CN114075453B - Catalytic cracking gasoline hydro-upgrading method - Google Patents
Catalytic cracking gasoline hydro-upgrading method Download PDFInfo
- Publication number
- CN114075453B CN114075453B CN202010826724.7A CN202010826724A CN114075453B CN 114075453 B CN114075453 B CN 114075453B CN 202010826724 A CN202010826724 A CN 202010826724A CN 114075453 B CN114075453 B CN 114075453B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- cosno
- gasoline
- hydro
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 59
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 160
- 239000002808 molecular sieve Substances 0.000 claims abstract description 54
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 46
- 239000010941 cobalt Substances 0.000 claims abstract description 44
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 44
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 37
- 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 36
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 36
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011733 molybdenum Substances 0.000 claims abstract description 35
- 239000011593 sulfur Substances 0.000 claims abstract description 33
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001336 alkenes Chemical class 0.000 claims abstract description 26
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- 230000009471 action Effects 0.000 claims abstract description 12
- 150000001993 dienes Chemical class 0.000 claims abstract description 10
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003568 thioethers Chemical class 0.000 claims abstract description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 93
- 238000002360 preparation method Methods 0.000 claims description 55
- 239000000843 powder Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 38
- 229910021641 deionized water Inorganic materials 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 36
- 239000012018 catalyst precursor Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 27
- 239000011777 magnesium Substances 0.000 claims description 27
- 229910052749 magnesium Inorganic materials 0.000 claims description 27
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 21
- 238000010992 reflux Methods 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 230000008569 process Effects 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 238000004073 vulcanization Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 101150033293 mocos gene Proteins 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 150000007522 mineralic acids Chemical class 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 238000000643 oven drying Methods 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 12
- 238000002715 modification method Methods 0.000 abstract description 3
- 239000012188 paraffin wax Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 20
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 230000023556 desulfurization Effects 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 238000006356 dehydrogenation reaction Methods 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 241000219782 Sesbania Species 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 239000004530 micro-emulsion Substances 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000005486 sulfidation Methods 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QZYDAIMOJUSSFT-UHFFFAOYSA-N [Co].[Ni].[Mo] Chemical compound [Co].[Ni].[Mo] QZYDAIMOJUSSFT-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910019058 CoSnO3 Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910018725 Sn—Al Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005732 thioetherification reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Classifications
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group 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
- B01J29/42—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
- B01J29/46—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
- B01J29/40—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
-
- 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
- B01J37/20—Sulfiding
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- 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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a hydrogenation modification method of catalytic cracking gasoline, firstly, under the action of a pre-hydrogenation catalyst, the full fraction catalytic cracking gasoline is subjected to a pre-hydrogenation reactor to remove diolefin, mercaptan and thioether, then a pre-hydrogenation product is subjected to selective hydrodesulfurization under the action of a hydrodesulfurization and isomerization catalyst, and meanwhile, straight-chain olefin is isomerized into single-branched-chain olefin or single-branched-chain paraffin to obtain clean gasoline with ultralow sulfur content; the pre-hydrogenation catalyst takes one or more of amorphous silicon aluminum, alumina, a Y molecular sieve and ZSM-5 as a carrier to impregnate one or more active components of cobalt, molybdenum and nickel. The catalytic cracking gasoline hydro-upgrading method is used for producing clean gasoline with ultralow sulfur and low octane number loss.
Description
Technical Field
The invention relates to the field of catalytic cracking gasoline hydrogenation, in particular to a catalytic cracking gasoline hydrogenation modification method.
Background
At present, the hydrodesulfurization catalyst for catalytically cracked gasoline realizes the purpose of desulfurizing and reducing olefin, and simultaneously, the catalyst is more important to keep the octane number without losing. CN107151563a provides a clean gasoline production process that couples ultra-deep desulfurization with high octane conversion of olefins. The production method comprises the following steps: contacting the full fraction gasoline with a sulfur transfer catalyst under the hydrogen condition to generate directional low-temperature sulfur transfer reaction, and then cutting oil products to obtain light fraction gasoline and heavy fraction gasoline; mixing light fraction gasoline with organic acid, and esterifying C5-C7 olefin under the action of an esterification catalyst; the heavy fraction gasoline, the selective hydrodesulfurization catalyst and the complementary desulfurization-hydrocarbon isomerization catalyst are subjected to selective hydrodesulfurization reaction and hydrocarbon isomerization reaction respectively; and mixing the treated light fraction gasoline with the treated heavy fraction gasoline to obtain the ultra-low sulfur high-octane gasoline. The production method provided by the invention is suitable for treating inferior gasoline, especially high-sulfur and high-olefin catalytic cracking gasoline, and can maintain or improve the octane number of the gasoline while ultra-deep desulfurization is performed. CN101508913a relates to a hydro-upgrading method for deep desulfurization and octane number recovery of full-fraction inferior gasoline. The poor full-cut gasoline is contacted and reacted with three different catalysts in a three-stage reaction zone, the reaction temperature of the first stage is lower, and a high-selectivity hydrodesulfurization catalyst is adopted to remove sulfur compounds which are difficult to remove and minimize olefin saturation; the second stage has higher reaction temperature, and adopts a complementary desulfurization-hydrocarbon single-branched-chain isomerization/aromatization catalyst to thoroughly remove sulfur compounds and further reduce the content of olefin; the third stage has lower reaction temperature, and the hydrocarbon multi-branched hydroisomerization catalyst is used for multi-branched isomerization of the residual olefin and the linear alkane Improving the octane number of the product. The invention can obtain good hydro-upgrading effect especially for middle-high sulfur and high olefin poor-quality catalytic cracking gasoline, can maintain or improve the octane number of the product and keep higher liquid yield of the product while greatly reducing the content of olefin and sulfur, and can produce clean gasoline with national IV or even higher standards. CN109647442a discloses a fully sulfided hydrofining catalyst and a method for preparing the same. The catalyst comprises MoS based on 100% of the catalyst mass 2 20.3-26.1％，NiS 2 5.8-7.4%, the rest is alumina; the specific surface area of the catalyst is 250-450 m 2 Per gram, the pore volume is 0.4-0.6 mL/g. The catalyst is a fully vulcanized catalyst, does not need vulcanization or activation, has higher hydrodesulfurization and denitrification activities, and can be used as a hydrofining catalyst.
Alumina carrier is widely used in heterogeneous catalyst, catalyst carrier and other fields, and the thermal stability, hydrothermal stability, coking resistance and other non-ideal performance of carrier alumina. Usually, an auxiliary agent is added for modification, so that the carrier performance is improved. The technology of modified alumina carrier is many, CN101898131A discloses a dehydrogenation catalyst taking Sn-containing alumina as a carrier and a preparation method thereof, the dehydrogenation catalyst takes Sn-containing alumina as the carrier, carbon nano fibers are loaded on the surface of a carrier pore canal, and a dehydrogenation active metal component is loaded by an impregnation method. The preparation method of the catalyst comprises the following steps: and introducing Sn into a carrier when alumina is glued, carrying out ethylene pyrolysis to load carbon nanofibers on the Sn-containing alumina carrier in situ, then impregnating a dehydrogenation active component, and carrying out heat treatment and water vapor treatment to obtain the final dehydrogenation catalyst. The catalyst of the invention is used in hydrocarbon dehydrogenation reaction process, especially propane dehydrogenation process, and has the advantages of high activity, high selectivity and the like, especially greatly improved stability. The most commonly used carrier of the gasoline hydrodesulfurization catalyst is alumina, and in order to improve the activity and stability of the catalyst, the composite carrier is prepared by using modified alumina such as silicon, titanium, magnesium, boron, phosphorus and the like, so that the pore structure, the surface acidity and the interaction between active components and the carrier of the catalyst can be modulated. In addition, the pore structure of the modulation carrier can also increase the specific surface of the carrier, and the performance of the carrier is more than several times superior to that of the similar products used at present.
Disclosure of Invention
The invention provides a hydrogenation modification method of catalytic cracking gasoline, which is a method for producing clean gasoline with ultralow sulfur content and small octane number loss by the processes of pre-hydrogenation, hydrodesulfurization and isomerization of the catalytic cracking gasoline.
