CN107344114B - Modified Y/ZSM-48 composite molecular sieve and preparation method and application thereof - Google Patents
Modified Y/ZSM-48 composite molecular sieve and preparation method and application thereof Download PDFInfo
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- CN107344114B CN107344114B CN201610288646.3A CN201610288646A CN107344114B CN 107344114 B CN107344114 B CN 107344114B CN 201610288646 A CN201610288646 A CN 201610288646A CN 107344114 B CN107344114 B CN 107344114B
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 195
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 190
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000011148 porous material Substances 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920002521 macromolecule Polymers 0.000 claims abstract description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 59
- 239000003054 catalyst Substances 0.000 claims description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 20
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 20
- 150000001336 alkenes Chemical class 0.000 claims description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000003921 oil Substances 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011541 reaction mixture Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- 238000011282 treatment Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 12
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- -1 tetraethylammonium halide Chemical class 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- HUTDDBSSHVOYJR-UHFFFAOYSA-H bis[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphaplumbetan-2-yl)oxy]lead Chemical compound [Pb+2].[Pb+2].[Pb+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O HUTDDBSSHVOYJR-UHFFFAOYSA-H 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 238000005342 ion exchange Methods 0.000 claims description 4
- 238000006317 isomerization reaction Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229950006187 hexamethonium bromide Drugs 0.000 claims description 3
- FAPSXSAPXXJTOU-UHFFFAOYSA-L trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;dibromide Chemical group [Br-].[Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C FAPSXSAPXXJTOU-UHFFFAOYSA-L 0.000 claims description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 52
- 239000002253 acid Substances 0.000 description 35
- 230000004048 modification Effects 0.000 description 18
- 238000012986 modification Methods 0.000 description 18
- 238000002156 mixing Methods 0.000 description 12
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000010335 hydrothermal treatment Methods 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Substances OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000002715 modification method Methods 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 229910001948 sodium oxide Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007320 rich medium Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 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
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
-
- 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
- C10G2300/70—Catalyst aspects
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- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a modified Y/ZSM-48 composite molecular sieve and a preparation method and application thereof. The modified Y/ZSM-48 composite molecular sieve has the following properties: the total pore volume is 0.46-0.85 ml/g, preferably 0.50-0.80 ml/g; wherein the mesoporous volume is 0.35-0.65 ml/g, preferably 0.40-0.60 ml/g; the mesoporous volume accounts for 55-90%, preferably 60-80% of the total pore volume; the molar ratio of the silicon oxide to the aluminum oxide is 10-35, preferably 12-30; the specific surface area is 480-850 m2Per g, preferably 550 to 800m2(ii) in terms of/g. The modified Y/ZSM-48 composite molecular sieve has larger-size mesoporous distribution, can provide more reaction spaces for macromolecules, improves the catalytic performance of the molecular sieve, has a simple preparation method, and is suitable for industrial application.
Description
Technical Field
The invention relates to a modified Y/ZSM-48 composite molecular sieve and a preparation method and application thereof.
Background
The modification work of molecular sieves has been widely concerned by researchers. The modification research of the molecular sieve mainly carries out desilication and dealumination through conventional acid, alkali and hydrothermal treatment modification, and simultaneously generates a large amount of secondary mesoporous structures. The large number of secondary pores generated facilitates the reaction and diffusion of macromolecules. The existing modification means is mainly that hydrothermal treatment at a certain temperature is firstly carried out and then acid treatment is carried out, so that the molecular sieve is dealuminized, the hydrothermal stability is improved, and a large number of secondary pore structures can be generated. However, the secondary pores of the molecular sieve prepared by the method are mainly concentrated on the surface and have limited amount, and the molecular sieve needs to be deeply treated to increase the amount of the secondary pores, so that the molecular sieve is excessively dealuminized, and the acid content of the molecular sieve is reduced and cannot meet the requirement. In recent years, the research of desiliconization through an alkaline solution has made great progress, the amount of secondary pores can be greatly increased by further carrying out alkaline treatment after acid washing, and simultaneously, the acid amount of the molecular sieve can be increased, so that the problem of insufficient acid amount caused by the original advanced treatment can be solved. However, a large amount of secondary pore structures can be manufactured by first performing hydrothermal treatment, then performing acid pickling and dealumination, and then further performing alkali washing and desiliconization, and meanwhile, the acid amount can meet the requirement. However, the aperture of the prepared secondary pore structure is mainly concentrated at 3-5 nm, and the method is still ineffective for the conversion of some aromatic macromolecules with two rings or more than two rings, so that the preparation of the molecular sieve with the larger pore structure is an important scientific research direction.
