CN106669811A - MCM-22/ZSM-22 composite molecular sieve catalyst and its preparation method and application - Google Patents
MCM-22/ZSM-22 composite molecular sieve catalyst and its preparation method and application Download PDFInfo
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- CN106669811A CN106669811A CN201510751279.1A CN201510751279A CN106669811A CN 106669811 A CN106669811 A CN 106669811A CN 201510751279 A CN201510751279 A CN 201510751279A CN 106669811 A CN106669811 A CN 106669811A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 60
- 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 60
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 34
- 239000003921 oil Substances 0.000 claims abstract description 14
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 11
- 239000010687 lubricating oil Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 36
- 229910052681 coesite Inorganic materials 0.000 claims description 26
- 229910052906 cristobalite Inorganic materials 0.000 claims description 26
- 229910052682 stishovite Inorganic materials 0.000 claims description 26
- 229910052905 tridymite Inorganic materials 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- 239000000499 gel Substances 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical group O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- -1 dimethylene imines Chemical group 0.000 claims description 7
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000002366 halogen compounds Chemical class 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002283 diesel fuel Substances 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 238000001802 infusion Methods 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 claims description 4
- 239000004927 clay Substances 0.000 claims description 4
- 229910052570 clay Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009415 formwork Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910001648 diaspore Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910001679 gibbsite Inorganic materials 0.000 claims description 3
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002199 base oil Substances 0.000 abstract description 6
- 238000009833 condensation Methods 0.000 abstract description 5
- 230000005494 condensation Effects 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 3
- 239000012263 liquid product Substances 0.000 abstract 1
- 230000001050 lubricating effect Effects 0.000 abstract 1
- 238000006317 isomerization reaction Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000126 substance Substances 0.000 description 10
- 239000001993 wax Substances 0.000 description 7
- 238000005336 cracking Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7484—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
-
- B01J35/615—
-
- B01J35/633—
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- 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
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1062—Lubricating oils
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1074—Vacuum distillates
Abstract
The invention discloses a MCM-22/ZSM-22 composite molecular sieve catalyst and its preparation method and application. The catalyst comprises by weight, 10-90% of a modified MCM-22/ZSM-22 composite molecular sieve, and a group VIII noble metal active component. The modified MCM-22/ZSM-22 composite molecular sieve comprises, weight, 0.1-10% of silicon dioxide. MCM-22 molecular sieves in the MCM-22/ZSM-22 composite molecular sieve coat ZSM-22 molecular sieves and the MCM-22/ZSM-22 composite molecular sieve comprises, by weight, 1.0-50% of MCM-22. The catalyst can reduce the condensation point of the waxy raw material oil, improves a yield of the liquid product and has a high viscosity index of the lubricating base oil in lubricating oil fraction isodewaxing.
Description
Technical field
The present invention relates to a kind of MCM-22/ZSM-22 composite molecular sieve catalysts and its preparation method and application, relate in particular to a kind of be suitable to MCM-22/ZSM-22 composite molecular sieve catalysts of lubricating oil isomerization dewaxing and its preparation method and application.
Background technology
The isomerization reaction of n-alkane is the important reaction of the isomerization-visbreaking process of the isomerization dewaxing process of petroleum refining process such as lubricating oil and diesel oil.N-alkane is the undesirable components in lube cut, so as to cause its pour point compared with high and low temperature poor performance.Improve these performances it is necessary to high-melting-point n-alkane therein is completely or partially removed.At present conventional process for dewaxing mainly has solvent dewaxing, catalytic dewaxing and isomerization dewaxing.
Solvent dewaxing is exactly to be removed using wax solubility property in a solvent, the shortcoming of this method be solvent select it is difficult, waste substantial amounts of organic solvent, harmful and pollute that environment, equipment investment and operating cost are high and product quality is limited by raw material.Catalytic dewaxing is exactly using the catalyst with shape-selective cracking function, make the wax component in fraction that selective catalytic cracking to occur, generate the hydro carbons compared with small molecule, such as United States Patent (USP) USP.4247388 and USP.4659311 are exactly the wax for using the method for catalytic dewaxing to remove in lubricating oil, the shortcoming of this method is the small-molecule substance due to the macromolecular compound of substantial amounts of high value being converted into low value, makes that base oil yield is low, viscosity index (VI) loss is big, by-product value is low.Compared with first two process for dewaxing, isomerization dewaxing is to make macromole wax that isomerization reaction to occur to generate isoparaffin, and isoparaffin has lower condensation point and pour point and higher viscosity index (VI) compared with the wax of same molecular amount, and in remaining in heavy distillate, so that fraction oil yield is greatly enhanced.