Therefore, the invention provides a catalytic cracking gasoline hydro-upgrading method, which comprises the following steps:
(1) The full fraction catalytic cracking gasoline is subjected to pre-hydrogenation treatment under the action of a pre-hydrogenation catalyst, and diolefin, mercaptan and thioether are removed to obtain a pre-hydrogenation product;
(2) Hydrodesulfurizing the pre-hydrogenated product under the action of hydrodesulfurization and isomerization catalyst, and isomerizing the linear olefin into single branched olefin or single branched alkane to obtain clean gasoline with ultralow sulfur content;
wherein the pre-hydrogenation catalyst comprises 8-18wt% of active components and a carrier, and the active components comprise one or more of cobalt, molybdenum and nickel; the carrier comprises one or more of amorphous silicon aluminum, aluminum oxide, a Y molecular sieve and ZSM-5;
the hydrodesulfurization and isomerization catalyst comprises a carrier and an active component, wherein the catalyst comprises a MoCoS active phase and/or a NiCoS active phase, and the catalyst comprises more than 3wt% of S.
The invention relates to a catalytic cracking gasoline hydro-upgrading method, wherein, in the hydro-desulfurization and isomerization catalyst, the carrier comprises 70.0-90.0wt% of Al based on the carrier 2 O 3 0.5 to 4.0wt% CoSnO 3 9.0 to 35.0 weight percent of ZSM-5 molecular sieve containing mesopores and macropores; based on the catalyst and calculated by the oxide mass, the content of molybdenum in the active component is 5.0-16.0wt%, the content of cobalt is 1.5-6.0wt%, and the content of magnesium is 0.2-4.5wt%.
The method for hydro-upgrading the catalytic cracking gasoline, which is disclosed by the invention, is characterized in that the carrier preferably comprises 76.0-84.0wt% of Al 2 O 3 ，1.5-4.0wt％CoSnO 3 9.0 to 25.0 weight percent of ZSM-5 molecular sieve containing mesopores and macropores; the content of molybdenum in the active component is 8.0-16.0wt% and cobalt containsThe content of magnesium is 1.5-5.0wt% and the content of magnesium is 0.2-3.5wt%.
The invention relates to a catalytic cracking gasoline hydro-upgrading method, wherein, in the hydro-desulfurization and isomerization catalyst, the carrier comprises 75.0-87.0wt% of Al based on the carrier 2 O 3 1.0 to 3.0wt% CoSnO 3 1.0 to 4.5wt% of La 2 Sn 3 O 7 9.0 to 35.0 weight percent of ZSM 5 molecular sieve containing mesopores and macropores; based on the catalyst, the active component contains molybdenum 5.0-16.0wt%, cobalt 1.5-6.0wt%, nickel 2.5-8.5wt% and magnesium 0.2-4.5wt% based on the amount of oxide.
The method for hydro-upgrading the catalytic cracking gasoline, which is disclosed by the invention, is characterized in that the carrier preferably comprises 76.0-85.0wt% of Al 2 O 3 ，1.5-3.0wt％CoSnO 3 ，1.5-3.5wt％La 2 Sn 3 O 7 9.0 to 25.0 weight percent of ZSM 5 molecular sieve containing mesopores and macropores; the active component contains 8.0-16.0wt% of molybdenum, 1.5-5.0wt% of cobalt and 0.2-3.5wt% of magnesium.
The catalytic cracking gasoline hydro-upgrading method of the invention, wherein the CoSnO is preferable 3 The preparation method comprises the following steps: respectively dissolving a tin source and a cobalt source, mixing and stirring uniformly, adding alkali liquor, reacting at 120-180 ℃ for 7-24h, cooling, washing and drying the obtained reactant to obtain precursor powder, and calcining the precursor powder at 560-800 ℃ for 2-6h to obtain CoSnO 3 。
The hydro-upgrading method of the catalytic cracking gasoline of the invention, wherein the pore diameter of the ZSM-5 molecular sieve containing mesopores and macropores is preferably 2-70 nm, and the total specific surface area is 300-350 m 2 /g、360～400m 2 Per gram or 410-450 m 2 /g。
The hydro-upgrading method of the catalytic cracking gasoline, which is disclosed by the invention, is preferable that the pore volume of the ZSM-5 molecular sieve containing mesopores and macropores is 0.20-0.24 m 3 /g、0.25～0.30m 3 /g or 0.31-0.35 m 3 /g。
In the catalytic gasoline hydro-upgrading method of the present invention, preferably, in the hydrodesulfurization and isomerization catalyst, the content of Co in the carrier is lower than the amount of Co carried by the catalyst, based on the mass of CoO.
The method for hydro-upgrading the catalytically cracked gasoline, disclosed by the invention, is characterized in that the preparation method of the gasoline hydrodesulfurization and isomerization catalyst comprises the following steps of:
(1) Preparation of slurry I: adding an acid solution containing styrene-butadiene rubber emulsion into CoSnO 3 The powder contains CoSnO as the acid solution of styrene-butadiene rubber emulsion based on the mass of styrene-butadiene rubber emulsion 3 5 to 30.0 weight percent of powder, and evenly mixing to obtain slurry I;
(2) Preparation of powder I: deionized water is added into pseudo-boehmite, slurry I is continuously added under the stirring condition, then ZSM-5 molecular sieve containing mesopores and macropores is added, and CoSnO is obtained through ultrasonic dispersion, suction filtration and drying 3 And pseudo-boehmite powder I;
(3) Preparation of the carrier: mixing the powder I with a binder, adding inorganic acid and deionized water, kneading, extruding, shaping, oven drying, and calcining to obtain CoSnO-containing powder 3 Is an alumina carrier of (a);
(4) Preparation of the impregnating solution: mixing a molybdenum-containing solution, a cobalt-containing solution and a magnesium-containing solution to obtain a mixed solution, regulating the pH value of the mixed solution to 2-4, and then adding a vulcanizing agent to obtain an impregnating solution containing Co, mo, mg and S;
(5) Preparation of a catalyst precursor: impregnating the carrier with impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor;
(6) Preparation of the catalyst: and after vulcanizing the catalyst precursor, cooling to room temperature, filtering, washing with deionized water, and then drying in vacuum to obtain the catalyst.
In the catalytic cracking gasoline hydro-upgrading method of the present invention, preferably, in the step (1), the pH value of the acid solution containing styrene-butadiene rubber emulsion is below 6; in the step (3), the roasting conditions are as follows: 480-700 ℃ for 4-10 hours; in the step (4), the addition amount of the vulcanizing agent in the impregnating solution is 80-130% of the theoretical sulfur carrying amount of the catalyst, and more preferably 90-115%; in the step (6), the vulcanizing step is as follows: refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant to react at 100-150 deg.c for 0.5-10 hr and sulfurizing; the temperature of the vacuum drying is 80-150 ℃.
The catalytic cracking gasoline hydro-upgrading method of the invention, wherein the step of vulcanizing is preferably as follows: refluxing the catalyst precursor at 65-75 deg.c for 0.5-1.5 hr, adding reductant to react at 100-140 deg.c for 2-6 hr and final sulfurizing.
