ag-containing compound is silver nitrate, the group VA element-containing compound is phosphoric acid, antimony nitrate or bismuth acetate, and the rare earth element-containing compound is a chloride or nitrate of a misch metal.
15. A method for producing gasoline components from naphtha and methanol comprises the steps of taking naphtha and methanol as reaction raw materials, enabling the reaction raw materials to be in a non-hydrogen state at 0.1-2.0 MPa and 250-500 ℃, and enabling the mass airspeed of raw material feeding to be 0.1-10.0 h-1Is contacted with the catalyst of claim 1 to react, and the liquid component in the product is collected.
16. The method according to claim 15, wherein the reaction raw material contains 10 to 90 mass% of naphtha and 10 to 90 mass% of methanol.
17. The method according to claim 15, wherein the reaction temperature is 300 to 450 ℃, the reaction pressure is 0.2 to 1.5MPa, and the feed mass space velocity of the raw material is 0.1 to 3.0h-1。
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| CN114433189B (en) * | 2020-10-19 | 2024-09-06 | 中国石油化工股份有限公司 | Aromatization catalyst and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340601A (en) * | 2000-08-30 | 2002-03-20 | 中国石油化工股份有限公司 | Aromatizing catalyst for light hydrocarbon and its preparing process |
| CN101244969A (en) * | 2008-03-25 | 2008-08-20 | 清华大学 | Device and method for continuous aromatization and catalyst regeneration |
| CN102078819A (en) * | 2009-11-26 | 2011-06-01 | 中国石油化工股份有限公司 | Light hydrocarbon aromatization catalyst and preparation method thereof |
| CN103464193A (en) * | 2013-08-09 | 2013-12-25 | 华电煤业集团有限公司 | Fluidized catalyst for alcohol ether and hydrocarbon aromatization, and preparation method and application method thereof |
| CN104549072A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Fluidized bed reaction system and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether |
| CN105195211A (en) * | 2014-06-16 | 2015-12-30 | 中国石油化工股份有限公司 | A kind of methanol and C4 hydrocarbon aromatization catalyst and aromatization method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100493712C (en) * | 2006-05-19 | 2009-06-03 | 天津大沽化工股份有限公司 | In Situ Synthesis of Ag/Al-ZSM-5 Zeolite |
| US9732013B2 (en) * | 2014-09-30 | 2017-08-15 | Exxonmobil Chemical Patents Inc. | Production of aromatics from methanol and co-feeds |
| CN105949019B (en) * | 2016-04-29 | 2019-12-03 | 浙江大学 | Catalyst and method for improving the selectivity of methanol to produce aromatic products |
-
2017
- 2017-09-28 CN CN201710896604.2A patent/CN109569703B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1340601A (en) * | 2000-08-30 | 2002-03-20 | 中国石油化工股份有限公司 | Aromatizing catalyst for light hydrocarbon and its preparing process |
| CN101244969A (en) * | 2008-03-25 | 2008-08-20 | 清华大学 | Device and method for continuous aromatization and catalyst regeneration |
| CN102078819A (en) * | 2009-11-26 | 2011-06-01 | 中国石油化工股份有限公司 | Light hydrocarbon aromatization catalyst and preparation method thereof |
| CN103464193A (en) * | 2013-08-09 | 2013-12-25 | 华电煤业集团有限公司 | Fluidized catalyst for alcohol ether and hydrocarbon aromatization, and preparation method and application method thereof |
| CN104549072A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Fluidized bed reaction system and method for preparing ethylene, propylene and aromatic hydrocarbon by converting methanol and/or dimethyl ether |
| CN105195211A (en) * | 2014-06-16 | 2015-12-30 | 中国石油化工股份有限公司 | A kind of methanol and C4 hydrocarbon aromatization catalyst and aromatization method |
Non-Patent Citations (5)
| Title |
|---|
| "C4烃类在ZSM-5分子筛催化剂上的芳构化（Ⅱ）";吴指南等;《石油化工》;19830501(第4期);全文 * |
| "Promoted effect of zinc-nickel bimetallic oxides supported on HZSM-5 catalysts in aromatization of methanol";Jia, YM et al.;《JOURNAL OF ENERGY CHEMISTRY》;20161119;第26卷(第3期);全文 * |
| "SELECTIVE CONVERSION OF METHANOL INTO AROMATIC-HYDROCARBONS OVER SILVER-EXCHANGED ZSM-5 ZEOLITES";INOUE, Y et al.;《MICROPOROUS MATERIALS》;20000310;第4卷(第5期);全文 * |
| "甲醇制芳烃催化剂开发进展";邢爱华等;《现代化工》;20130320;第33卷(第3期);全文 * |
| "稀土改性HZSM-5催化剂上石脑油馏分非临氢芳构化制取高辛烷值汽油";吕明智等;《四川大学学报(自然科学版)》;20110328;第48卷(第2期);全文 * |
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