It is many with regard to the report of isomerization dewaxing catalyst at present, for example, United States Patent (USP) US5990371, US5833837, US5817907, US5149421, US5135638, US5110445, US4919788, US4419420, US4601993, US4599162, US4518485 etc. all relates to Isodewaxing Technology, the acidic components for wherein using mainly have modenite, SAPO-11, SAPO-31, SAPO-41, ZSM-23, SSZ-32, ZSM-22 type molecular sieves etc., for the molecular sieve of different structure, due to its unique pore passage structure and physico-chemical property, so being adapted to different purposes.ZSM-5 molecular sieve has three-dimensional ten-ring structure pore, NU-87 molecular sieves have two-dimentional ten-ring structure pore, ZSN-22, EU-1, SAPO-11 structure molecular screen has one-dimensional ten-ring structure pore, and MCM-22 has two kinds of independent polynary ring channel systems, one kind is two-dimentional sinusoidal wave form, the ten-ring duct of intersection, these molecular sieves in the isomerization reaction of hydrocarbon molecules, with unique effect.But, due to pore passage structure and the nuance of physico-chemical property, make its effect for being applied to isomerization dewaxing be not quite similar again.These materials can to a certain extent make paraffin hydrocarbon that isomerization reaction occurs, but for some reactions, such as lube cut, due to wherein containing very complicated component, it is not that identical molecule participates in reaction, so for the molecular sieve with homogeneous structural just occurs some adaptive problems, the catalysis material of good match is capable of to a kind of molecule, for other component may be less desirable.
For the n-alkane in lube cut and diesel oil, due to its condensation point it is higher, cause lubricating oil and research of cold flow properties of diesel fuel poor, isomerization dewaxing is to make high-melting-point long-chain normal paraffin and polycyclic naphthene hydrocarbon in wax component be converted into the isoparaffin of the relatively low unilateral chain of fusing point and the monocyclic naphthenes of belt length side chain using the bifunctional catalyst with special pore structure.But the high alkane fusing point of isomerisation degree is higher on the contrary, so must just control the isomerisation degree of wax molecule, this just proposes strict requirements to the Acidity and pore structure and hydrogenation component of acidic components.In general acidic components will have the acid centre and the pore structure with space restriction effect of moderate strength, and active metal component has quick hydrogenation/dehydrogenation activity, prevents the further isomery of tertiary carbonium ion, or even cracking.Due to cracking reaction so that high carbon number alkane transformations are the low-carbon alkanes of small molecule so as to reduce the yield of purpose product, therefore should as far as possible promote the carrying out of isomerization reaction, while suppressing the generation of cracking reaction as far as possible.US6204426 proposes to adopt the mixture of SAPO-11, SAPO- 31, SAPO-41, ZSM-22, ZSM-23, ZSM-35 etc. to prepare isomerization catalyst for carrier, US5833837 proposes the production procedure that oil base oil is lubricated using dual catalyst system, that is, SAPO-11, SAPO- 31, SAPO-41 catalyst series is respectively adopted to carry out the isomerization of light lubricant component and carry out the isomerization of heavy lubricating oil component using ZSM-5 catalyst.But the equal Shortcomings part of both flow processs, the former can not effectively play the synergism of each mixed molecular sieve component, and the latter extends technological process, increased operation difficulty, considerably increases cost of investment.
The content of the invention
To overcome weak point of the prior art, the invention provides a kind of paraffin hydrocarbon selective isomerization catalyst that activity is high, selectivity is good and its preparation method and application, the catalyst can not only reduce the condensation point of waxy feeds oil, and can also improve the yield of fluid product, in particular for lube cut isomerization dewaxing process, with lube base oil viscosity index (VI) it is high the characteristics of.
A kind of MCM-22/ZSM-22 composite molecular sieve catalysts, containing modified MC M-22/ZSM-22 composite molecular screen and the VIIIth race's noble metal active component, based on the weight content of catalyst, modified MC M-22/ZSM-22 composite molecular screen content is 10 ~ 90%, preferably 20% ~ 80%, VIIIth race's bullion content is 0.1 % ~ 1.5%, wherein silica weight content is 0.1% ~ 10%, preferably 0.5% ~ 5% in described modified MC M-22/ZSM-22 composite molecular screen（The silicon dioxide in MCM-22/ZSM-22 composite molecular screens is not included）, balance of inorganic refractory oxide, MCM-22 molecular sieves are wrapped in around ZSM-22 molecular sieves in the MCM-22/ZSM-22 composite molecular screens, and the weight content of MCM-22 is 1.0 ~ 50%, preferably 5.0 ~ 30% in MCM-22/ZSM-22 composite molecular screens.