The method for hydro-upgrading the catalytically cracked gasoline, disclosed by the invention, is characterized in that the preparation method of the gasoline hydrodesulfurization and isomerization catalyst comprises the following steps of:
(I) Preparation of the carrier:
adding an acid solution containing styrene-butadiene rubber emulsion into CoSnO 3 In the powder, the mass of the styrene-butadiene rubber emulsion and the addition amount of the acid liquor containing the styrene-butadiene rubber emulsion are CoSnO 3 5 to 30.0 weight percent of powder, and evenly mixing to obtain slurry (1);
adding sodium polyacrylate and/or ammonium polyacrylate into deionized water, and adding La 2 Sn 3 O 7 The addition amount of the sodium polyacrylate and/or the ammonium polyacrylate is La 2 Sn 3 O 7 2-20wt% of (a) to obtain a slurry (2);
adding deionized water into 50-70% pseudo-boehmite, continuing adding 55-80% slurry (1) under stirring, adding 50-80% ZSM-5 molecular sieve containing mesopores-macropores, adding 50-60% slurry (2), sequentially adding the rest pseudo-boehmite, the rest slurry (1), the rest ZSM-5 molecular sieve containing mesopores-macropores and the rest slurry (2), performing ultrasonic dispersion, suction filtration and drying to obtain the product containing CoSnO 3 And pseudo-boehmite;
mixing the powder with a binder, adding inorganic acid and deionized water, kneading, extruding to form strips, drying, and roasting at 480-700 ℃ for 4-10 hours to obtain the La-containing powder 2 Sn 3 O 7 、CoSnO 3 Is an alumina carrier of (a);
(II) preparation of the catalyst:
mixing molybdenum-containing solution, cobalt-containing solution, nickel-containing solution and magnesium-containing solution, regulating the pH value of the mixed solution to 2-4, and then dissolving a vulcanizing agent to obtain an impregnating solution containing Co, mo, ni, mg and S;
Impregnating the carrier with impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor;
and (3) vulcanization: refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant to react at 100-150 deg.c for 0.5-10 hr and sulfurizing;
cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150deg.C to obtain the final catalyst product.
The hydro-upgrading method of the catalytic cracking gasoline, disclosed by the invention, is preferable that the addition amount of the vulcanizing agent in the impregnating solution is 85-120% of the theoretical sulfur carrying amount of the catalyst.
The method for hydro-upgrading the catalytic cracking gasoline provided by the invention is characterized in that the preparation method of the pre-hydrogenation catalyst comprises the following steps:
(1) Adjusting the pH value of the solution containing the active components to 2-4, and then adding a vulcanizing agent to obtain an impregnating solution;
(2) Impregnating the carrier with impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor;
(3) Refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant to react at 100-150 deg.c for 0.5-10 hr and sulfurizing;
(4) Cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150deg.C to obtain the final catalyst product.
The catalytic cracking gasoline hydro-upgrading method of the invention, wherein the conditions of the pre-hydrotreatment are preferably as follows: the reaction temperature is 90-155 ℃, the reaction pressure is 1.5-4.5MPa, and the liquid volume space velocity is 2-7h -1 Hydrogen oil volume ratio is 4-7:1;
the conditions of the hydrodesulfurization are as follows: reverse-rotationThe reaction temperature is 220-300 ℃, the reaction pressure is 1.5-4.5MPa, and the volume space velocity is 2.5-5h -1 The volume ratio of hydrogen to oil is 180-400:1.
The invention provides a catalytic cracking gasoline hydro-upgrading method, which is specifically described as follows:
firstly, the full fraction FCC gasoline is subjected to a pre-hydrogenation catalyst, diolefin, mercaptan and thioether are removed through a pre-hydrogenation reactor, then the pre-hydrogenation product is subjected to selective hydrodesulfurization under the action of a hydrodesulfurization and isomerization catalyst, and meanwhile, straight-chain olefin is isomerized into single-branched-chain olefin or single-branched-chain paraffin, so that clean gasoline with ultralow sulfur content is obtained.
The pre-hydrogenation catalyst takes one or more of amorphous silicon aluminum, aluminum oxide, a Y molecular sieve and ZSM-5 as a carrier, and takes one or more of cobalt, molybdenum and nickel as an active component; the active component accounts for 8-18wt% of the catalyst. In the catalyst active component, molybdenum and cobalt exist in MoCoS form, nickel and cobalt exist in NiCoS form, and the catalyst contains more than 3wt% of sulfur, preferably 3-15wt% of sulfur, and more preferably 3-6wt% of sulfur.
The preparation method of the pre-hydrogenation catalyst comprises the following steps: mixing one or more of molybdenum-containing solution, cobalt-containing solution and nickel-containing solution, regulating pH value of the mixed solution to 2-4, and dissolving vulcanizing agent such as ammonium sulfide to obtain impregnating solution containing Co, mo and/or Ni and S; impregnating the carrier with impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor; and (3) vulcanization: refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant, such as hydrazine hydrate solution, accounting for over 10% of the catalyst volume, and heating at 100-150 deg.c for 0.5-10 hr to complete the sulfurization; cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150deg.C to obtain the final catalyst product.
The sulfidation catalyst has low sulfidation temperature, and avoids the generation of spinel structure with low activity between active metal and carrier alumina, thereby improving the reaction activity of the catalyst. And meanwhile, the vulcanizing is carried out at low temperature, so that the energy consumption is reduced, and the production cost is saved.
The pre-hydrogenation reaction is mainly that micromolecular mercaptan and thioether are subjected to a thioetherification reaction with diolefin (unsaturated monoolefin and high selective hydrogenation activity of the catalyst) under the action of a pre-hydrogenation catalyst, and simultaneously double bonds are isomerized (namely terminal olefin is converted into internal olefin), and the rest diolefin is saturated.
The conditions of the pre-hydrogenation reaction are as follows: the reaction temperature is 90-155 ℃, the reaction pressure is 1.5-4.5MPa, and the liquid volume space velocity is 2-7h -1 The volume ratio of hydrogen to oil is 4-7:1.
The hydrodesulfurization and isomerization reaction process conditions are as follows: the reaction temperature is 220-300 ℃, the reaction pressure is 1.5-4.5MPa, and the volume space velocity is 2.5-5h -1 The volume ratio of hydrogen to oil is 180-400:1.
The catalyst for hydrodesulfurization and isomerization of the catalytically cracked gasoline comprises a carrier and an active component, wherein the carrier comprises Al 2 O 3 ZSM-5 molecular sieve containing mesopores and macropores and CoSnO 3 The catalyst is loaded with cobalt, molybdenum and magnesium and is used for producing clean gasoline with ultra-low sulfur and high octane number.
Further, in the catalyst for hydrodesulfurization and isomerization of the catalytically cracked gasoline, the carrier comprises 70.0 to 90.0 weight percent of Al based on the carrier 2 O 3 ，0.5-4.0wt％CoSnO 3 9.0 to 35.0 weight percent of ZSM-5 molecular sieve containing mesopores and macropores; the catalyst comprises more than 3% of sulfur, preferably 3-15% of sulfur, more preferably 3-6% of sulfur, by weight, based on the catalyst, of molybdenum content of 5.0-16.0% by weight, cobalt content of 1.5-6.0% by weight and magnesium content of 0.2-4.5% by weight of oxide mass.
Further preferably, the catalyst support comprises 76.0 to 84.0wt% Al 2 O 3 ，1.5-4.0wt％CoSnO 3 9.0 to 25.0 weight percent of ZSM-5 molecular sieve containing mesopores and macropores, the active component molybdenum content is 8.0 to 16.0 weight percent, the cobalt content is 1.5 to 5.0 weight percent, and the magnesium content is 0.2 to 3.5 weight percent based on oxide.
The invention also provides a preparation method of the hydrodesulfurization and isomerization catalyst for the catalytically cracked gasoline, which comprises the following steps:
(I) Preparation of the carrier: adding an acid solution containing styrene-butadiene rubber emulsion into CoSnO 3 In the powder, toThe mass of the styrene-butadiene rubber emulsion, and the addition amount of the acid solution containing the styrene-butadiene rubber emulsion is CoSnO 3 5 to 30.0 weight percent of powder, and evenly mixing to obtain slurry (1); adding deionized water into pseudo-boehmite, continuing to add slurry (1) under stirring, adding ZSM-5 molecular sieve containing mesopores and macropores, performing ultrasonic dispersion, suction filtration and drying to obtain a product containing CoSnO 3 And pseudo-boehmite powder; mixing the above powder with binder such as sesbania powder, adding inorganic acid such as nitric acid and deionized water, kneading, extruding to form strips, oven drying, and calcining at 480-700deg.C for 4-10 hr to obtain CoSnO-containing powder 3 Is an alumina carrier of (a).
Preparation method of carrier of the invention, coSnO 3 The carrier has a space occupying effect, and has a part of through macropores, so that the carrier has good stability and good selectivity.