Kouming et al (MCM-22 molecular sieve modification research progress [ J)]Contemporary chemical industry, 2015, 44 (11): 2629-2634) through the structural change of the molecular sieve after the alkali treatment and the hydrothermal treatment of the MCM-22 molecular sieve, the molecular sieve after the alkali treatment maintains the original microporous structure and has more mesoporous structures and macroporous structures. Engineering and time of year (influence of modification of Y molecular sieve on its structure and acidity [ J)]Petrochemical technology and applications, 2011, 29 (5): 401-405), which shows that a large number of secondary pores can be formed on the Y molecular sieve after modification such as hydrothermal treatment, hydrothermal-oxalic acid treatment and the like, and this shows that the water vapor treatment can play a role in expanding pores, the mesoporous pore volume can be further increased after non-framework aluminum is removed by oxalic acid, the acid type and acid amount of the Y molecular sieve can be adjusted in a large range, the total acid amount is reduced after modification, the strong L acid amount is increased after hydrothermal treatment, and the strong B acid amount can be increased by hydrothermal-oxalic acid combined dealumination. Qin Zhen et al (physicochemical properties of small-grain Y molecular sieves with different Si/Al ratios and hydrocracking performance [ J ]]Petrochemical, 2013, 42 (10): 1080-1085) shows that the framework stability of the small-grain Y molecular sieve is increased along with the increase of the silicon-aluminum ratio; the acid amount is reduced along with the increase of the silicon-aluminum ratio, and small crystal grain Y molecular sieves with different silicon-aluminum ratios have different acid center distributions; the pore structure of the small-grain Y molecular sieve is not obviously changed along with the ratio of silicon to aluminum, and compared with the industrial Y molecular sieve, the small-grain Y molecular sieve has larger specific surface area, which is beneficial to heavy oil conversion. The small crystal grain Y molecular sieve with the silicon-aluminum ratio of 5.2 has moderate acidity, developed pore passages, better framework stability, high activity of the hydrocracking catalyst taking the small crystal grain Y molecular sieve as the carrier, high light oil selectivity and high chemical raw material yield, and is the preferable light oil type hydrocracking catalystAn active component. Wangyangmajun et al (research progress on modification of ultrastable Y molecular sieves [ J)]Silicate report, 2015, 34 (11): 3243-3250) introduces methods of dealumination modification, supported acid modification, supported cation or oxide modification, molecular sieve compound modification and the like of the ultrastable Y molecular sieve, and shows that the ultrastable Y molecular sieve has good crystallinity, higher silicon-aluminum ratio, larger pore size and pore volume, high specific surface area and hydrothermal stability, and proper acid amount and acid strength after modification, so that the ultrastable Y molecular sieve can be used as a carrier or an acid component to prepare a catalyst and shows good catalytic performance. Meanwhile, the modification research of the ultrastable Y molecular sieve is considered to be continued, on one hand, the research on the aspect of acid center, namely the USY molecular sieve has B acid and L acid centers, and how to prepare the catalyst with specific acid centers to achieve the optimal catalytic activity is a problem to be overcome; on the other hand, the recycling frequency of the catalyst prepared by the ultrastable Y molecular sieve (or the modified ultrastable Y molecular sieve) is required to be improved, the production cost is reduced, and the production efficiency is improved. Penghua et al (influence of modified Y molecular sieves on middle distillate selective hydrocracking catalysts [ J)]Petro-chemical (petroleum processing), 2006 (supplement): 171-173) shows that the modified Y molecular sieve has lower total acid content and higher L acid ratio, which is beneficial to improving the middle distillate selectivity of the catalyst and keeping better activity; in the product (A)<370 ℃ distillate) conversion of 60%, the middle distillate (150 ℃ distillate and 370 ℃) selectivity of the pilot-sized catalyst HC-670 is 68.3%, while the middle distillate selectivity of the same industrial catalyst is only 61.8%. Li Ming Xiao et al (influence of hydrothermal and nitric acid treatments on the Performance of modified Y molecular sieves [ J)]Petrochemical, 2012, 43 (4): 412-419) shows that the dealumination amount of the Y molecular sieve is increased, the specific surface area is reduced and the total acid amount is reduced along with the increase of the hydrothermal treatment temperature; with the increase of the concentration of nitric acid, non-framework aluminum in the Y molecular sieve is removed, and the relative crystallinity, the specific surface area and the silicon-aluminum ratio are increased. The activity and selectivity of the hydrocracking catalyst prepared by the modified Y molecular sieve are improved, wherein the hydrocracking catalyst prepared by the Y molecular sieve through hydrothermal treatment at 680 ℃ and nitric acid treatment at 0.6mol/L has good n-dodecane conversion rateMiddle oil (C)4~8Hydrocarbon) selectivity, yield of medium oil 51.07%. Kingwenlan (hydrocracking performance of combined modified Y-type molecular sieve [ J)]Journal of fuel chemistry, 2009, 37 (4): 454-458) shows that the addition of CTAB can keep the Y-type molecular sieve at a high relative crystallinity and improve the SiO performance during the dealumination of oxalic acid in the Y-type molecular sieve2/Al2O3In contrast, the unit cell constant is reduced. The acid content of the Y-type molecular sieve with CTAB participating in modification is obviously reduced, and the reason is determined by the improvement of the silicon-aluminum ratio and the amine poisoning of partial acid sites. The hydrocracking catalyst prepared by CTAB participating in the modified Y-shaped molecular sieve has higher activity and yield of middle distillate oil, and has the VGO conversion rate 2.42 percent higher and the yield of the middle distillate oil 4.20 percent higher than that of the middle distillate oil type hydrocracking catalyst which is industrially applied at present. The reason is that the Y-type molecular sieve with CTAB participating in modification has richer mesopores, so that macromolecules in VGO can be more close to the acid sites of the catalyst, and simultaneously, a cracked product can quickly leave the active sites of the catalyst to avoid secondary cracking, so that the catalyst has higher activity and the yield of middle distillate oil.
Patent 200610001864.0 describes a method for modifying a Y-type molecular sieve, which comprises adding a surfactant during the acid dealumination process to obtain a Y-type molecular sieve with a high silica-alumina ratio (the molar silica-alumina ratio of silica to alumina is 9-15), and maintaining a high crystallinity, wherein the secondary pores of the modified Y-type molecular sieve are greatly increased, and the acid structure is further improved. Patent 200810104303.2 describes a modification method of an HY type molecular sieve, which comprises the steps of impregnating an HY type molecular sieve with a certain amount of 5-10% silica sol, drying at 120 ℃, roasting at 450 ℃, and finally dealuminizing with an ammonium fluoride aqueous solution with a certain concentration to obtain a micro-mesoporous modified molecular sieve. Patent 200810105644.1 describes a method for modifying NaY type molecular sieve, which uses a screen to separate the ion exchange resin from the molecular sieve slurry, and uses the concentration difference to realize the exchange between hydrogen ions and sodium ions without contacting the two, thereby alleviating the problem of subsequent wastewater treatment. The sodium oxide content of the obtained modified molecular sieve can be reduced to 1wt% and the crystallinity is kept above 80%. Patent 201110331019.0 discloses a method for modifying NaY molecular sieve, which comprises adding mixed acid into a mixture of NaY molecular sieve, buffer solution and water, pulping uniformly, adjusting the pH value to 4.0-6.5, carrying out exchange reaction at 70-95 ℃, washing, and drying. The method realizes no ammonium discharge and alleviates the problem of subsequent wastewater treatment. The sodium oxide content of the obtained modified molecular sieve can be reduced to 0.5wt%, and the crystallinity is kept above 85%. Patent 201310114414.2 discloses a modification method of a USY molecular sieve, which comprises the steps of modifying 0.10-0.35 mol/L citric acid at 50-120 ℃, adding 0.1-3.5 ml/min ammonium fluosilicate solution after the temperature is raised to 60-90 ℃, reacting for 1-6 hours after the ammonium fluosilicate solution is added, washing, and drying to obtain the modified USY molecular sieve. The specific surface, the secondary pore volume and the proportion of the medium and strong acid of the molecular sieve are obviously improved. Patents 201310240740.8 and 201410131823.8 describe a combined modification method of a mesoporous-rich ultrastable Y molecular sieve, which comprises the steps of mixing a solution of an organic acid and an inorganic salt solution, heating the mixed solution in a closed container under the condition of stirring, carrying out a reaction for a set time, washing the reaction, carrying out suction filtration to neutrality, and drying to obtain the modified molecular sieve. The modified molecular sieve has obviously raised secondary pore content, increased Si/Al ratio and reduced unit cell constant. Patent 201410131458.0 discloses a method for modifying USY molecular sieve, which comprises modifying ammonium fluorosilicate and citric acid mixed solution at 50-120 deg.C to obtain modified USY molecular sieve rich in secondary pore structure, high crystallinity and rich medium and strong acid. Patent 201510131458.0 discloses a modified Y-type molecular sieve and its modification method, which comprises treating Y-type molecular sieve with alkaline solution, and removing aluminum and supplementing silicon to obtain Y-type molecular sieve with high Si/Al ratio. The modified molecular sieve has the characteristics of large proportion of strong acid, especially large proportion of strong B acid.
The prior research results show that different molecular sieve modification technologies can be adopted to realize the modulation of different properties of the molecular sieve. The Y/ZSM-48 composite molecular sieve has two crystal phases of the Y molecular sieve and the ZSM-48 molecular sieve, integrates the advantages of the two molecular sieves, shows excellent catalytic performance when being applied to the field of petroleum refining, and has the characteristics of high cracking activity, excellent hydroisomerization performance, good middle distillate oil selectivity and high viscosity index of a hydrocracking tail oil product.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a modified Y/ZSM-48 composite molecular sieve and a preparation method and application thereof. The modified Y/ZSM-48 composite molecular sieve has larger-size mesoporous distribution, can provide more reaction spaces for macromolecules, improves the catalytic performance of the molecular sieve, has a simple preparation method, and is suitable for industrial application.
The modified Y/ZSM-48 composite molecular sieve has the following properties: the total pore volume is 0.46-0.85 ml/g, preferably 0.50-0.80 ml/g; wherein the mesoporous volume is 0.35-0.65 ml/g, preferably 0.40-0.60 ml/g; the mesoporous volume accounts for 55-90%, preferably 60-80% of the total pore volume; the molar ratio of the silicon oxide to the aluminum oxide is 10-35, preferably 12-30; the specific surface area is 480-850 m2Per g, preferably 550 to 800m2/g。
The preparation method of the modified Y/ZSM-48 composite molecular sieve comprises the following steps:
(1) roasting the Y-type molecular sieve at high temperature, then contacting unsaturated olefin with the roasted Y-type molecular sieve, carrying out roasting carbon deposition reaction in an inert gas atmosphere, and then carrying out desiliconization treatment on the surface of the Y-type molecular sieve to obtain a modified Y-type molecular sieve;
(2) adding modified Y-type molecular sieve powder into a solution containing sodium hydroxide and a template agent, aging for 0.5-12 hours at 50-180 ℃ under a closed condition, cooling to room temperature, then adding white carbon black, continuously and uniformly stirring to obtain a reaction mixture gel system, crystallizing the reaction mixture for 2-5 days at 150-180 ℃ under a closed condition, and finally cooling, washing, drying, roasting and ion exchanging to obtain a hydrogen Y/ZSM-48 composite zeolite molecular sieve;
(3) adding a hydrogen Y/ZSM-48 composite molecular sieve into a pressure-resistant container filled with an organic alkali solution under the condition of stirring, sealing the system, boosting the pressure to 0.2-1.0 MPa, then heating to 50-90 ℃, carrying out constant-temperature treatment for 0.5-3 hours, releasing the pressure, carrying out suction filtration, drying and roasting to obtain the modified Y/ZSM-48 composite molecular sieve.
In the method of the invention, the Y-type molecular sieve in the step (1) has the following properties: the mole ratio of silicon oxide/aluminum oxide is 4.8-20, and the specific surface area is 650-860 m2The pore volume is 0.33-55 ml/g.
In the method, the high-temperature roasting temperature in the step (1) is 350-650 ℃, and the time is 1-12 hours.
In the method, the unsaturated olefin in the step (1) is a mixture of normal or isomeric olefin and diolefin with the carbon number of 2-10; wherein the olefin is in sufficient contact with the molecular sieve, which means that unsaturated olefin diffuses into the molecular sieve; when a gaseous unsaturated olefin is used, the gaseous unsaturated olefin is contacted with the molecular sieve under the following conditions: the pressure is 0.1-1.0 MPa, and the contact time is 0.1-2 hours; when a liquid unsaturated hydrocarbon is used, the liquid unsaturated olefin is contacted with the molecular sieve under the following conditions: the pressure is 0.1-1.0 MPa, the contact time is 0.5-4 hours, and the molecular sieve is completely immersed in the liquid olefin. The olefin is fully contacted with the molecular sieve at normal temperature, and the unsaturated hydrocarbon state is a normal-temperature phase state.
In the method, the inert gas in the step (1) is one of nitrogen, helium and argon, the temperature of the carbon deposition roasting reaction is 450-650 ℃, and the time is 1-8 hours.
In the method of the invention, the desiliconization treatment process in the step (1) is as follows: adding the Y-type molecular sieve subjected to carbon deposition reaction into 0.35-1.20 mol/L sodium hydroxide solution, treating at 50-90 ℃ for 0.5-3 hours, and washing until the pH value is less than 10; the mass ratio of the addition amount of the Y-type molecular sieve to water in the solution is 1: 3-20.
In the method of the invention, the molar ratio of the reaction mixture gel system in the step (2) is calculated by the following substances (excluding the modified Y-type molecular sieve): 1.1 to 1.4Na2O:21~25SiO20.4 to 0.6 parts of a template agent 350 to 450H2O; wherein the template agent is hexamethonium bromide and/or hexamethonium chloride; modifying the Y-type component based on the mass of the gel of the reaction mixtureThe addition amount of the sub-sieve accounts for 5-20 wt%, preferably 8-15 wt% of the reaction mixture gel system.
In the method of the invention, the drying conditions in the step (2) are as follows: the drying temperature is 50-120 ℃, and the drying time is 8-24 hours.
In the method, the roasting conditions in the step (2) are as follows: the roasting temperature is 450-650 ℃, and the roasting time is 1-6 hours.
In the method, the ion exchange in the step (2) is ammonium exchange, the exchange frequency is 1-2 times, the exchange temperature is 80-120 ℃, the used ammonium salt is 0.5-3.0 mol/L ammonium nitrate solution, the liquid-solid ratio (ml/g) in the exchange process is 5-15, and the exchange time is 1.0-3.0 hours each time.
In the method, the organic alkali in the step (3) is one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide, and the concentration of the organic alkali solution is 0.05-0.35 mol/L, preferably 0.10-0.30 mol/L.
In the method of the present invention, tetraethylammonium halide, tetrapropylammonium halide or tetrabutylammonium halide may also be directly added in step (3) to form tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide by reacting it with sodium hydroxide.
In the method, the pressure increase in the step (3) is realized by introducing compressed air, nitrogen or inert gas into a pressure-resistant container.
In the method, in the step (3), the pH value is filtered until the pH value is less than 9, and the drying condition is that the drying is carried out for 6-24 hours at the temperature of 80-120 ℃.
In the method, the roasting condition in the step (3) is roasting for 2-8 hours at the temperature of 450-650 ℃.
The modified Y/ZSM-48 composite molecular sieve can be used for preparing a hydrocracking catalyst, and the obtained hydrocracking catalyst is particularly suitable for conversion of condensed ring macromolecules and isomerization reaction of straight-chain paraffin in a hydrocracking process, wherein the reaction conditions are all in the presence of hydrogen, the reaction pressure is 10-20 MPa, the reaction temperature is 350-430 ℃, the volume ratio of hydrogen to oil is 500-1800, and the liquid hourly volume space velocity is 0.5-5.0 h-1。
The method of the invention adopts high-pressure alkali treatment to the Y/ZSM-48 composite molecular sieve in the organic alkali solution, the organic alkali not only fills the pore channels of the composite molecular sieve to destroy the structure of the composite molecular sieve to a limited extent, but also promotes the formation of larger mesopores by the destruction to a limited extent under certain pressure, and simultaneously keeps the advantages of good ring-opening performance of the Y-shaped molecular sieve and excellent isomerization performance of the ZSM-48 molecular sieve. The method further penetrates the original mesopores of about 4nm in the composite molecular sieve to form a mesopore structure of about 8nm, and is more favorable for improving the ring-opening performance. Compared with the traditional modification method, the Y/ZSM-48 composite molecular sieve prepared by the invention has larger mesoporous structure distribution, simultaneously reduces the silica-alumina ratio of the molecular sieve in the alkali treatment process, and greatly improves the acid content of the composite molecular sieve, so that the molecular sieve prepared by the method has good catalytic activity and diffusion performance, can preferentially convert condensed ring macromolecules and reduce the content of straight-chain alkane in the hydrocracking process, and has wide application prospect.
Drawings
FIG. 1 is a graph of the pore size distribution of the Y/ZSM-48 composite molecular sieve prepared in example 1.
FIG. 2 is an XRD diffractogram of the Y/ZSM-48 composite molecular sieve prepared in example 1.
Detailed Description
The following examples further illustrate the preparation of the present invention, but are not to be construed as limiting the process of the present invention. The Y-type molecular sieve added in the process of preparing the Y/ZSM-48 composite molecular sieve has the following properties: the molar ratio of the silicon oxide to the aluminum oxide is 10, and the specific surface area is 757m2(ii) in terms of/g. The pressure-resistant container is a high-pressure reaction kettle, the maximum bearing pressure is 15MPa, and the maximum temperature is 300 ℃.
Example 1
(1) Roasting the Y-type molecular sieve at 550 deg.c for 4 hr, and soaking the roasted Y-type molecular sieve in liquid C under 0.3MPa10H18Calcining for 2 hr in nitrogen atmosphere at 500 deg.C for 2 hr to obtain carbon deposit, and calciningTreating the Y-type molecular sieve in 0.50mol/L sodium hydroxide solution (the mass ratio of the addition amount of the molecular sieve to the water in the solution is 1: 8) at 70 ℃ for 2.0 hours, and washing until the pH value is less than 10 to obtain a modified Y-type molecular sieve;
(2) adding modified Y-type molecular sieve powder into a solution containing sodium hydroxide and hexamethonium bromide, aging for 3 hours at 80 ℃ under a closed condition, adding white carbon black, continuously and uniformly stirring to obtain a reaction mixture gel system, crystallizing the reaction mixture for 3 days at 170 ℃ under the closed condition, cooling, washing, drying for 12 hours at 90 ℃, roasting for 3 hours at 550 ℃, and finally performing ammonium exchange for 2 times by adopting 2.0mol/L ammonium nitrate solution at 90 ℃, wherein the liquid-solid ratio (ml/g) in the ammonium exchange process is 15, and the exchange time is 1.5 hours each time, thereby finally obtaining the hydrogen Y/ZSM-48 composite molecular sieve. The molar ratio of the reaction mixture (excluding the modified Y-type molecular sieve) is: 1.3Na2O:22SiO20.55 ammonium hexamethobromide 380H2O; the modified Y-type molecular sieve was added in an amount of 14wt% of the reaction mixture.
(3) Mixing a hydrogen type Y/ZSM-48 composite molecular sieve and a tetrapropylammonium hydroxide solution in a high-pressure reaction kettle under the stirring condition, introducing nitrogen to control the system pressure to be 0.4MPa, then heating to 70 ℃, continuously stirring at a constant temperature for 2 hours, relieving the pressure, cooling, carrying out suction filtration until the pH value is less than 9, drying for 12 hours at 120 ℃, and roasting for 3 hours at 500 ℃ to obtain the modified Y/ZSM-48 composite molecular sieve. The concentration of the tetrapropylammonium hydroxide solution is 0.12mol/L, and the mass ratio of the Y/ZSM-48 composite molecular sieve to water in the solution is 1: 9. Specific properties are shown in table 1.
Example 2
(1) Roasting the Y-type molecular sieve at 450 deg.c for 6 hr, and soaking the roasted Y-type molecular sieve in liquid C under 0.4MPa8H14Calcining for 1 hour in nitrogen atmosphere at 550 ℃ for 2 hours to carry out carbon deposition reaction, treating the carbon deposited Y-type molecular sieve in 0.80mol/L sodium hydroxide solution (the mass ratio of the addition amount of the molecular sieve to water in the solution is 1: 15) at 80 ℃ for 1.5 hours, and washing until the pH value is less than 10 to obtain the modified Y-type molecular sieveScreening;
(2) adding modified Y-type molecular sieve powder into a solution containing sodium hydroxide and hexamethonium chloride, aging for 1.0 hour at 120 ℃ under a closed condition, adding white carbon black, continuously and uniformly stirring to obtain a reaction mixture gel system, crystallizing the reaction mixture for 5 days at 160 ℃ under the closed condition, cooling, washing, drying for 18 hours at 100 ℃, roasting for 5 hours at 490 ℃, and finally performing ammonium exchange for 2 times by adopting 2.0mol/L ammonium nitrate solution at 90 ℃, wherein the liquid-solid ratio (ml/g) in the ammonium exchange process is 15, the exchange time is 1.5 hours each time, and the Y/ZSM-48 composite molecular sieve is finally obtained. The molar ratio of the reaction mixture (excluding the modified Y-type molecular sieve) is: 1.2Na2O:24SiO20.58 hexamethonium chloride 410H2O; the amount of modified Y-type molecular sieve added was 12wt% of the reaction mixture.
(3) Mixing a hydrogen type Y/ZSM-48 composite molecular sieve and a tetrabutylammonium hydroxide solution in a high-pressure reaction kettle under the stirring condition, introducing air to control the system pressure to be 0.6MPa, then heating to 80 ℃, continuously stirring at a constant temperature for 1 hour, relieving the pressure, cooling, performing suction filtration until the pH value is less than 9, drying at 110 ℃ for 18 hours, and roasting at 550 ℃ for 4 hours to obtain the modified Y/ZSM-48 composite molecular sieve. The concentration of the tetrabutylammonium hydroxide solution is 0.15mol/L, and the mass ratio of the Y/ZSM-48 composite molecular sieve to water in the solution is 1: 11. Specific properties are shown in table 1.
Example 3
Steps (1) and (2) were the same as in example 1.
(3) Mixing a hydrogen type Y/ZSM-48 composite molecular sieve and a tetraethylammonium hydroxide solution in a high-pressure reaction kettle under the stirring condition, introducing nitrogen to control the system pressure to be 0.25MPa, then heating to 70 ℃, continuously stirring at constant temperature for 3 hours, relieving the pressure, cooling, performing suction filtration until the pH value is less than 9, drying at 100 ℃ for 24 hours, and roasting at 520 ℃ for 6 hours to obtain the modified Y/ZSM-48 composite molecular sieve. The concentration of the tetraethyl ammonium hydroxide solution is 0.10mol/L, and the mass ratio of the hydrogen Y/ZSM-48 composite molecular sieve to water in the solution is 1: 10. Specific properties are shown in table 1.
Example 4
Steps (1) and (2) were the same as in example 2.
(3) Mixing a hydrogen type Y/ZSM-48 composite molecular sieve and a tetrabutylammonium hydroxide solution in a high-pressure reaction kettle under the stirring condition, introducing air to control the system pressure to be 0.6MPa, then heating to 75 ℃, continuously stirring at a constant temperature for 2 hours, relieving the pressure, cooling, performing suction filtration until the pH value is less than 9, drying at 90 ℃ for 18 hours, and roasting at 580 ℃ for 3 hours to obtain the modified Y/ZSM-48 composite molecular sieve. The concentration of the tetrapropylammonium hydroxide solution is 0.20mol/L, and the mass ratio of the hydrogen type Y/ZSM-48 composite molecular sieve to water in the solution is 1: 15. Specific properties are shown in table 1.
Example 5
Steps (1) and (2) were the same as in example 1.
(3) Mixing a hydrogen type Y/ZSM-48 composite molecular sieve and a tetraethylammonium hydroxide solution in a high-pressure reaction kettle under the stirring condition, introducing nitrogen to control the system pressure to be 0.25MPa, then heating to 60 ℃, continuously stirring at constant temperature for 3 hours, relieving the pressure, cooling, performing suction filtration until the pH value is less than 9, drying at 100 ℃ for 24 hours, and roasting at 520 ℃ for 6 hours to obtain the modified Y/ZSM-48 composite molecular sieve. The concentration of the tetraethyl ammonium hydroxide solution is 0.10mol/L, and the mass ratio of the hydrogen Y/ZSM-48 composite molecular sieve to water in the solution is 1: 10. Specific properties are shown in table 1.
Example 6
Steps (1) and (2) were the same as in example 2.
(3) Mixing a hydrogen type Y/ZSM-48 composite molecular sieve and a tetrabutylammonium hydroxide solution in a high-pressure reaction kettle under the stirring condition, introducing air to control the system pressure to be 0.70MPa, then heating to 65 ℃, continuously stirring at a constant temperature for 1.5 hours, relieving pressure, cooling, performing suction filtration until the pH value is less than 9, drying at 90 ℃ for 18 hours, and roasting at 580 ℃ for 3 hours to obtain the modified Y/ZSM-48 composite molecular sieve. The concentration of the tetrapropylammonium hydroxide solution is 0.15mol/L, and the mass ratio of the hydrogen type Y/ZSM-48 composite molecular sieve to water in the solution is 1: 15. Specific properties are shown in table 1.
Example 7
Steps (1) and (2) were the same as in example 1.
(3) Mixing a hydrogen type Y/ZSM-48 composite molecular sieve and a tetraethylammonium hydroxide solution in a high-pressure reaction kettle under the stirring condition, introducing nitrogen to control the system pressure to be 0.30MPa, then heating to 80 ℃, continuously stirring at constant temperature for 1.0 hour, relieving the pressure, cooling, performing suction filtration until the pH value is less than 9, drying at 100 ℃ for 24 hours, and roasting at 520 ℃ for 6 hours to obtain the modified Y/ZSM-48 composite molecular sieve. The concentration of the tetraethyl ammonium hydroxide solution is 0.15mol/L, and the mass ratio of the hydrogen Y/ZSM-48 composite molecular sieve to water in the solution is 1: 10. Specific properties are shown in table 1.
Example 8
Steps (1) and (2) were the same as in example 2.
(3) Mixing a hydrogen type Y/ZSM-48 composite molecular sieve and a tetrabutylammonium hydroxide solution in a high-pressure reaction kettle under the stirring condition, introducing air to control the system pressure to be 0.7MPa, then heating to 65 ℃, continuously stirring at a constant temperature for 2 hours, relieving the pressure, cooling, performing suction filtration until the pH value is less than 9, drying at 90 ℃ for 18 hours, and roasting at 580 ℃ for 3 hours to obtain the modified Y/ZSM-48 composite molecular sieve. The concentration of the tetrapropylammonium hydroxide solution is 0.18mol/L, and the mass ratio of the hydrogen type Y/ZSM-48 composite molecular sieve to water in the solution is 1: 15. Specific properties are shown in table 1.
Example 9
Steps (1) and (2) were the same as in example 1.
(3) Mixing a hydrogen type Y/ZSM-48 composite molecular sieve and a tetraethylammonium hydroxide solution in a high-pressure reaction kettle under the stirring condition, introducing nitrogen to control the system pressure to be 0.45MPa, then heating to 65 ℃, continuously stirring at a constant temperature for 2.0 hours, relieving the pressure, cooling, performing suction filtration until the pH value is less than 9, drying for 24 hours at 100 ℃, and roasting for 6 hours at 520 ℃ to obtain the modified Y/ZSM-48 composite molecular sieve. The concentration of the tetraethyl ammonium hydroxide solution is 0.15mol/L, and the mass ratio of the hydrogen Y/ZSM-48 composite molecular sieve to water in the solution is 1: 10. Specific properties are shown in table 1.
Example 10
Steps (1) and (2) were the same as in example 2.
(3) Mixing a hydrogen type Y/ZSM-48 composite molecular sieve and a tetrabutylammonium hydroxide solution in a high-pressure reaction kettle under the stirring condition, introducing air to control the system pressure to be 0.55MPa, then heating to 65 ℃, continuously stirring at a constant temperature for 2 hours, relieving the pressure, cooling, performing suction filtration until the pH value is less than 9, drying at 90 ℃ for 18 hours, and roasting at 580 ℃ for 3 hours to obtain the modified Y/ZSM-48 composite molecular sieve. The concentration of the tetrapropylammonium hydroxide solution is 0.25mol/L, and the mass ratio of the hydrogen type Y/ZSM-48 composite molecular sieve to water in the solution is 1: 15. Specific properties are shown in table 1.
Comparative example 1
The same procedure as in example 1 except that the reaction in step (3) was carried out under atmospheric pressure.
Comparative example 2
The same as example 1 except that in step (3), the tetrapropylammonium hydroxide solution was replaced with a 0.25mol/L sodium hydroxide solution (i.e., high-pressure inorganic base treatment).
TABLE 1 physicochemical Properties of modified Y/ZSM-48 composite molecular sieves
The application of the modified Y/ZSM-48 composite molecular sieve carrier comprises the following steps:
ion exchange: the molecular sieves prepared in example 1 and comparative example 1 were washed to neutrality, dried, and then ion-exchanged with 1mol/L ammonium nitrate in a water bath at 80 ℃ to make the sodium oxide content less than 0.5%, washed, and dried to obtain a hydrogen type molecular sieve.
Preparing a catalyst: uniformly mixing alumina powder, amorphous silicon aluminum and modified molecular sieve powder, adding an acid solution, fully rolling and forming, drying for 8 hours at 100 ℃, and finally roasting for 8 hours at 600 ℃ to obtain a catalyst carrier; preparing a metal dipping solution of W and Ni to dip the obtained catalyst carrier, then drying the catalyst carrier for 6 hours at the temperature of 120 ℃, and finally roasting the catalyst carrier for 6 hours at the temperature of 470 ℃ to obtain the hydrocracking catalyst. The catalyst properties are shown in table 2.
Catalyst evaluation conditions: the evaluation apparatus was a 200m1 compact hydrogenation apparatus, and the catalyst was presulfided before the activity evaluation. The properties of the raw oil and the reaction process conditions used for evaluating the catalyst activity are shown in tables 3 and 4, and the results of comparing the catalyst reaction performance are shown in table 5. When the catalyst is evaluated, raw oil firstly passes through a hydrofining catalyst bed layer and then directly enters a hydrocracking catalyst bed layer, and the organic nitrogen content in the raw oil is controlled to be lower than 20ppm when the raw oil passes through the hydrofining catalyst bed layer.
TABLE 2 composition of the catalyst
TABLE 3 Process conditions
TABLE 4 Properties of the raw materials
TABLE 5 catalyst reactivity
The hydrocracking reaction result shows that compared with other molecular sieves, the modified Y/ZSM-48 composite molecular sieve with the mesoporous structure characteristic has the same conversion rate, the reaction temperature is 3-8 ℃ lower, and the BMCI value of a tail oil product, the content of naphthenic hydrocarbon with more than two rings and the content of straight-chain alkane in the tail oil are lower. The molecular sieve prepared by the method has better accessibility of active sites, and is beneficial to the hydrogenation ring opening of polycyclic aromatic hydrocarbon and the isomerization of straight-chain alkane.
Claims (18)
1. A preparation method of a modified Y/ZSM-48 composite molecular sieve is characterized by comprising the following steps: the method comprises the following steps:
(1) roasting the Y-type molecular sieve at high temperature, then contacting unsaturated olefin with the roasted Y-type molecular sieve, carrying out roasting carbon deposition reaction in an inert gas atmosphere, and then carrying out desiliconization treatment on the surface of the Y-type molecular sieve to obtain a modified Y-type molecular sieve;
(2) adding modified Y-type molecular sieve powder into a solution containing sodium hydroxide and a template agent, aging for 0.5-12 hours at 50-180 ℃ under a closed condition, cooling to room temperature, then adding white carbon black, continuously and uniformly stirring to obtain a reaction mixture gel system, crystallizing the reaction mixture for 2-5 days at 150-180 ℃ under a closed condition, and finally cooling, washing, drying, roasting and ion exchanging to obtain a hydrogen Y/ZSM-48 composite zeolite molecular sieve;
(3) adding a hydrogen Y/ZSM-48 composite molecular sieve into a pressure-resistant container filled with an organic alkali solution under the condition of stirring, sealing the system, boosting the pressure to 0.2-1.0 MPa, then heating to 50-90 ℃, carrying out constant-temperature treatment for 0.5-3 hours, releasing the pressure, carrying out suction filtration, drying and roasting to obtain the modified Y/ZSM-48 composite molecular sieve.
2. The method of claim 1, wherein: the Y-type molecular sieve in the step (1) has the following properties: the mole ratio of silicon oxide/aluminum oxide is 4.8-20, and the specific surface area is 650-860 m2The pore volume is between 0.33 and 55 mL/g.
3. The method of claim 1, wherein: the high-temperature roasting temperature in the step (1) is 350-650 ℃, and the time is 1-12 hours.
4. The method of claim 1, wherein: the unsaturated olefin in the step (1) is a mixture of normal or isomeric olefin and diolefin with the carbon atom number of 2-10; the full contact of the olefin and the molecular sieve means that the unsaturated olefin diffuses into the molecular sieve.
5. The method of claim 4, wherein: when a gaseous unsaturated olefin is used, the gaseous unsaturated olefin is contacted with the molecular sieve under the following conditions: the pressure is 0.1-1.0 MPa, and the contact time is 0.1-2 hours.
6. The method of claim 4, wherein: when a liquid unsaturated hydrocarbon is used, the liquid unsaturated olefin is contacted with the molecular sieve under the following conditions: the pressure is 0.1-1.0 MPa, the contact time is 0.5-4 hours, and the molecular sieve is completely immersed in the liquid olefin.
7. The method of claim 1, wherein: the inert gas in the step (1) is one of nitrogen, helium and argon, the temperature of the carbon deposition roasting reaction is 450-650 ℃, and the time is 1-8 hours.
8. The method of claim 1, wherein: the desiliconization treatment process in the step (1) is as follows: adding the Y-type molecular sieve subjected to carbon deposition reaction into 0.35-1.20 mol/L sodium hydroxide solution, treating at 50-90 ℃ for 0.5-3 hours, and washing until the pH value is less than 10; the mass ratio of the addition amount of the Y-type molecular sieve to water in the solution is 1: 3-20.
9. The method of claim 1, wherein: the molar ratio of the reaction mixture gel system in the step (2) is calculated by the following substances, wherein the modified Y-type molecular sieve is not included: 1.1 to 1.4Na2O:21~25SiO20.4 to 0.6 parts of a template agent 350 to 450H2O; wherein the template agent is hexamethonium bromide and/or hexamethonium chloride; based on the mass of the reaction mixture gel, the addition amount of the modified Y-type molecular sieve accounts for 5-20 wt% of the reaction mixture gel system.
10. The method of claim 1, wherein: the drying conditions in the step (2) are as follows: the drying temperature is 50-120 ℃, and the drying time is 8-24 hours.
11. The method of claim 1, wherein: the roasting conditions in the step (2) are as follows: the roasting temperature is 450-650 ℃, and the roasting time is 1-6 hours.
12. The method of claim 1, wherein: and (3) exchanging ions for ammonium, wherein the exchange times are 1-2 times, the exchange temperature is 80-120 ℃, the ammonium salt is 0.5-3.0 mol/L ammonium nitrate solution, the liquid-solid ratio in the exchange process is 5-15 mL/g, and the exchange time is 1.0-3.0 hours each time.
13. The method of claim 1, wherein: the organic alkali in the step (3) is one or more of tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide, and the concentration of the organic alkali solution is 0.05-0.35 mol/L.
14. The method of claim 1, wherein: and (3) directly adding tetraethylammonium halide, tetrapropylammonium halide or tetrabutylammonium halide to react with sodium hydroxide to generate tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide.
15. The method of claim 1, wherein: and (3) pressurizing by introducing compressed air, nitrogen or inert gas into the pressure-resistant container.
16. The method of claim 1, wherein: and (4) performing suction filtration in the step (3) until the pH value is less than 9, and drying for 6-24 hours at the temperature of 80-120 ℃.
17. The method of claim 1, wherein: and (3) roasting for 2-8 hours at the temperature of 450-650 ℃.
18. The Y/ZSM-48 composite molecular sieve prepared by the method according to any one of claims 1 to 17, wherein the Y/ZSM-48 composite molecular sieve is used for preparing a hydrocracking catalyst, the hydrocracking catalyst is used for conversion of condensed ring macromolecules and isomerization reaction of linear alkanes in a hydrocracking process, the reaction conditions are that the reaction pressure is 10-20 MPa, the reaction temperature is 350-430 ℃, the volume ratio of hydrogen to oil is 500-1800, and the liquid hourly volume space velocity is 0.5-5.0 h in the presence of hydrogen-1。
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| CN105540608A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Y-Beta composite molecular sieve having double mesoporous structure, and preparation method thereof |
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| CN105540608A (en) * | 2014-11-03 | 2016-05-04 | 中国石油化工股份有限公司 | Y-Beta composite molecular sieve having double mesoporous structure, and preparation method thereof |
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