Contain inorganic refractory oxide in catalyst of the present invention, inorganic refractory oxide is one or more in aluminium oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, zirconium oxide and clay, preferably aluminium oxide and/or silicon oxide, more preferably aluminium oxide.Its precursor can be selected from boehmite, boehmite, diaspore, gibbsite and visit one or more in aluminum stone, preferably boehmite.
Catalyst property of the present invention is as follows：BET specific surfaces are 200～350m2/g, and pore volume is 0.3～0.5ml/g.The specific surface and pore volume of catalyst is to adopt ASAP in the present invention
2400, low temperature liquid nitrogen absorption method is calculated through BET.
A kind of preparation method of alkane hydroisomerization catalyst, its step is：
1）
Prepare MCM-22/ZSM-22 composite molecular screens；
2）
Tetraethyl orthosilicate is loaded on above-mentioned molecular sieve, then Jing high-temperature vapors are processed, and through dry and roasting, obtain modified MCM-22/ZSM-22 composite molecular screens；
3）
By step 2）The composite molecular screen and inorganic refractory oxide of preparation is mixed and made into catalyst carrier；
4）
To contain the expensive active metal component of the VIIIth race with conventional infusion process to load on carrier, then by drying, calcination process, obtain final catalyst.
The inventive method, step 1）The preparation of middle MCM-22/ZSM-22 composite molecular screens includes following content, and ZSM-22 molecular sieves are added in silica-alumina gel, and described silica-alumina gel mole is consisted of：Al2O3/SiO2=0.01 ~ 0.05, OH-/SiO2=0.02 ~ 0.35, R/SiO2=0.15 ~ 1.0, H2O/SiO2=5 ~ 50, halogen compounds and SiO2Mol ratio be organic formwork agent for 0.03 ~ 0.5, R.Preferably：Al2O3/SiO2=0.02 ~ 0.04, OH-/SiO2=0.01 ~ 0.10, R/SiO2=0.25 ~ 0.7, H2O/SiO2=10 ~ 40, halogen compounds and SiO2Mol ratio be 0.05 ~ 0.3.Wherein organic formwork agent R can be dimethylene imines, may also be the mixed templates of one or more composition in dimethylene imines and hydro carbons, organic amine, alcohols, ketone.Described halogen compounds are CH3I、CH3CHCl2、CHCl3Deng one or more in the organohalogen compound containing 1 ~ 3 carbon atom.Involved silicon source, silicon source and alkali source are the compound commonly used in Zeolite synthesis, such as silicon source is silica gel, Ludox or waterglass, silicon source is hydrochlorate of sodium metaaluminate, aluminium hydroxide, activated alumina or aluminum etc., and described alkali source is sodium hydroxide or potassium hydroxide etc..The addition of described ZSM-22 molecular sieves is silicon dioxide（In terms of the silicone content in silica-alumina gel）The 0.5 ~ 20 of weight, preferably 1.0 ~ 15.The crystallization under self-generated pressure hydrothermal condition, wherein crystallization temperature are 100 DEG C ~ 200 DEG C, and preferably 110 DEG C ~ 150 DEG C, crystallization time is 16 hours ~ 120 hours, preferably 20 hours ~ 70 hours.Obtain composite molecular screen.
Step 2）Described MCM-22/ZSM-22 composite molecular screens will be through modification, the modifying agent for being used is tetraethyl orthosilicate, and mode of loading can be using infusion process and kneading method, preferably infusion process, preparation can select organic alkoxide or ether, preferably methanol or ethanol containing teos solution.On the basis of molecular sieve, the load capacity of tetraethyl orthosilicate（With SiO2Meter）For 0.1% ~ 10%, preferably 0.5% ~ 5%, dip time 1 hour ~ 10 hours, preferably 3 hours ~ 6 hours, again the high-temperature vapors of Jing 100% were processed the composite molecular screen Jing after tetraethyl orthosilicate dipping, and actual conditions is as follows：Processing pressure 0.1MPa ~ 5.0MPa, preferred 0.5MPa ~ 3.0MPa, 100 DEG C ~ 500 DEG C for the treatment of temperature, preferably 150 DEG C ~ 350 DEG C, process time 0.5 hour ~ 5 hours, preferably 1.0 hours ~ 3.0 hours.
Step 3）Described inorganic refractory oxide is one or more in aluminium oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, zirconium oxide and clay, preferably aluminium oxide and/or silicon oxide, more preferably aluminium oxide.Its precursor can be selected from boehmite, boehmite, diaspore, gibbsite and visit one or more in aluminum stone, preferably boehmite.