(II) preparation of the catalyst:
mixing molybdenum-containing solution, cobalt-containing solution and magnesium-containing solution, regulating the pH value of the mixed solution to 2-4, and dissolving a vulcanizing agent such as ammonium sulfide to obtain an impregnating solution containing Co, mo, mg and S; impregnating CoSnO-containing articles with impregnating solutions 3 Aging for more than 4 hours under a closed condition to obtain a catalyst precursor; and (3) vulcanization: refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reducing agent hydrazine hydrate solution to react at 100-150 deg.c for 0.5-10 hr and sulfurizing; cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150deg.C to obtain the final catalyst product.
Because of diversified sources and poor quality of gasoline, the content of colloid, sulfur, arsenic and other impurities in the gasoline has obvious influence on the activity of the catalyst, and even no obvious temperature rise of a catalyst bed layer and catalyst deactivation can be caused. In order to improve the impurity resistance of the catalyst, the invention also provides another catalyst for hydrodesulfurization and isomerization of gasoline, which comprises a carrier and active components, wherein the carrier comprises 75.0 to 87.0 weight percent of Al based on the carrier 2 O 3 ，1.0-3.0wt％CoSnO 3 ，1.0-4.5wt％,La 2 Sn 3 O 7 ，9.0-35.0wt％The ZSM 5 molecular sieve containing mesopores and macropores comprises, by oxide, 5.0-16.0wt% of active component molybdenum, 1.5-6.0wt% of cobalt, 2.5-8.5wt% of nickel and 0.2-4.5wt% of magnesium, wherein the catalyst comprises a MoCoS active phase and a NiCoS active phase, and contains more than 3% of sulfur, preferably 3-15wt% of sulfur, more preferably 3-8wt% of sulfur.
Further preferably, the catalyst support comprises 76.0 to 85.0wt% Al 2 O 3 ，1.5-4.0wt％CoSnO 3 ，1.5-3.5wt％La 2 Sn 3 O 7 9.0 to 25.0 weight percent of ZSM 5 molecular sieve containing mesopores and macropores; the active component contains 8.0-16.0wt% of molybdenum, 1.5-5.0wt% of cobalt and 0.2-3.5wt% of magnesium.
The invention also provides a preparation method of the other gasoline hydrodesulfurization and isomerization catalyst, which comprises the following steps:
(I) Preparation of the carrier:
adding an acid solution containing styrene-butadiene rubber emulsion into CoSnO 3 The powder comprises CoSnO as the acid solution of styrene-butadiene rubber emulsion based on the mass of styrene-butadiene rubber emulsion 3 5 to 30.0 weight percent of powder, and evenly mixing to obtain slurry (1);
sodium polyacrylate and/or ammonium polyacrylate (added in La) 2 Sn 3 O 7 2-20 wt%) of the above-mentioned raw materials are added into deionized water, then La is added 2 Sn 3 O 7 Obtaining La-containing 2 Sn 3 O 7 A slurry (2);
adding deionized water into 50-70% pseudo-boehmite, continuing adding 55-80% slurry (1) under stirring, adding 50-80% ZSM-5 molecular sieve containing mesopores-macropores, adding 50-60% slurry (2), sequentially adding the rest pseudo-boehmite, the rest slurry (1), the rest ZSM-5 molecular sieve containing mesopores-macropores and the rest slurry (2), performing ultrasonic dispersion, suction filtration and drying to obtain the product containing La 2 Sn 3 O 7 Powders of CoSnO3 and pseudo-boehmite;
mixing the above powder with adhesive sesbania powder, adding inorganic acid such as nitric acid and deionized water, and kneadingExtruding, baking at 480-700 deg.c for 4-10 hr to obtain La-containing material 2 Sn 3 O 7 、CoSnO 3 Is an alumina carrier of (a).
Preparation method La of the vector of the present invention 2 Sn 3 O 7 、CoSnO 3 The carrier has a space occupying effect, has partially communicated macropores, has good stability and selectivity, can adjust the phase structure of the alumina and the acid-base property of the surface of the carrier to form a proper La-Sn-Al ratio, and further reduces the binding force of the alumina carrier with the metal active component in the process of high Wen Chengxiang, thereby improving the dispersibility of the active metal on the surface of the carrier. Effectively inhibit colloid, arsenic, lead and other impurities from being adsorbed on the surface of the catalyst, cover the active site center and improve the impurity resistance of the catalyst. The cobalt-molybdenum-nickel catalyst prepared by the carrier is particularly beneficial to the formation of CoMoS active phase, reduces the consumption of active metal and improves the desulfurization activity of the hydrogenation catalyst. The preparation method of the catalyst carrier of the invention comprises the steps of pseudo-boehmite and CoSnO 3 Slurry (1), ZSM-5 molecular sieve containing mesoporous and macroporous, and La 2 Sn 3 O 7 The slurry (2) is added twice, so that the anti-coking performance of the carrier is improved, the strength of the carrier is improved, the activity of the surface of the prepared cobalt-molybdenum-nickel catalyst is reduced due to the fact that the colloid covers the active site center, and the activity of the catalyst can be recovered after the catalyst is regenerated.
(II) preparation of the catalyst:
mixing molybdenum-containing solution, cobalt-containing solution, nickel-containing solution and magnesium-containing solution, regulating the pH value of the mixed solution to 2-4, and dissolving a vulcanizing agent such as ammonium sulfide to obtain an impregnating solution containing Co, mo, ni, mg and S; impregnating the carrier with impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor; and (3) vulcanization: refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant, such as sodium sulfide solution, to react at 100-150 deg.c for 0.5-10 hr and final sulfurizing; cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150deg.C to obtain the final catalyst product.
In the invention, la 2 Sn 3 O 7 Is prepared and ofWithout limitation, it can be prepared, for example, as follows: mixing lanthanum-containing salt solution with sodium stannate, adjusting pH to 10.5-12 with alkali solution, aging, filtering, washing, drying, and calcining at 800-950 deg.C to obtain La 2 Sn 3 O 7 。
Further preferably, the vulcanization process: refluxing the catalyst precursor at 65-75 deg.c for 0.5-1.5 hr, adding reductant, such as hydrazine hydrate solution, accounting for over 10% of the catalyst volume, and heating at 100-140 deg.c for 2-6 hr to complete the sulfurization. Wherein the addition amount of the reducing agent is more preferably 20-70%, and most preferably 20-50% of the catalyst volume.
In the present invention, coSnO 3 The preparation method of (2) is not limited, and conventional preparation methods are adopted. The CoSnO 3 Can be prepared according to the following method: respectively dissolving a tin source and a cobalt source, mixing and stirring uniformly, adding alkali liquor, reacting for 7-24 hours at 120-180 ℃, cooling, washing and drying the obtained reactant to obtain precursor powder. Calcining the precursor powder for 2-6 hours at 560-800 ℃ to obtain CoSnO 3 . The invention comprises 0.5 to 4.0wt percent of CoSnO 3 Introducing the catalyst into an alumina carrier, preparing the vulcanized cobalt-molybdenum hydrodesulfurization catalyst, effectively controlling the growth of cobalt grains of the load, inhibiting the aggregation of the cobalt grains, promoting the formation of MoCoS active phase and being beneficial to improving the desulfurization activity of the catalyst.
Further improvements in controlling CoSnO in alumina supports 3 The content of Co (all calculated as CoO) in the alumina carrier is lower than the content of Co carried by the catalyst.
Of course, the unavoidable production of MoCoS active phase, moS, in the catalysts of the present invention 2 、CoS 2 The phase even has molybdenum oxide and cobalt oxide. In order to form as much active MoCoS phase as possible, the present invention introduces CoSnO directly unlike Co, sn and other oxides 3 Introducing the catalyst into an alumina carrier, preparing the vulcanized cobalt-molybdenum hydrodesulfurization-isomerization catalyst, effectively controlling the growth of cobalt grains of a load, inhibiting the aggregation of the cobalt grains, promoting the formation of MoCoS active phase and being beneficial to improving the desulfurization activity of the catalyst. The cobalt in the alumina carrier is calculated as oxide, and the Co content is low The amount of Co loaded on the catalyst is favorable for improving the dispersibility of the active components on the surface of the carrier, improving the utilization rate of the active components and ensuring good stability of the catalyst.
The ZSM-5 molecular sieve containing mesopores and macropores is preferably a molecular sieve of CN 110510632A. The carrier of the invention contains alumina and CoSnO 3 And the ZSM-5 molecular sieve containing mesopores and macropores promotes the isomerization reaction of terminal linear chain, especially single linear chain alkane, while hydrodesulfurizing.
The pore diameter of the ZSM-5 molecular sieve containing mesopores and macropores is 2-70 nm, and the total specific surface area is 300-350 m 2 Per gram or 360-400 m 2 Per gram, again or 410-450 m 2 The range of/g.
The ZSM-5 molecular sieve pore volume containing mesopores and macropores is 0.20-0.24 m 3 Per gram or 0.25-0.30 m 3 Per gram, or 0.31 to 0.35m 3 The range of/g. The macropore content is controlled to be 3-45% of the total pores, and the mesopore content is controlled to be 5-65% of the total pores. Adjusting CoSnO according to raw material properties and product control indexes 3 The content and the styrene-butadiene rubber emulsion content, and the pore structure is adjusted.
The preparation method of the ZSM-5 molecular sieve containing mesopores and macropores is preferably carried out according to the following steps: preparing silicon source, aluminum source, inorganic acid or inorganic base and deionized water into mixture gel, wherein the mol ratio of each component calculated by oxide is 1.0SiO 2 :0.00025～0.5Al 2 O 3 :10～80H 2 O, regulating the pH value to 9.5-13.0, and stirring and refluxing the mixture in a container at 60-100 ℃ for 2-48 h; adding the rubber microemulsion into the gel after the reflux in the step 1 according to the ratio (R) of the dry basis mass of the rubber microemulsion to the mass of silicon element in the silicon source of 0.5-50, filtering the synthesized product, washing with water, drying at 80-140 ℃ for 2-12 h, and roasting at 500-600 ℃ for 4-10 h when crystallizing at 150-200 ℃ for 12-72 h, thus obtaining the mesoporous-macroporous ZSM-5 molecular sieve.
The carrier of the gasoline hydrodesulfurization and isomerization catalyst comprises Al 2 O 3 ，CoSnO 3 ，La 2 Sn 3 O 7 ZSM-5 molecular sieve containing mesopores and macropores and loaded with molybdenum, cobalt, nickel and magnesiumAn isoactive ingredient. The low-temperature vulcanization is used for preparing the vulcanization type cobalt-molybdenum hydrodesulfurization and isomerization catalyst, which is beneficial to regulating the hydrodesulfurization isomerization activity and the hydrodedehydrogenation activity of the catalyst, inhibiting the olefin saturation active center, and has low olefin saturation activity, high hydrodesulfurization-isomerization activity and low octane number loss. The catalyst is used for producing clean gasoline meeting national standards of five countries and six countries by catalytically cracking gasoline.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The raw material reagents used in the invention are all commercial products.
Example 1
Preparation of a Pre-hydrogenation catalyst
111g of alumina and 12.0g of sesbania powder are added into a kneader, evenly mixed, evenly kneaded by adding nitric acid, 260g of ZSM-5 and deionized water, and formed by kneading and extruding. Drying at 130 ℃ for 9 hours, and roasting at 550 ℃ for 6 hours to obtain a carrier, wherein the carrier comprises the following components: ZSM-5 was 70% and alumina 30%.
The preparation method of the pre-hydrogenation catalyst comprises the following steps: preparing impregnating solution of molybdenum, cobalt and nickel elements according to the proportion of 7wt% of molybdenum oxide, 1.5wt% of cobalt oxide and 3.6wt% of nickel oxide in the catalyst, mixing molybdenum-containing solution, cobalt and nickel solution, regulating the pH value of the mixed solution to 2.6, and dissolving ammonium sulfide to obtain the impregnating solution containing Co, mo, ni and S; impregnating a carrier with impregnating solution containing Co, mo, ni and S, and aging for 5 hours under a closed condition to obtain a catalyst precursor; catalyst sulfiding process: the catalyst precursor was added to a flask with reflux, refluxed at 65 ℃ for 1.0 hour, 43mL of hydrazine hydrate and 90mL of deionized water were added, the temperature was raised to 110 ℃ for further reflux for 4 hours, the sulfidation was completed, and the temperature was lowered to room temperature. Filtering, washing with deionized water, and vacuum drying to obtain the pre-hydrogenation catalyst product.
Preparation of hydrodesulfurization and isomerization catalysts
1. Preparation of mesoporous-macroporous ZSM-5 molecular sieve
Firstly, water glass with the concentration of 40%, aluminum sulfate, sodium hydroxide and deionized water are calculated according to the mole ratio of oxide to be 1SiO 2 :0.02Al 2 O 3 :0.55Na 2 O:62.4H 2 Adding O into a crystallization kettle, refluxing and stirring for 24 hours at 80 ℃, adding rubber microemulsion into the mixture gel according to the proportion of R=2.5 before crystallization, filtering a synthesized product when the mixture gel is crystallized for 48 hours at 190 ℃, washing with water, drying for 6 hours at 120 ℃, and roasting for 6 hours at 550 ℃, thus obtaining the product 1. Crystallinity 95%; the pore diameter of the mesopores and macropores is 2-58 nm, and the pore volume is 0.23m 3 Per g, total specific surface area of 304m 2 /g; the silicon/aluminum molar ratio of the product mesoporous-macroporous ZSM-5 molecular sieve is 48.
2. Preparation of CoSnO 3
22.5g SnCl 4 ·5H 2 O was dissolved in deionized water to give solution (a), 22.2g of CoCl 2 ·6H 2 O is dissolved in deionized water to obtain a solution (b), the solution (b) is added into the solution (a) under stirring and is uniformly stirred, naOH solution is added and is uniformly stirred, the obtained mixture is transferred into a reaction tank to react for 11 hours at 140 ℃, and after cooling, the obtained reactant is washed and dried to obtain precursor powder. Calcining the precursor powder for 3.0h at 700 ℃ to obtain CoSnO 3 。CoSnO 3 Grinding for later use.
3. Preparation of the vector
An acid solution (ph=6) containing 1.2g of styrene-butadiene rubber emulsion was added to 6.2g of cosno 3 Uniformly mixing the powder to obtain slurry (1); 245.7g of pseudo-boehmite is added with deionized water, then the slurry (1) is added into the pseudo-boehmite under the stirring condition, then 21.8g of ZSM-5 molecular sieve containing mesopores and macropores is added, and then the mixture is subjected to ultrasonic dispersion, suction filtration and drying to obtain the product containing CoSnO 3 And pseudo-boehmite powder; mixing the above powder with herba Hyperici Japonici powder, adding nitric acid and deionized water, kneading, extruding, shaping, oven drying, and calcining at 540 deg.C for 5.5 hr to obtain CoSnO-containing powder 3 Is a carrier 1 of alumina. The alumina content of the carrier 1 was 86wt%, CoSnO 3 3.1wt% and 10.9wt% ZSM-5.
4. Preparation of the catalyst
Preparing an impregnating solution of molybdenum, cobalt and magnesium according to the proportion of 0.3wt% of molybdenum oxide, 2.1wt% of cobalt oxide and 1.8wt% of magnesium oxide in the catalyst, regulating the pH value of the solution to 2.2 by adopting nitric acid, adding 32g of ammonium sulfide into the solution, and dissolving to obtain the impregnating solution containing Mo, co, mg and S. And spraying and dipping the impregnating solution of Co, mo, mg and S into the alumina carrier by adopting a normal-temperature isovolumetric spraying and dipping method, and aging for 8 hours at room temperature under a closed condition to obtain the catalyst precursor. Catalyst sulfiding process: the catalyst precursor was added to the flask with reflux, refluxed at 75 ℃ for 25min, continuously added with 50mL of hydrazine hydrate and 100mL of deionized water, the temperature was raised to 110 ℃ for continuous reflux for 4 hours, the vulcanization was completed, and the temperature was lowered to room temperature. Filtering, washing with deionized water, and vacuum drying to obtain Co-Mo-S catalyst product 1.