Step 4）The preferred platinum of VIIIth race's noble metal and/or palladium.Most preferably platinum.Metal acid, metal acid-salt, chloride, ammino-complex, hydroxo complex or their mixture of the VIIIth race's noble metal are adopted for raw material, using the method including dipping, precipitation, deposition, addition adhesive bonding or mechanical press, the combination of noble metal and composite molecular screen is realized.
Catalyst of the present invention can apply to various waxy feeds isomery processing procedures, and waxy feeds can be waxy feeds such as diesel oil, white oil, the atmospheric heavy distillate of more than 140 DEG C of initial boiling point（AGO）, vacuum distillate（VGO）, hydrocracking tail oil, lubricating oil or paraffin etc., be particularly suitable for the processing procedure of lubricating oil.The waxy feeds higher for sulfur-bearing, nitrogen impurity content typically need to carry out carrying out isomery process after hydrofinishing again.Paraffin selective isomerization reaction condition is in crude lube stock：Hydrogen Vapor Pressure 2MPa ~ 20MPa, 260 DEG C ~ 400 DEG C of temperature, the h of volume space velocity 0.5-1~4.0h-1, hydrogen to oil volume ratio 200 ~ 1000, optimum condition is：Hydrogen Vapor Pressure 5MPa ~ 10MPa, 320 DEG C ~ 380 DEG C of temperature, volume space velocity 1.0h-1~3.0h-1, hydrogen to oil volume ratio 300 ~ 500.
Compared with prior art, a kind of alkane hydroisomerization catalyst of the invention and its preparation method and application has the advantage that：
（1）The MCM-22/ZSM-22 composite molecular screens that the present invention is provided are different from the composite molecular sieve of MCM-22 and ZSM-22 molecular sieves simple physical mixing，Composite molecular screen has the pore passage structure feature and acidic character of two kinds of molecular sieves of MCM-22 and ZSM-22 concurrently，Namely ZSM-22 molecular sieve surfaces " absorption " MCM-22 molecular sieves，Due to the column type supercage that the section of MCM-22 zeolites is twelve-ring，Supercage free internal space 0.71*0.71*0.91nm，The pocket with larger absorbability can be formed in crystal outer surface，Two subchannels are provided for reactant，Prevention has the reactant contact active center of side chain，Avoid the generation of highly-branched chain isomerous body，Simultaneously while making catalyst that there is preferable long chain alkane isomerization function，The generation of the side reactions such as cracking reaction can be reduced，Improve isomerisation selectivity；
（2）The present invention adds organohalogen compound in the preparation process of composite molecular screen, is more prone to can MCM-22 molecular sieves, and equably is grown in around ZSM-22, it is to avoid aggregation occurs and ZSM-22 molecular sieve pore passages are blocked；
（3）The present invention selects kinetic diameter than larger tetraethyl orthosilicate（Molecular diameter>0.8nm）As modifying agent, because its molecular volume is than larger, can be with the hydroxy combining of molecular sieve surface, can be with the acid centre of autotelic covering " outer layer " molecular sieve catalyst, it is to avoid here occurs the cracking reaction of non-selectivity；There is reactant contact more likely to select at the ZSM-22 molecular sieves aperture of type, isomerisation selectivity is improved.
（4）The paraffin hydro heterogeneous catalyst prepared using the MCM-22/ZSM-22 composite molecular screens with appropriate mass ratio, for the hydro-isomerization dealkylation reaction of lube cut in, pour point high with purpose product yield（Condensation point）The characteristics of low and viscosity index (VI) is high.
Specific embodiment
The preparation process of catalyst of the present invention is further illustrated below by embodiment, but be invention should not be deemed limited in below example, if no special instructions percentage composition is weight/mass percentage composition to following examples.
Embodiment
1
First by 4.26g NaAlO2Mix homogeneously in 500 milliliters of stainless steel cauldrons with 19.08g sodium hydroxide solutions, under agitation by 33g silica gel, 408.2g deionized waters, 18.96g hexamethylene imines（HMI）In sequentially adding kettle, 1.65g CH are added3I, finally adds 55g
ZSM-22.After continuing to stir 10 minutes, reactor is sealed, crystallization 15h at 120 DEG C.After crystallization terminates, solid product (MCM-22/ZSM-22) is isolated, the weight content of MCM-22 is 25.4%.
Tetraethyl orthosilicate 5.5g is taken, the methanol solution of 150g tetraethyl orthosilicates is configured to, above-mentioned MCM-22/ZSM-22 molecular sieve 100g are taken, in being impregnated into above-mentioned solution, is impregnated 6.5 hours, then again the high-temperature vapors of Jing 100% are processed, and actual conditions is as follows：Processing pressure 1.0MPa, 350 DEG C for the treatment of temperature, process time 3.5 hours.Obtain SiO2Load capacity is 1.5% modified MC M-22/ZSM-22 composite molecular screen, and numbering is S-1.
Embodiment
2
First by 1.488g NaAlO2Mix homogeneously in 500 milliliters of stainless steel cauldrons with 36.06g sodium hydroxide solutions, under agitation by 23g silica gel, 3.3gCHCl3 、359.3g deionized waters, 3.00gHMI are sequentially added in kettle, finally add 100g ZSM-22.After continuing to stir 10 minutes, reactor is sealed, crystallization 20h at 130 DEG C.After crystallization terminates, solid product (MCM-22/ZSM-22) is isolated, the weight content of MCM-22 is 11.1%.
Tetraethyl orthosilicate 16.8g is taken, the methanol solution of 150g tetraethyl orthosilicates is configured to, above-mentioned MCM-22/ZSM-22 molecular sieve 100g are taken, in being impregnated into above-mentioned solution, is impregnated 2.5 hours, then again the high-temperature vapors of Jing 100% are processed, and actual conditions is as follows：Processing pressure 1.5MPa, 350 DEG C for the treatment of temperature, process time 2.0 hours.Obtain SiO2Load capacity is 4.8% modified MC M-22/ZSM-22 composite molecular screen, and numbering is S-2.
Embodiment
3
First by 1.136g NaAlO2Mix homogeneously in 500 milliliters of stainless steel cauldrons with 24.04g sodium hydroxide solutions, under agitation 22g silica gel, 237g deionized waters, 12g HMI and 6g hexamethylene are sequentially added in kettle, finally add 120g ZSM-22.After continuing to stir 10 minutes, reactor is sealed, crystallization 15h at 120 DEG C.After crystallization terminates, solid product (MCM-22/ZSM-22) is isolated, numbering is S-3
The weight content of MCM-22 is 7.5%.
Tetraethyl orthosilicate 10.8g is taken, the methanol solution of 150g tetraethyl orthosilicates is configured to, above-mentioned MCM-22/ZSM-22 molecular sieve 100g are taken, in being impregnated into above-mentioned solution, is impregnated 6.5 hours, then again the high-temperature vapors of Jing 100% are processed, and actual conditions is as follows：Processing pressure 1.5MPa, 350 DEG C for the treatment of temperature, process time 4.0 hours.Obtain SiO2Load capacity is 3.1% modified MC M-22/ZSM-22 composite molecular screen, and numbering is S-2.
Embodiment
4
With embodiment 1, the ZSM-22 molecular sieves that difference is added are 150g to the preparation process of composite molecular screen MCM-22/ZSM-22 of the present invention, and the weight content of MCM-22 is 8.32%, SiO2Load capacity is 1.1% modified MC M-22/ZSM-22 composite molecular screen, and numbering is S-4,
Embodiment
5
With embodiment 1, it is 90g that difference adds ZSM-22 molecular sieves to the preparation process of composite molecular screen MCM-22/ZSM-22 of the present invention, and the weight content of MCM-22 is 14.1%, SiO2Load capacity is 2.8% modified MC M-22/ZSM-22 composite molecular screen, and numbering is S-5.
Embodiment
6
The preparation of catalyst E-1 of the present invention
Take above-mentioned modified MCM-22/ZSM-22 composite molecular screens and 100 grams（In terms of aluminium oxide）Aluminium hydroxide（The SB of German Condean companies production）It is sufficiently mixed and 10 grams of sesbania powder mix homogeneously, is subsequently adding 230ml water and 14ml concentrated nitric acids（Mass concentration is 66.5%）, abundant kneading makes paste plastic, the cylindrical bars of a diameter of 1.5mm are extruded on banded extruder, cylindrical bars are dried 16 hours at 100 DEG C, and then 550 DEG C of roastings obtain catalyst carrier of the present invention in 4 hours in air atmosphere, and the dipping method using common filling hole is with containing H2PtCl6Solution saturation impregnates, then 100 DEG C of dryings 8 hours, 500 DEG C of roasting 3h in air atmosphere again, and catalyst of the present invention is obtained, and numbering is E-1, and its physico-chemical property is shown in Table 1, and reaction result is shown in Table 3.
Embodiment
7
The preparation of catalyst E-2 of the present invention
With embodiment 7, difference is to use the MCM-22/ZSM-22 composite molecular screens of the preparation of embodiment 2 to the preparation process of catalyst E-2 of the present invention, the catalyst of the present invention prepared, and numbering is E-2, and its physico-chemical property is shown in Table 1, and reaction result is shown in Table 3.
Embodiment
8
~
10
The preparation of catalyst E-3 ~ E-5 of the present invention
The preparation process of catalyst E-3 ~ E-5 of the present invention is with embodiment 1, molecular sieve used by difference respectively is the molecular sieve of the preparation of embodiment 3 to 5, aluminium hydroxide is different with the amount of the amount of the noble metal of load, catalyst E-3 ~ the E-5 of the present invention for preparing, its physico-chemical property is shown in Table 1, and reaction result is shown in Table 3.
Comparative example
1
The preparation of comparative catalyst C-1 of the present invention
The preparation method of comparative catalyst of the present invention is with embodiment 5, it is a difference in that used molecular sieve with the method synthesis ZSM-22 molecular sieves provided in CN200510066975, molecular sieve numbering is Z-1, the comparative catalyst C-1 of the present invention for preparing, its physico-chemical property is shown in Table 1, and reaction result is shown in Table 3.
Comparative example
2
The preparation method of comparative catalyst of the present invention is a difference in that the same United States Patent (USP) of used molecular sieve with embodiment 1（USP 4,954,325）Provided in method synthesis MCM-22 molecular sieves, molecular sieve numbering be M-1, the comparative catalyst C-2 of the present invention for preparing, its physico-chemical property is shown in Table 1, and reaction result is shown in Table 3.
Comparative example
3
The preparation of comparative catalyst C-3 of the present invention
With embodiment 1, the molecular sieve used by difference is that two kinds of molecular sieves of ZSM-22 and MCM-22 press 4 to the preparation process of comparative catalyst C-3 of the present invention:1（Mass ratio）Mechanical mixture, the comparative catalyst C-3 of the present invention for preparing, its physico-chemical property is shown in Table 1, and reaction result is shown in Table 3.
Table 1 is respectively implemented（Relatively）Example prepares the main physico-chemical property of catalyst
Note：（1）1. on the basis of catalyst quality, ZSM-22 and MCM-22 mixed molecular sieves, mass ratio 4 are 2. represented:1（2）S represents specific surface area, and V represents pore volume.
Catalyst prepared by above example and comparative example is evaluated using the medium-sized fixed bed reactors of 200ml, and loaded catalyst is 200ml, and prereduction is carried out to catalyst before charging, makes the noble metal on catalyst be changed into reduction-state, and reducing condition is as follows：In presence of hydrogen, 300 DEG C ~ 500 DEG C of temperature, pressure 0.5MPa ~ 10MPa, 1 hour ~ 12 hours time,
Evaluate used raw oil main character and be shown in Table 2.
The raw oil main character of table 2
The evaluating catalyst condition of table 3 and result
The evaluation result of table 3 shows, compared with comparative catalyst, using the present invention provide catalyst, for the hydroprocessing processes of lube cut in, when lube base oil pour point is close, C5 +Liquid is received and improves more than 5wt%, and lube base oil yield improves more than 10wt%, and the viscosity index (VI) of product improves 10 ~ 24 units, illustrate catalyst of the present invention during process crude lube stock, and effect is with significantly improving.
Claims (20)
1. a kind of MCM-22/ZSM-22 composite molecular sieve catalysts, it is characterised in that：Containing modified MC M-22/ZSM-22 composite molecular screen and the VIIIth race's noble metal active component in the catalyst, based on the weight content of catalyst,
Modified MC M-22/ZSM-22 composite molecular screen content is 10 ~ 90%, and the VIIIth race's bullion content is 0.1
% ~ 1.5%, silica weight content is 0.1% ~ 10% in wherein described modified MC M-22/ZSM-22 composite molecular screen, balance of MCM-22/ZSM-22 composite molecular screens, MCM-22 molecular sieves are wrapped in around ZSM-22 molecular sieves in the MCM-22/ZSM-22 composite molecular screens, and the weight content of MCM-22 is 1.0 ~ 50% in MCM-22/ZSM-22 composite molecular screens.
2. catalyst according to claim 1, it is characterised in that：Based on the weight content of catalyst, modified MC M-22/ZSM-22 composite molecular screen content is 20% ~ 80%, silica weight content is 0.5% ~ 5% in wherein described modified MC M-22/ZSM-22 composite molecular screen, MCM-22 molecular sieves are wrapped in around ZSM-22 molecular sieves in the MCM-22/ZSM-22 composite molecular screens, and the weight content of MCM-22 is 5.0 ~ 30% in MCM-22/ZSM-22 composite molecular screens.
3. catalyst according to claim 1, it is characterised in that：Contain inorganic refractory oxide in catalyst, inorganic refractory oxide is one or more in aluminium oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, zirconium oxide and clay.
4. catalyst according to claim 3, it is characterised in that：Inorganic refractory oxide is aluminium oxide, and its precursor is selected from boehmite, boehmite, diaspore, gibbsite and visits one or more in aluminum stone.
5. catalyst according to claim 1, it is characterised in that：Catalyst property is as follows：BET specific surfaces are 200～350m2/g, and pore volume is 0.3～0.5ml/g.
6. the preparation method of catalyst described in claim 1, it is characterised in that：Including following content：
Prepare MCM-22/ZSM-22 composite molecular screens；
Tetraethyl orthosilicate is loaded on above-mentioned molecular sieve, then Jing high-temperature vapors are processed, and through dry and roasting, obtain modified MCM-22/ZSM-22 composite molecular screens；
By step 2）The composite molecular screen and inorganic refractory oxide of preparation is mixed and made into catalyst carrier；
To contain the expensive active metal component of the VIIIth race with conventional infusion process to load on carrier, then by drying, calcination process, obtain final catalyst.
7. the preparation method of catalyst according to claim 6, it is characterised in that：Step 1）The preparation of middle MCM-22/ZSM-22 composite molecular screens includes following content, and ZSM-22 molecular sieves are added in silica-alumina gel, and described silica-alumina gel mole is consisted of：Al2O3/SiO2=0.01 ~ 0.05, OH-/SiO2=0.02 ~ 0.35, R/SiO2=0.15 ~ 1.0, H2O/SiO2=5 ~ 50, halogen compounds and SiO2Mol ratio be organic formwork agent for 0.03 ~ 0.5, R.
8. the preparation method of catalyst according to claim 7, it is characterised in that： Al2O3/SiO2=0.02 ~ 0.04, OH-/SiO2=0.01 ~ 0.10, R/SiO2=0.25 ~ 0.7, H2O/SiO2=10 ~ 40, halogen compounds and SiO2Mol ratio be 0.05 ~ 0.3.
9. the preparation method of catalyst according to claim 6, it is characterised in that：Organic formwork agent R is dimethylene imines, or for the mixed templates of one or more composition in dimethylene imines and hydro carbons, organic amine, alcohols, ketone.
10. the preparation method of catalyst according to claim 6, it is characterised in that：Described halogen compounds are CH3I、CH3CHCl2、CHCl3One or more in organohalogen compound.
The preparation method of 11. catalyst according to claim 6, it is characterised in that：Involved silicon source is silica gel, Ludox or waterglass in gel rubber system, and silicon source is the hydrochlorate of sodium metaaluminate, aluminium hydroxide, activated alumina or aluminum, and alkali source is sodium hydroxide or potassium hydroxide.
The preparation method of 12. catalyst according to claim 6, it is characterised in that：The addition of described ZSM-22 molecular sieves is 0.5 ~ 20 of silica weight in gel, and the crystallization under self-generated pressure hydrothermal condition, wherein crystallization temperature are 100 DEG C ~ 200 DEG C, and crystallization time obtained composite molecular screen for 16 hours ~ 120 hours.
The preparation method of 13. catalyst according to claim 12, it is characterised in that：The addition of ZSM-22 molecular sieves is 1.0 ~ 15 of silica weight in gel, and the crystallization under self-generated pressure hydrothermal condition, wherein crystallization temperature are 110 DEG C ~ 150 DEG C, and crystallization time is 20 hours ~ 70 hours.
The preparation method of 14. catalyst according to claim 6, it is characterised in that：Step 2）Described MCM-22/ZSM-22 composite molecular screen modifications adopt infusion process, and dip time 1 hour ~ 10 hours, the high-temperature vapors of Jing 100% process again of the composite molecular screen Jing after tetraethyl orthosilicate dipping, actual conditions is as follows：Processing pressure 0.1MPa ~ 5.0MPa, 100 DEG C ~ 500 DEG C for the treatment of temperature, process time 0.5 hour ~ 5 hours.
The preparation method of 15. catalyst according to claim 6, it is characterised in that：Step 3）Described inorganic refractory oxide is one or more in aluminium oxide, titanium oxide, silicon oxide, boron oxide, magnesium oxide, zirconium oxide and clay.
The preparation method of 16. catalyst according to claim 6, it is characterised in that：Step 4）VIIIth race's noble metal is platinum and/or palladium, with the metal acid of the VIIIth race's noble metal, metal acid-salt, chloride, ammino-complex, hydroxo complex or their mixture as raw material, using the method including dipping, precipitation, deposition, addition adhesive bonding or mechanical press, the load of noble metal and composite molecular screen is realized.
Application of the catalyst described in 17. claim 1 in waxy feeds isomery processing procedure, it is characterised in that：Waxy feeds are the waxy feeds of more than 140 DEG C of initial boiling point.
18. applications according to claim 17, it is characterised in that：Waxy feeds are diesel oil, white oil, atmospheric heavy distillate, vacuum distillate, hydrocracking tail oil, lubricating oil or paraffin.
19. applications according to claim 18, it is characterised in that：Waxy feeds are lubricating oil, and reaction condition is：Hydrogen Vapor Pressure 2MPa ~ 20MPa, 260 DEG C ~ 400 DEG C of temperature, the h of volume space velocity 0.5-1~4.0h-1, hydrogen to oil volume ratio 200 ~ 1000.
20. applications according to claim 19, it is characterised in that：Hydrogen Vapor Pressure 5MPa ~ 10MPa, 320 DEG C ~ 380 DEG C of temperature, volume space velocity 1.0h-1~3.0h-1, hydrogen to oil volume ratio 300 ~ 500.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510751279.1A CN106669811A (en) | 2015-11-09 | 2015-11-09 | MCM-22/ZSM-22 composite molecular sieve catalyst and its preparation method and application |
| DE102016121067.6A DE102016121067A1 (en) | 2015-11-09 | 2016-11-04 | Modified composite molecular sieve, process for its preparation and use, and catalyst and its use |
| GB1618794.0A GB2547964B (en) | 2015-11-09 | 2016-11-08 | Modified composite molecular sieve and preparation method and application thereof, and catalyst and application thereof |
| FR1660767A FR3043341B1 (en) | 2015-11-09 | 2016-11-08 | MODIFIED COMPOSITE MOLECULAR SIEVE AND METHOD FOR PREPARING AND APPLICATION THEREOF, AND CATALYST AND APPLICATION THEREOF |
| US15/347,166 US10392318B2 (en) | 2015-11-09 | 2016-11-09 | Modified composite molecular sieve and preparation method thereof, and paraffin isomerization catalyst |
| KR1020160148947A KR102229053B1 (en) | 2015-11-09 | 2016-11-09 | Modified composite molecular sieve and preparation method and application thereof, and catalyst and application thereof |
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| CN201510751279.1A CN106669811A (en) | 2015-11-09 | 2015-11-09 | MCM-22/ZSM-22 composite molecular sieve catalyst and its preparation method and application |
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| CN111841618A (en) * | 2020-06-29 | 2020-10-30 | 润泰化学（泰兴）有限公司 | Preparation method and application of catalyst for synthesizing 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate |
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| CN112973779A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | Post-treatment method of ZSM-22 molecular sieve and application of post-treatment method in preparation of liquid fuel by synthesis gas one-step method |
| CN113694962A (en) * | 2021-09-30 | 2021-11-26 | 中化泉州石化有限公司 | Isomerization dewaxing catalyst for hydrocracking tail oil and preparation method thereof |
| CN115283007A (en) * | 2022-08-25 | 2022-11-04 | 中山大学 | Preparation of platinum metal nanocluster HA molecular sieve and application of platinum metal nanocluster HA molecular sieve in synthesis of 1,2,3, 4-tetrahydroquinoline |
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| CN112007692A (en) * | 2019-05-31 | 2020-12-01 | 国家能源投资集团有限责任公司 | Catalyst for dewaxing lubricant base oil produced by Fischer-Tropsch wax synthesis and preparation method and application thereof |
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| CN113694962A (en) * | 2021-09-30 | 2021-11-26 | 中化泉州石化有限公司 | Isomerization dewaxing catalyst for hydrocracking tail oil and preparation method thereof |
| CN113694962B (en) * | 2021-09-30 | 2023-06-13 | 中化泉州石化有限公司 | Isomerization dewaxing catalyst for hydrocracking tail oil and preparation method thereof |
| CN115283007A (en) * | 2022-08-25 | 2022-11-04 | 中山大学 | Preparation of platinum metal nanocluster HA molecular sieve and application of platinum metal nanocluster HA molecular sieve in synthesis of 1,2,3, 4-tetrahydroquinoline |
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