Example 2
1. The procedure for preparing mesoporous-macroporous ZSM-5 molecular sieves was the same as in example 1, except for the different 1.2SiO ratios 2 :0.02Al 2 O 3 :0.55Na 2 O:62.4H 2 O, the pore diameter of the mesopores and macropores is 2-67 nm, and the pore volume is 0.25m 3 Per gram, total specific surface area of 318m 2 /g; the silicon/aluminum mole ratio of the product mesoporous-macroporous ZSM-5 molecular sieve is 53. Acid solution pH containing styrene-butadiene rubber emulsion=5.5.
2. Preparation of CoSnO 3 The procedure of (2) is the same as in example 1.
3. The procedure for the preparation of the support was as in example 1, the support comprising 78% by weight of alumina, 3.6% by weight of CoSnO 3 8.4wt% of ZSM-5 molecular sieve containing mesopores and macropores.
4. The procedure for the preparation of the catalyst was as in example 1, the catalyst active component having a molybdenum content of 12.4% by weight, a cobalt content of 1.6% by weight and a magnesium content of 1.1% by weight. The addition amount of ammonium sulfide is 105% of the theoretical sulfur carrying amount of the catalyst.
Example 3
1. The procedure for preparing mesoporous-macroporous ZSM-5 molecular sieves was the same as in example 1, except that the batch ratios were different from 0.85SiO 2 :0.02Al 2 O 3 :0.55Na 2 O:62.4H 2 O, the pore diameter of the mesopores and macropores is 2-56 nm, and the pore volume is 0.28m 3 Per g, total specific surface area 308m 2 And/g. Acid solution containing styrene-butadiene rubber emulsion ph=5.
2. Preparation of CoSnO 3 The procedure of (2) is the same as in example 1.
3. The procedure for the preparation of the support was as in example 1, the support comprising 89% by weight of alumina, 1.4% by weight of CoSnO 3 9.6wt% of ZSM-5 molecular sieve containing mesopores and macropores.
4. The procedure for the preparation of the catalyst was as in example 1, with the active component molybdenum content of 11.3% by weight, the cobalt content of 3.0% by weight and the magnesium content of 1.3% by weight. The addition amount of ammonium sulfide is 115% of the theoretical sulfur carrying amount of the catalyst.
Example 4
1. The procedure for preparing mesoporous-macroporous ZSM-5 molecular sieves was the same as in example 1, except for the different 1.5SiO ratios 2 :0.02Al 2 O 3 :0.55Na 2 O:62.4H 2 O, the pore diameter of the mesopores and macropores is 2-67 nm, and the pore volume is 0.25m 3 Per gram, total specific surface area of 318m 2 /g; the silicon/aluminum mole ratio of the product mesoporous-macroporous ZSM-5 molecular sieve is 53. Acid solution containing styrene-butadiene rubber emulsion ph=6.
2. Preparation of CoSnO 3 The procedure of (2) is the same as in example 1.
3. The procedure for the preparation of the support was as in example 1, the support comprising 81% by weight of alumina, 2.1% by weight of CoSnO 3 16.4wt% of ZSM-5 molecular sieve containing mesopores and macropores.
4. The procedure for the preparation of the catalyst was as in example 1, with catalyst 4 having a molybdenum content of 9.8% by weight, a cobalt content of 4.6% by weight and a magnesium content of 0.9% by weight. The addition amount of the ammonium sulfide is 100% of the theoretical sulfur carrying amount of the catalyst.
Example 5
Based on the mass of the styrene-butadiene rubber emulsion, the adding amount of the styrene-butadiene rubber emulsion is CoSnO according to the acid solution (pH is 6) 3 16wt% of powder, preparation of CoSnO-containing 3 To obtain a slurry (1);
according to the addition amount of sodium polyacrylate accounting for CoSnO 3 16 wt% of the productIs prepared to contain La 2 Sn 3 O 7 Is a slurry (2);
adding deionized water into 60% pseudo-boehmite under stirring, continuously adding 70% slurry (1) under stirring, then adding 55% ZSM-5 molecular sieve containing mesoporous macropores of example 4, then adding 50% slurry (2), finally sequentially adding the rest pseudo-boehmite, the rest slurry (1), the rest ZSM-5 molecular sieve containing mesoporous macropores and the rest slurry (2), and performing ultrasonic dispersion, suction filtration and drying to obtain the product containing La 2 Sn 3 O 7 、CoSnO 3 And pseudo-boehmite;
mixing the above powder with sesbania powder, adding nitric acid and deionized water, kneading, extruding to form strips, oven drying, and calcining at 650deg.C for 5 hr to obtain La-containing powder 2 Sn 3 O 7 、CoSnO 3 Is an alumina carrier of (a).
Alumina content 78wt% in support 5, coSnO 3 Content 1.4wt%, la 2 Sn 3 O 7 2.8wt% of ZSM-5 molecular sieve containing mesoporous and macroporous 17.8wt%.
Mixing molybdenum-containing solution, cobalt-containing solution, nickel-containing solution and magnesium-containing solution, regulating the pH value of the mixed solution to 3, and dissolving ammonium sulfide to obtain an impregnating solution containing Co, mo, ni, mg and S; impregnating a carrier with impregnating solution containing Co, mo, ni, mg and S, and aging for 5 hours under a closed condition to obtain a catalyst precursor; and (3) vulcanization: refluxing the catalyst precursor at 70 ℃ for 1.5 hours, adding 32g of sodium sulfide solution, continuously reacting for 6 hours under the heating condition of 130 ℃, and ending vulcanization; cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 120 ℃ to obtain the final catalyst product. The addition amount of the ammonium sulfide is 125% of the theoretical sulfur carrying amount of the catalyst.
The catalyst contained 11.7wt% of molybdenum, 2.2wt% of cobalt, 3.1wt% of nickel and 0.5wt% of magnesium, based on the amount of the oxidized substance.
FCC gasoline (sulfur content 140.3mg/kg, olefin content 32.7v%, arsenic content 114 μg/kg and colloid content 1.67 mg/mL) is treated by a pre-hydrogenation reactor to remove diolefin, mercaptan and thioetherDouble bond isomerization (i.e., conversion of terminal olefins to internal olefins) and saturation of the remaining diolefins. The reaction temperature is 120 ℃, the reaction pressure is 1.8MPa, and the liquid volume space velocity is 4h -1 The hydrogen oil volume ratio is 4:1. The pre-hydrogenation product with 100% of diolefin removed is subjected to deep desulfurization and isomerization under the action of hydrodesulfurization-isomerization catalyst 1-5 by a hydrodesulfurization unit, and the reaction process conditions are as follows: reactor temperature 265 ℃, reaction pressure 2.0MPa and volume space velocity 3.6h -1 Hydrogen oil volume ratio 330. Sample analysis after about 60 hours of reaction, the results are shown in Table 1.
TABLE 1 catalyst hydrodesulfurization-isomerization reaction results
As can be seen from Table 1, the hydrodesulfurization and isomerization catalyst reacted at a reactor temperature of 265℃with an octane number loss of 0.2 to 0.4 units, a low octane number loss, a high liquid yield, a high desulfurization rate, good activity, a liquid yield of 97.9% or more, a single branched olefin increment of 10.3% or more, and a single branched alkane increment of 12.3% or more. Further, it was found that the olefin saturation ratios of the catalysts 1 to 5 obtained in examples were 12.3%,11.6%,13.2%,14.6% and 9.4%, respectively.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (14)
1. The hydro-upgrading method for the catalytic cracking gasoline is characterized by comprising the following steps of:
(1) The full fraction catalytic cracking gasoline is subjected to pre-hydrogenation treatment under the action of a pre-hydrogenation catalyst, and diolefin, mercaptan and thioether are removed to obtain a pre-hydrogenation product;
(2) Hydrodesulfurizing the pre-hydrogenated product under the action of hydrodesulfurization and isomerization catalyst, and isomerizing the linear olefin into single branched olefin or single branched alkane to obtain clean gasoline with ultralow sulfur content;
wherein the pre-hydrogenation catalyst comprises 8-18wt% of active components and a carrier, and the active components comprise one or more of cobalt, molybdenum and nickel; the carrier comprises one or more of amorphous silicon aluminum, aluminum oxide, a Y molecular sieve and ZSM-5;
the hydrodesulfurization and isomerization catalyst comprises a carrier and an active component, wherein the catalyst comprises a MoCoS active phase and/or a NiCoS active phase, and the catalyst comprises more than 3wt% of S;
In the hydrodesulfurization and isomerization catalyst, the carrier comprises 70.0 to 90.0 weight percent of Al based on the carrier 2 O 3 0.5 to 4.0wt% CoSnO 3 9.0 to 35.0 weight percent of ZSM-5 molecular sieve containing mesopores and macropores; based on the catalyst and calculated by the oxide mass, the content of molybdenum in the active component is 5.0-16.0wt%, the content of cobalt is 1.5-6.0wt%, and the content of magnesium is 0.2-4.5wt%;
the preparation method of the hydrodesulfurization and isomerization catalyst comprises the following steps:
(1) Preparation of slurry I: adding an acid solution containing styrene-butadiene rubber emulsion into CoSnO 3 The powder contains CoSnO as the acid solution of styrene-butadiene rubber emulsion based on the mass of styrene-butadiene rubber emulsion 3 5 to 30.0 weight percent of powder, and evenly mixing to obtain slurry I;
(2) Preparation of powder I: deionized water is added into pseudo-boehmite, slurry I is continuously added under the stirring condition, then ZSM-5 molecular sieve containing mesopores and macropores is added, and CoSnO is obtained through ultrasonic dispersion, suction filtration and drying 3 And pseudo-boehmite powder I;
(3) Preparation of the carrier: mixing the powder I with a binder, adding inorganic acid and deionized water, kneading, extruding, shaping, oven drying, and calcining to obtain CoSnO-containing powder 3 Is an alumina carrier of (a);
(4) Preparation of the impregnating solution: mixing a molybdenum-containing solution, a cobalt-containing solution and a magnesium-containing solution to obtain a mixed solution, regulating the pH value of the mixed solution to 2-4, and then adding a vulcanizing agent to obtain an impregnating solution containing Co, mo, mg and S;
(5) Preparation of a catalyst precursor: impregnating the carrier with impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor;
(6) Preparation of the catalyst: and after vulcanizing the catalyst precursor, cooling to room temperature, filtering, washing with deionized water, and then drying in vacuum to obtain the catalyst.
2. The method for hydro-upgrading a catalytically cracked gasoline according to claim 1, wherein in the step (1), the pH of the acid solution containing styrene-butadiene rubber emulsion is 6 or less; in the step (3), the roasting conditions are as follows: 480-700 ℃ for 4-10 hours; in the step (4), the addition amount of the vulcanizing agent in the impregnating solution is 80-130% of the theoretical sulfur carrying amount of the catalyst; in the step (6), the vulcanizing step is as follows: refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant to react at 100-150 deg.c for 0.5-10 hr and sulfurizing; the temperature of the vacuum drying is 80-150 ℃.
3. The catalytic gasoline hydro-upgrading process according to claim 2, wherein the step of sulfiding is: refluxing the catalyst precursor at 65-75 deg.c for 0.5-1.5 hr, adding reductant to react at 100-140 deg.c for 2-6 hr and final sulfurizing.
4. The catalytic gasoline hydro-upgrading process according to claim 1, wherein the carrier comprises 76.0-84.0wt% Al 2 O 3 ，1.5-4.0wt％CoSnO 3 9.0 to 25.0 weight percent of ZSM-5 molecular sieve containing mesopores and macropores; the active component contains 8.0-16.0wt% of molybdenum, 1.5-5.0wt% of cobalt and 0.2-3.5wt% of magnesium.
5. The hydro-upgrading method for the catalytic cracking gasoline is characterized by comprising the following steps of:
(1) The full fraction catalytic cracking gasoline is subjected to pre-hydrogenation treatment under the action of a pre-hydrogenation catalyst, and diolefin, mercaptan and thioether are removed to obtain a pre-hydrogenation product;
(2) Hydrodesulfurizing the pre-hydrogenated product under the action of hydrodesulfurization and isomerization catalyst, and isomerizing the linear olefin into single branched olefin or single branched alkane to obtain clean gasoline with ultralow sulfur content;
wherein the pre-hydrogenation catalyst comprises 8-18wt% of active components and a carrier, and the active components comprise one or more of cobalt, molybdenum and nickel; the carrier comprises one or more of amorphous silicon aluminum, aluminum oxide, a Y molecular sieve and ZSM-5;
The hydrodesulfurization and isomerization catalyst comprises a carrier and an active component, wherein the catalyst comprises a MoCoS active phase and/or a NiCoS active phase, and the catalyst comprises more than 3wt% of S;
in the hydrodesulfurization and isomerization catalyst, the carrier comprises 75.0 to 87.0 weight percent of Al based on the carrier 2 O 3 1.0 to 3.0wt% CoSnO 3 1.0 to 4.5wt% of La 2 Sn 3 O 7 9.0 to 35.0 weight percent of ZSM-5 molecular sieve containing mesopores and macropores; based on the catalyst, the active component contains molybdenum 5.0-16.0wt%, cobalt 1.5-6.0wt%, nickel 2.5-8.5wt% and magnesium 0.2-4.5wt% based on the amount of oxide.
6. The method for hydro-upgrading a catalytically cracked gasoline according to claim 5, wherein the carrier comprises 76.0-85.0wt% Al 2 O 3 ，1.5-3.0wt％CoSnO 3 ，1.5-3.5wt％La 2 Sn 3 O 7 9.0 to 25.0 weight percent of ZSM-5 molecular sieve containing mesopores and macropores; the active component contains 8.0-16.0wt% of molybdenum, 1.5-5.0wt% of cobalt and 0.2-3.5wt% of magnesium.
7. The method for hydro-upgrading a catalytically cracked gasoline according to claim 5, wherein the method for preparing the hydrodesulfurization and isomerization catalyst comprises the steps of:
(I) Preparation of the carrier:
adding an acid solution containing styrene-butadiene rubber emulsion into CoSnO 3 In the powderThe mass of the styrene-butadiene rubber emulsion is CoSnO, and the addition amount of the acid liquor containing the styrene-butadiene rubber emulsion is CoSnO 3 5 to 30.0 weight percent of powder, and evenly mixing to obtain slurry 1;
adding sodium polyacrylate and/or ammonium polyacrylate into deionized water, and adding La 2 Sn 3 O 7 The addition amount of the sodium polyacrylate and/or the ammonium polyacrylate is La 2 Sn 3 O 7 2-20wt% of (a) to obtain slurry 2;
adding deionized water into 50-70% pseudo-boehmite, continuing adding 55-80% slurry 1 under stirring, adding 50-80% ZSM-5 molecular sieve containing mesopores-macropores, adding 50-60% slurry 2, sequentially adding the rest pseudo-boehmite, the rest slurry 1, the rest ZSM-5 molecular sieve containing mesopores-macropores and the rest slurry 2, performing ultrasonic dispersion, suction filtration and drying to obtain CoSnO-containing powder 3 And pseudo-boehmite;
mixing the powder with a binder, adding inorganic acid and deionized water, kneading, extruding to form strips, drying, and roasting at 480-700 ℃ for 4-10 hours to obtain the La-containing powder 2 Sn 3 O 7 、CoSnO 3 Is an alumina carrier of (a);
(II) preparation of the catalyst:
mixing molybdenum-containing solution, cobalt-containing solution, nickel-containing solution and magnesium-containing solution, regulating the pH value of the mixed solution to 2-4, and then dissolving a vulcanizing agent to obtain an impregnating solution containing Co, mo, ni, mg and S;
Impregnating the carrier with impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor;
and (3) vulcanization: refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant to react at 100-150 deg.c for 0.5-10 hr and sulfurizing;
cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150deg.C to obtain the final catalyst product.
8. The method for hydro-upgrading catalytically cracked gasoline as defined in claim 7, wherein the amount of sulfiding agent added in the impregnation liquid is 85-120% of the theoretical sulfur loading of the catalyst.
9. The catalytic gasoline hydro-upgrading process according to claim 1 or 5, wherein the CoSnO 3 The preparation method comprises the following steps: respectively dissolving a tin source and a cobalt source, mixing and stirring uniformly, adding alkali liquor, reacting at 120-180 ℃ for 7-24h, cooling, washing and drying the obtained reactant to obtain precursor powder, and calcining the precursor powder at 560-800 ℃ for 2-6h to obtain CoSnO 3 。
10. The method for hydro-upgrading catalytically cracked gasoline according to claim 1 or 5, wherein the mesoporous-macroporous ZSM-5 molecular sieve has a pore diameter of 2-70 nm and a total specific surface area of 300-350 m 2 /g、360～400m 2 Per gram or 410-450 m 2 /g。
11. The catalytic gasoline hydro-upgrading method according to claim 1 or 5, wherein the mesoporous-macroporous ZSM-5 molecular sieve has a pore volume of 0.20-0.24 m 3 /g、0.25～0.30m 3 /g or 0.31-0.35 m 3 /g。
12. The method for hydro-upgrading a catalytically cracked gasoline according to claim 1 or 5, wherein in the hydrodesulfurization and isomerization catalyst, co is contained in the carrier in an amount lower than the amount of Co supported by the catalyst, based on the mass of CoO.
13. The catalytic gasoline hydro-upgrading process according to claim 1 or 5, wherein the preparation method of the pre-hydrogenation catalyst comprises the steps of:
(1) Adjusting the pH value of the solution containing the active components to 2-4, and then adding a vulcanizing agent to obtain an impregnating solution;
(2) Impregnating the carrier with impregnating solution, and aging for more than 4 hours under a closed condition to obtain a catalyst precursor;
(3) Refluxing the catalyst precursor at 60-80 deg.c for 0.3-2.0 hr, adding reductant to react at 100-150 deg.c for 0.5-10 hr and sulfurizing;
(4) Cooling to room temperature, filtering, washing with deionized water, and vacuum drying at 80-150deg.C to obtain the final catalyst product.
14. The catalytic gasoline hydro-upgrading process according to claim 1 or 5, wherein the pre-hydrotreating conditions are: the reaction temperature is 90-155 ℃, the reaction pressure is 1.5-4.5MPa, and the liquid volume space velocity is 2-7h -1 Hydrogen oil volume ratio is 4-7:1;
the conditions of the hydrodesulfurization are as follows: the reaction temperature is 220-300 ℃, the reaction pressure is 1.5-4.5MPa, and the volume space velocity is 2.5-5h -1 The volume ratio of hydrogen to oil is 180-400:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010826724.7A CN114075453B (en) | 2020-08-17 | 2020-08-17 | Catalytic cracking gasoline hydro-upgrading method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010826724.7A CN114075453B (en) | 2020-08-17 | 2020-08-17 | Catalytic cracking gasoline hydro-upgrading method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114075453A CN114075453A (en) | 2022-02-22 |
| CN114075453B true CN114075453B (en) | 2023-05-26 |
Family
ID=80280833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010826724.7A Active CN114075453B (en) | 2020-08-17 | 2020-08-17 | Catalytic cracking gasoline hydro-upgrading method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114075453B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108993583A (en) * | 2018-09-11 | 2018-12-14 | 福州大学 | A kind of gasoline selective hydrodesulfurizationmodification-heterogeneous catalyst and preparation method |
| CN109082297A (en) * | 2018-09-11 | 2018-12-25 | 福州大学 | A kind of modifying catalytically cracked gasoline method |
| CN109647442A (en) * | 2018-12-25 | 2019-04-19 | 中国石油天然气股份有限公司 | Completely vulcanized hydrofining catalyst, preparation method thereof and distillate oil hydrofining method |
| CN110510632A (en) * | 2018-05-22 | 2019-11-29 | 中国石油天然气股份有限公司 | Mesoporous-macroporous ZSM-5 molecular sieve and preparation method thereof |
| CN111468142A (en) * | 2020-04-08 | 2020-07-31 | 中国石油天然气股份有限公司 | Co-Mo-S catalyst and preparation method thereof |
-
2020
- 2020-08-17 CN CN202010826724.7A patent/CN114075453B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110510632A (en) * | 2018-05-22 | 2019-11-29 | 中国石油天然气股份有限公司 | Mesoporous-macroporous ZSM-5 molecular sieve and preparation method thereof |
| CN108993583A (en) * | 2018-09-11 | 2018-12-14 | 福州大学 | A kind of gasoline selective hydrodesulfurizationmodification-heterogeneous catalyst and preparation method |
| CN109082297A (en) * | 2018-09-11 | 2018-12-25 | 福州大学 | A kind of modifying catalytically cracked gasoline method |
| CN109647442A (en) * | 2018-12-25 | 2019-04-19 | 中国石油天然气股份有限公司 | Completely vulcanized hydrofining catalyst, preparation method thereof and distillate oil hydrofining method |
| CN111468142A (en) * | 2020-04-08 | 2020-07-31 | 中国石油天然气股份有限公司 | Co-Mo-S catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114075453A (en) | 2022-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109097104B (en) | A kind of FCC gasoline method for modifying | |
| CN101508910B (en) | Ultra-deep desulfurization-octane value recovery hydrogenation modification method for faulty gasoline | |
| CN109201072B (en) | Catalytic cracking gasoline pre-hydrogenation catalyst and preparation method thereof | |
| CN109092352B (en) | FCC gasoline polymerization catalyst and preparation method thereof | |
| WO2020052143A1 (en) | Method for upgrading catalytically cracked gasoline | |
| CN117399011B (en) | Preparation method of nickel-copper catalytic material for hydrocarbon saturated hydrogenation | |
| CN111468142A (en) | Co-Mo-S catalyst and preparation method thereof | |
| CN101508908B (en) | Method for producing ultra-clean gasoline | |
| CN109082303B (en) | FCC gasoline cleaning method | |
| CN114075453B (en) | Catalytic cracking gasoline hydro-upgrading method | |
| CN100478423C (en) | Selective hydrogenation desulfuration catalyst for catalytically cracking gasoline and its preparation method | |
| CN114073979B (en) | Gasoline hydrodesulfurization and isomerization catalyst and preparation method thereof | |
| CN101508909B (en) | Selective hydrogenation desulfurization and highly-branched chain isomerous coupling modification method for faulty gasoline | |
| CN110038617B (en) | Hydrocracking catalyst and preparation method thereof | |
| CN111097501A (en) | Bulk phase catalyst for inferior diesel oil hydrotreating and preparation method thereof | |
| CN114471719B (en) | Hydrofining catalyst based on modified aluminum-based MOFs material and preparation method thereof | |
| CN113680347A (en) | Hydrofining catalyst, preparation method thereof and application thereof in oil refining and aromatic ring saturation regulation | |
| CN109468140B (en) | Catalyst for saturated hydrogenation of hydrocarbons and preparation method thereof | |
| CN108993583B (en) | Gasoline selective hydrodesulfurization-isomerization catalyst and preparation method thereof | |
| CN109097096B (en) | Method for pre-hydrogenation of catalytic cracking gasoline | |
| CN109097103B (en) | Method for producing clean gasoline from catalytic cracking gasoline | |
| CN110038619B (en) | Production method of hydrocracking catalyst | |
| CN109097105B (en) | A kind of FCC gasoline Olefin decrease method | |
| CN109468141B (en) | C4Process for the saturation hydrogenation of distillates | |
| CN101508913B (en) | Deep desulfurization-octane value recovery hydrogenation modification combined method for faulty full-distillation gasoline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |