CN118002193A - Isomerization dewaxing catalyst and preparation method thereof - Google Patents
Isomerization dewaxing catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN118002193A CN118002193A CN202211395096.7A CN202211395096A CN118002193A CN 118002193 A CN118002193 A CN 118002193A CN 202211395096 A CN202211395096 A CN 202211395096A CN 118002193 A CN118002193 A CN 118002193A
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- China
- Prior art keywords
- catalyst
- molecular sieve
- alumina
- preparation
- titanium
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 118
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000006317 isomerization reaction Methods 0.000 title claims description 62
- 239000002808 molecular sieve Substances 0.000 claims abstract description 45
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000002131 composite material Substances 0.000 claims abstract description 32
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 12
- 238000005470 impregnation Methods 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- 238000004898 kneading Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 32
- 239000011148 porous material Substances 0.000 claims description 32
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 26
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 20
- 229910000510 noble metal Inorganic materials 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- -1 halide salt Chemical class 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 57
- 239000000243 solution Substances 0.000 description 44
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 37
- 238000007142 ring opening reaction Methods 0.000 description 37
- 239000010687 lubricating oil Substances 0.000 description 24
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical group C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 23
- 238000011156 evaluation Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 229910052782 aluminium Inorganic materials 0.000 description 16
- 239000012065 filter cake Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 13
- 238000005336 cracking Methods 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 11
- 239000002199 base oil Substances 0.000 description 9
- 125000003367 polycyclic group Chemical group 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000004517 catalytic hydrocracking Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 125000003963 dichloro group Chemical group Cl* 0.000 description 8
- 238000007654 immersion Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 241000219793 Trifolium Species 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 239000012876 carrier material Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 150000001924 cycloalkanes Chemical class 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229940094933 n-dodecane Drugs 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910002835 Pt–Ir Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
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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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
-
- 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
- B01J29/7492—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
-
- 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
- C10G45/62—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 platinum group metals or compounds thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
- C10M101/02—Petroleum fractions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J2229/42—Addition of matrix or binder particles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/102—Aliphatic fractions
- C10M2203/1025—Aliphatic fractions used as base material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of an isomerism dewaxing catalyst, which comprises the following steps: (1) preparation of a catalyst carrier: mixing a mesoporous molecular sieve, amorphous silica-alumina and a titanium-aluminum composite oxide, adding an extrusion aid and a binder, kneading the mixture, extruding, forming, drying and roasting to obtain a catalyst carrier, wherein the drying condition is 100-130 ℃ for 1-24 h, and the roasting condition is 400-600 ℃ for 4-24 h; (2) Putting the catalyst carrier into the impregnating solution for impregnation treatment, wherein the impregnation time is 2-24 hours; (3) And drying and roasting the impregnated catalyst carrier to obtain a catalyst finished product.
Description
Technical Field
The invention belongs to the technical field of lubricating oil isomerization dewaxing, and particularly relates to an isomerization dewaxing catalyst and a preparation method thereof, which can be used for producing high-viscosity index lubricating oil base oil.
Background
The lubricating oil isomerization dewaxing technology is an effective means for producing API II and III high-quality lubricating oil base oil. The traditional lubricating oil isomerization dewaxing catalyst mainly aims at hydroisomerization conversion of paraffin in raw materials so as to reduce low-temperature flow properties such as pour point and the like of lubricating oil base oil, but the paraffin isomerization conversion process inevitably causes great loss of viscosity index of the lubricating oil base oil. Petroleum-based lubricating oil feedstocks contain a large amount of naphthenes in addition to paraffins, typically in amounts of 50wt% or more. The traditional lubricating oil isomerization dewaxing catalyst can not convert naphthenes due to the limitation of pore channels and acidity of a carrier material, and the product quality of lubricating oil base oil is affected.
ALZAID A H et al, THE KINETICS of DECALIN RING opening over a Ir/H-beta catalyst, indicate that decalin molecules can undergo ring opening reactions, beta-cracking reactions, gamma-cracking reactions, isomerism reactions and dehydrogenation reactions in a cracking system, and the conversion rate can reach more than 80%. However, the above-mentioned naphthene ring-opening reaction is carried out under a cracking system, and the total acid amount and acid strength of the cracking catalyst are higher as compared with those of the lube oil isodewaxing catalyst, whereas the total acid amount of the lube oil isodewaxing catalyst is lower, and the acid strength is concentrated in the middle and low ranges, so that the naphthene ring-opening reaction is not easy to occur under the isodewaxing reaction system.
Li Qingjun et al in the section of "research on hydroisomerization law of Long-chain alkane and bicycloalkane Mixed raw materials-influence of technological conditions" indicate that decalin has very low conversion rate under the traditional isomerization dewaxing catalytic system, and the reaction is mainly dehydrogenation reaction, and tetrahydronaphthalene and naphthalene are generated, and ring opening or isomerization products are not detected. The analysis is that the molecular critical diameter of decalin is 0.68-0.92 nm, the molecular sieve size of the isomerization dewaxing catalyst is 0.45nm multiplied by 0.55nm, and the molecular diameter of decalin exceeds the pore size of the molecular sieve, so decalin molecules are difficult to enter the pore of the molecular sieve, and dehydrogenation reaction mainly occurs on the metal site on the outer surface of the molecular sieve.
Amel Djeddi et al, "Selective Ring-Opening of Methylcyclopentane Over Titania-Supported Monometallic(Pt,Ir)and Bimetallic(Pt-Ir)Catalysts", disclose that Pt, ir single metal catalysts and Pt-Ir bimetallic catalysts were prepared using TiO 2 metal oxide as a support. The prepared catalyst can promote the selective ring-opening and cracking reaction of methyl cyclopentane under the conditions of normal pressure and 180-400 ℃. The high activity and high selectivity of the catalyst at low temperature can be attributed to the high hydrogen storage capacity of the TiO 2 with metallic function at low temperature, which is advantageous for reversely spilling the supplied hydrogen to the highly dispersed Pt, ir nanoparticles. With the increase of the reaction temperature, the ring opening selectivity of naphthenes is greatly reduced, and the cracking selectivity is remarkably increased. Taking Pt/TiO 2 catalyst as an example, the reaction temperature is increased by 340 ℃ from 300 ℃, the ring opening selectivity of the catalyst is reduced from 96% to 76%, and the cracking selectivity is increased from 4% to 22%.
Chinese patent CN103773467 and CN103773468 propose a method for producing lubricating oil base oil by hydroisomerization dewaxing, wherein the raw oil firstly enters a hydrocracking reaction zone to contact with a noble metal hydrocracking catalyst containing a Y-type molecular sieve or amorphous silicon-aluminum for reaction, a polycyclic naphthene ring opening reaction occurs, and then enters an isomerization dewaxing reaction zone to carry out normal paraffin isomerization reaction. The method of the invention enables the ring-opening reaction of the polycyclic naphthenes with more than two rings in the raw material to occur, reduces the content of the polycyclic naphthenes with low viscosity index components in the product, and reduces the loss of the viscosity index in the isomerization dewaxing process. According to the technical scheme, the hydrocracking catalyst and the isomerization dewaxing catalyst are respectively filled in the two reactors, so that the production flow is increased, and the production cost is increased; if the hydrocracking catalyst and the isomerization dewaxing catalyst are filled in the same reactor to form different catalyst beds, the hydrocracking reaction temperature and the isomerization dewaxing reaction temperature are difficult to match, the filling volume of the isomerization dewaxing catalyst is reduced, the production efficiency is reduced, and once the hydrocracking catalyst is polluted, the ring-opening effect of naphthenes cannot be ensured.
In conclusion, under the traditional lubricating oil isomerization dewaxing catalytic reaction system and reaction conditions, naphthene selective ring-opening reaction is difficult to occur. The prior art means can realize the conversion of naphthene at low temperature by using titanium dioxide, but the ring opening selectivity of naphthene is greatly reduced and the cracking selectivity is obviously increased along with the increase of the reaction temperature. If the naphthene ring opening and paraffin isomerization reactions are performed on the hydrocracking catalyst and the isomerization dewaxing catalyst, respectively, the production flow is increased and the production efficiency is lowered.
Disclosure of Invention
In view of the defects of the technology, the invention aims to provide an isomerization dewaxing catalyst and a preparation method thereof, so that the isomerization dewaxing catalyst of lubricating oil has paraffin isomerization function and naphthene selective ring opening function, thereby realizing ring opening conversion of naphthene in the isomerization dewaxing process of lubricating oil, reducing the loss of viscosity index in the isomerization dewaxing process of lubricating oil by reducing the contents of dicyclo and polycyclic naphthene with lower viscosity index, and further improving the product quality of lubricating oil base oil.
The scheme adopted by the invention is a preparation method of an isomerism dewaxing catalyst, which comprises the following steps:
(1) Preparation of a catalyst carrier: mixing a mesoporous molecular sieve, amorphous silica-alumina and a titanium-aluminum composite oxide, adding an extrusion aid and a binder, kneading the mixture, extruding, forming, drying and roasting to obtain a catalyst carrier, wherein the drying condition is 100-130 ℃ for 1-24 h, and the roasting condition is 400-600 ℃ for 4-24 h;
(2) Putting the catalyst carrier into the impregnating solution for impregnation treatment, wherein the impregnation time is 2-24 hours;
(3) And drying and roasting the impregnated catalyst carrier to obtain a catalyst finished product.
In the invention, the raw materials are contacted with the noble metal hydroisomerization dewaxing catalyst containing the mesoporous molecular sieve, the amorphous silicon aluminum and the titanium aluminum composite oxide in an isomerization dewaxing reaction zone, the noble metal/amorphous silicon aluminum and the noble metal/titanium aluminum composite oxide catalyst components can synergistically promote the selective ring-opening reaction of monocyclic, bicyclic and polycyclic naphthenes in the raw materials, promote the conversion of the bicyclic and polycyclic naphthenes with lower viscosity index in the base oil into the monocyclic naphthenes and paraffin with higher viscosity index, reduce the content of the bicyclic and polycyclic naphthenes with lower viscosity index, reduce the loss of the viscosity index in the isomerization dewaxing process, and be beneficial to the production of the high-viscosity index lubricating oil base oil.
Meanwhile, as the catalytic materials such as amorphous silicon aluminum with large pore volume, titanium aluminum composite oxide and the like are added, a diffusion channel is constructed for reactants and products, the phenomenon that isomerization and ring-opening reaction products stay on a catalyst to continue to undergo secondary cracking reaction is avoided, and the liquid yield in the lubricating oil isomerization dewaxing process is improved.
The selective ring-opening reaction of cycloalkane in the method of the present invention means a ring-opening reaction process of a cyclic hydrocarbon in which the number of carbons occurring through the hydrogenation process is not reduced.
Preferably, the preparation method of the invention, the step (1) further comprises the steps of mixing the mesoporous molecular sieve, amorphous silica-alumina and titanium-aluminum composite oxide and tabletting for shaping.
Preferably, in the preparation method according to the present invention, in the step (1), the mesoporous molecular sieve is at least one selected from the group consisting of silicoaluminophosphate molecular sieves (SAPO-11, SAPO-31, SAPO-41), zeolite molecular sieves having an MTT framework structure (ZSM-23, SSZ-32, EU-13, ISI-4 and KZ-1), and zeolite molecular sieves having a TON framework structure (θ -1, ISI-1, KZ-2, NU-10 and ZSM-22).
Preferably, in the preparation method of the invention, in the step (1), the silicon oxide content in the amorphous silica-alumina is 5-75wt%, the pore volume is 0.5-1.6 mL/g, the specific surface area is 300-600 m 2/g, the average pore diameter is 8-14 nm, and the infrared acidity is generally 0.25-0.55 mmol/g.
Preferably, in the preparation method of the invention, in the step (1), the content of silicon oxide in the amorphous silicon aluminum is 15-50 wt%, the pore volume is 1.0-1.4 mL/g, the specific surface area is 350-500 m 2/g, the average pore diameter is 10-13 nm, and the infrared acidity is 0.35-0.45 mmol/g.
Preferably, in the preparation method of the invention, in the step (1), the titanium oxide content in the titanium-aluminum composite oxide is 5-50 wt%, the pore volume is 0.7-1.5 mL/g, the specific surface area is 300-450 m 2/g, and the average pore diameter is 8-16 nm.
Preferably, in the preparation method of the present invention, in the step (1), the titanium oxide content is 10 to 50wt%, the pore volume is 0.8 to 1.2mL/g, the specific surface area is 320 to 450m 2/g, and the average pore diameter is 13 to 15nm.
Preferably, in the preparation method according to the present invention, in the step (1), the binder comprises alumina, aluminum hydroxide, pseudo-boehmite, alumina sol or silica sol, preferably a small pore alumina or small pore pseudo-boehmite material.
Preferably, in the preparation method, in the step (1), the drying temperature is 100-120 ℃ and the drying time is 1-12 h; the roasting temperature is 500-550 ℃ and the roasting time is 4-12 h.
Preferably, in the preparation method, in the step (2), the soaking time is 4-16 hours; the impregnation method is selected from any one of ion exchange, isovolumetric impregnation and coprecipitation.
The invention also provides an isomerization dewaxing catalyst prepared by the preparation method of claims 1-10, wherein the isomerization dewaxing catalyst carrier contains 5-90 wt% of mesoporous molecular sieve, 5-70 wt% of amorphous silicon-aluminum, 0.2-20 wt% of titanium-aluminum composite oxide and 0-30 wt% of binder; the active metal component of the isodewaxing catalyst at least contains one noble metal component of Pt, pd, ru, rh and Ni, the noble metal content is 0.1-2.0wt%, the metal salt is at least one of halide salt, amine complex salt, nitrate, carbonate, bicarbonate, carboxylate and formate, the specific surface area of the isodewaxing catalyst is 100-250 m 2/g, the pore volume is 0.25-0.65 mL/g, and the infrared acidity is generally 0.25-0.65 mmol/g.
Preferably, the isomerization dewaxing catalyst of the invention, wherein the isomerization dewaxing catalyst carrier contains 40 to 80wt% of mesoporous molecular sieve, 10 to 50wt% of amorphous silicon-aluminum, 1.0 to 10wt% of titanium-aluminum composite oxide and 0 to 20wt% of binder; the content of noble metal is 0.2-0.8 wt%, the specific surface area of the isomerization dewaxing catalyst is preferably 120-200 m 2/g, the pore volume is preferably 0.30-0.50 mL/g, and the infrared acidity is preferably 0.35-0.60 mmol/g.
The invention has the beneficial effects that:
The beneficial effects 1 are that: according to the invention, by adding amorphous silicon aluminum with proper acidity and pore channel structure, titanium aluminum composite oxide and other ring-opening functional components into the traditional lubricating oil isomerization dewaxing catalyst, the lubricating oil isomerization dewaxing catalyst has higher acid quantity and larger pore volume, a reaction place is provided for cycloparaffin ring-opening reaction, and the lubricating oil isomerization dewaxing catalyst has cycloparaffin ring-opening function.
The beneficial effects are 2: by adjusting the acidity and the addition proportion of ring-opening components such as amorphous silicon aluminum, titanium aluminum composite oxide and the like, the isomerization activity and the ring-opening activity of the lubricating oil isomerization dewaxing catalyst are matched, under the reaction condition of the traditional isomerization dewaxing catalyst, the catalyst can simultaneously carry out paraffin isomerization and naphthene selective ring-opening reaction, the conversion rate of decalin can reach more than 20 percent, and the ring-opening selectivity can reach more than 60 percent.
The beneficial effects are 3: the selective ring opening of cycloalkane is mainly characterized in that hexatomic cycloalkane is isomerically converted into pentatomic ring at an acid position, the pentatomic ring is selectively opened again, the selective ring opening activity of the pentatomic ring is far higher than that of the hexatomic ring, however, the raw material is easy to generate side reactions such as cracking besides the hexatomic ring/pentatomic ring isomerism and ring opening reaction at the acid position, and the yield of the target product is reduced. The invention creatively compounds noble metal/amorphous silicon aluminum and noble metal/titanium aluminum composite oxide functional components with cycloparaffin ring opening function, builds a step diffusion channel for macromolecules such as polycyclic cycloparaffin, realizes rapid diffusion of reactants and products, avoids isomerization and excessive residence of ring-opening reaction products on the catalyst to continue secondary cracking reaction, and ensures higher liquid yield in the reaction process. Compared with the traditional heterogeneous dewaxing catalyst, the novel heterogeneous dewaxing catalyst added with the amorphous silicon-aluminum and titanium-aluminum composite oxide can improve the liquid yield in the reaction process by 2-6 percent.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The test methods in the following examples are conventional methods unless otherwise specified; the reagents and compounds, unless otherwise specified, are commercially available.
Example 1
(1) SAPO-11 molecular sieve synthesis
The SAPO-11 molecular sieve synthesis was performed according to patent CN 202011142569.3. The specific operation is as follows: 109 g of pseudo-boehmite (75 wt% Al 2O3) and 636 g of deionized water are stirred uniformly, 185 g of phosphoric acid (85 wt% H 3PO4) is added and stirred for 2 hours, and 97 g of di-n-propylamine is added and stirred for 2 hours; 80 g of silica sol (30 wt% SiO 2) was added and stirred for 2 hours to form an initial gel of the reaction. The reaction mixture was charged into a 2L stainless steel autoclave, and hydrothermal crystallization was carried out at a constant temperature of 110℃and 120℃and 130℃for 1 hour and at a constant temperature of 200℃for 24 hours, respectively, with stirring rate of 200 rpm. The reaction product is washed and filtered, and the filter cake is dried for 10 hours at 110 ℃ to obtain the SAPO-11 molecular sieve with the SiO 2/Al2O3 mol ratio of about 0.5.
(2) Amorphous silicon aluminum preparation
Amorphous silica alumina preparation was carried out according to patent CN 1218089. The specific operation is as follows: adding 0.35L of aluminum sulfate solution into 0.4L of distilled water, heating and stirring until the aluminum sulfate solution is dissolved to obtain aluminum sulfate solution A with the Al 2O3 concentration of 8g/100mL, and adding a proper amount of distilled water into concentrated ammonia water to dilute the concentrated ammonia water into 10% diluted ammonia water solution B. 0.5L of distilled water was added to 0.24L of concentrated water glass having a modulus of 3.0 to obtain a diluted water glass solution C. And simultaneously dropwise adding the solution A and the solution B into a reaction kettle containing 0.2L of distilled water at 70 ℃, adjusting the flow rate of the solution A to complete the reaction within 1.5h, adjusting the flow rate of the solution B to keep the pH value of a reaction system at about 8.5, and controlling the temperature of the system at 55 ℃. After the aluminum sulfate reaction is completed, stopping adding ammonia water, stabilizing the generated alumina sol for 15min, then dropwise adding 0.62L of solution C within 10min, and aging for 50min under the conditions of the system temperature of 60-65 ℃ and the pH value of 8.5. Filtering the colloid solution after aging to obtain a wet filter cake, adding distilled water into the filter cake again for washing, and filtering to obtain a filter cake D. The filter cake was added again to distilled water and 1.76ml of phosphoric acid, stirred for 30min and filtered to give filter cake E. The filter cake E was dried at 110℃for 8 hours to give amorphous silica alumina having a SiO 2% by weight content of about 45% by weight.
(3) Preparation of titanium-aluminum composite oxide
The preparation of the titanium aluminum composite oxide was carried out according to CN 102451670. The specific operation is as follows: controlling the temperature of a glue tank to be 35 ℃, adding 2L of Al 2O3 concentration sodium aluminate solution F with the concentration of 40G/L and 0.2L of TiO 2 concentration titanium sulfate solution G with the concentration of 50G/L into a 5L glue tank at the same time, and controlling the flow rate of the solutions to finish the adding of the two solutions within 50 min; simultaneously, CO 2 gas with the concentration of 40v percent is ventilated and introduced, and the flow rate of CO 2 is rapidly regulated, so that the pH of the system is kept at about 10. After the solution F and the solution G are added dropwise, 0.2L of the solution G and 10wt% of Na 2CO3 solution are added simultaneously, the pH value is kept to be about 9.5 by adjusting the flow rate of the Na 2CO3 solution, the reaction time is 0.5h, CO 2 is stopped being introduced, and then ventilation is stabilized for 40min. The reaction product is washed and filtered, and the filter cake is dried for 8 hours at 110 ℃ to obtain the titanium aluminum composite oxide with the TiO 2 weight percent content of about 50 weight percent.
(4) Isomerization dewaxing catalyst preparation
100G of SAPO-11 molecular sieve, 21.4g of amorphous silicon aluminum, 7.2g of titanium aluminum composite oxide and 6.4g of sesbania powder are uniformly mixed to obtain a mixture H, 18.4g of 10% HNO 3 solution is dropwise added into 14.3g of SB powder and stirred to obtain aluminum gel I, the aluminum gel I is added into the mixture H, a proper amount of deionized water is dropwise added and uniformly mixed, the mixture is extruded and molded by a clover-shaped pore plate with the diameter of 1.6mm, and the extrudate is dried at 120 ℃ for 10H and baked at 550 ℃ for 12H to obtain the carrier. The obtained carrier is immersed in a dichloro tetra ammine platinum aqueous solution with the Pt content of 1wt% by an isovolumetric immersion method, and the immersed carrier is dried for 10 hours at 120 ℃ and baked for 12 hours at 450 ℃ to obtain the isodewaxing catalyst A1 with the Pt upper amount of 0.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.
(5) Evaluation of catalyst Performance
The hydrocarbon composition of industrial hydrocracking tail oil is simulated, and a mixture of n-dodecane and decalin with the weight percentage of 80:20 is prepared as a model compound. The performance evaluation of the catalyst is carried out on the micro fixed bed reactor, the micro fixed bed reactor is provided with a product tank, and the product tank is provided with a 0 ℃ refrigerating device for cooling the product, so that the reaction product can be discharged and weighed periodically. 1.5g of 40-60 mesh catalyst is filled into a constant temperature area of the reactor, and quartz sand is filled at two ends of the reactor. Firstly, under the conditions of reaction pressure of 0.1MPa, reaction temperature of 450 ℃ and gas-catalyst ratio of 300:1, hydrogen is used for carrying out constant-temperature reduction on the catalyst for 2 hours, then a model compound is injected into a reaction system under the conditions of reaction pressure of 8MPa, volume space velocity of 1.0h -1 and hydrogen-oil volume ratio of 1200, and the hydro-conversion performance of the isodewaxing catalyst on n-dodecane and decalin is inspected by adjusting the reaction temperature, and the evaluation results are shown in tables 2,3 and 4.
Example 2
(1) ZSM-22 molecular sieve synthesis
ZSM-22 molecular sieve synthesis was carried out according to patent CN 106853972. The specific operation is as follows: under stirring, 38g of Al 2(SO4)3·18H2 O is dissolved in 3000g of water, 90g of KOH is then added, and the mixture is fully stirred to form a clear solution A; 250g of 1, 6-hexamethylenediamine (DAH) is weighed and added into the solution A, 1000g of silica sol (containing 2 wt% of SiO) is added into the solution A after dissolution, and uniform gel B is formed after stirring; gel B was transferred to a 5L stainless steel reactor and reacted hydrothermally at 160℃with stirring at 400rpm for 48h. The reaction product was washed and filtered, and the filter cake was dried at 110℃for 10 hours to give a ZSM-22 molecular sieve having a SiO 2/Al2O3 molar ratio of about 80.
(2) Amorphous silicon aluminum preparation
Amorphous silica alumina preparation was carried out according to patent CN 1218089. The specific operation is as follows: 0.35L of aluminum sulfate solution is added into 0.4L of distilled water, heated and stirred until the aluminum sulfate solution is dissolved, aluminum sulfate solution A1 with the concentration of Al 2O3 being 8g/100mL is obtained, and a proper amount of distilled water is added into the concentrated ammonia water to dilute the concentrated ammonia water into 10% diluted ammonia water solution B1. 0.5L of distilled water was added to 0.24L of concentrated water glass having a modulus of 3.0 to obtain a diluted water glass solution C1. And simultaneously dropwise adding the solution A1 and the solution B1 into a reaction kettle containing 0.2L of distilled water at 70 ℃, adjusting the flow rate of the solution A1 to complete the reaction within 2.0h, adjusting the flow rate of the solution B1 to keep the pH value of a reaction system at about 7.0, and controlling the temperature of the system at 70 ℃. After the aluminum sulfate reaction is completed, stopping adding ammonia water, stabilizing the generated alumina sol for 15min, then dropwise adding 0.16L of solution C within 5min, and aging for 50min under the conditions of the system temperature of 65-70 ℃ and the pH value of 7.5. Filtering the colloid solution after aging to obtain a wet filter cake, adding distilled water into the filter cake again for washing, and filtering to obtain a filter cake D1. The filter cake was again added with distilled water and 3.15ml of phosphoric acid, stirred for 30min and filtered to give filter cake E1. The filter cake E1 was dried at 110℃for 8 hours to give amorphous silica alumina having a SiO 2 weight percent of about 20 wt%.
(3) Isomerization dewaxing catalyst preparation
As shown in example 1, 100g of ZSM-22 molecular sieve, 55g of amorphous silicon aluminum, 9g of titanium aluminum composite oxide and 6.4g of sesbania powder are uniformly mixed to obtain a mixture H1, 23g of 10% HNO 3 solution is dropwise added into 18g of SB powder and stirred to obtain aluminum gel I1, the aluminum gel I1 is added into the mixture H1, a proper amount of deionized water is dropwise added and uniformly mixed, the mixture is extruded and molded by a clover template with the diameter of 1.6mm, and the extrudate is dried at 120 ℃ for 10H and baked at 550 ℃ for 12H to obtain the carrier. The obtained carrier is immersed in a dichloro tetra-ammine platinum aqueous solution with the Pt weight percentage content of 1wt% by an isovolumetric immersion method, the immersed carrier is dried for 10 hours at 120 ℃, and the carrier is roasted for 12 hours at 450 ℃ to obtain the isomerization dewaxing catalyst B1 with the Pt upper amount of 0.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.
(4) Evaluation of catalyst Performance
Catalyst evaluation was performed according to the evaluation procedure described in example 1, and the evaluation results are shown in tables 2, 3 and 4.
Example 3
(1) ZSM-23 molecular sieve synthesis
ZSM-23 molecular sieve synthesis was carried out as described in patent CN 110683558A. The specific operation is as follows: under stirring, 66.4g of Al 2(SO4)3·18H2 O is dissolved in 3500g of water, 50g of NaOH is added, and the mixture is fully stirred to form a clear solution A; 270g of isopropyl amine (IPA) was weighed and added to solution A, after dissolution, 1200g of silica sol (containing SiO 2 wt%) was added to solution A and stirred to form a homogeneous gel B. Gel B was transferred to a 10L stainless steel reactor and reacted hydrothermally at 170℃with stirring at 200rpm for 24h. The reaction product is washed and filtered, and the filter cake is dried for 10 hours at 110 ℃ to obtain the ZSM-23 molecular sieve with the SiO 2/Al2O3 mol ratio of about 60.
(3) Isomerization dewaxing catalyst preparation
The amorphous silicon aluminum is shown in example 2, the titanium aluminum composite oxide is shown in example 1, 100g of ZSM-23 molecular sieve, 42g of amorphous silicon aluminum, 8.4g of titanium aluminum composite oxide and 6.4g of sesbania powder are uniformly mixed to obtain a mixture H2, 21.4g of 10% HNO 3 solution is dropwise added into 16.7g of SB powder to obtain aluminum gel I2, the aluminum gel I2 is added into the mixture H2, a proper amount of deionized water is dropwise added to uniformly mix, the mixture is extruded and molded by a clover template with the diameter of 1.6mm, and the extrudate is dried at 120 ℃ for 10H and baked at 550 ℃ for 12H to obtain the carrier. The obtained carrier is immersed in a dichloro tetra-ammine platinum aqueous solution with the Pt weight percentage content of 1wt% by an isovolumetric immersion method, the immersed carrier is dried for 10 hours at 120 ℃, and the carrier is roasted for 12 hours at 450 ℃ to obtain the isodewaxing catalyst C1 with the Pt upper amount of 0.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.
(4) Evaluation of catalyst Performance
Catalyst evaluation was performed according to the evaluation procedure described in example 1, and the evaluation results are shown in tables 2, 3 and 4.
Example 4
100G of the SAPO-11 molecular sieve, 22.5g of amorphous silicon aluminum and 2.5g of titanium aluminum composite oxide material are uniformly mixed by using the SAPO-11 molecular sieve, amorphous silicon aluminum and titanium aluminum composite oxide as a carrier material, the mixture is pressed into tablets by a tablet press, and the formed product is dried at 120 ℃ for 10 hours and baked at 550 ℃ for 12 hours to obtain the carrier. The obtained carrier is immersed in a dichloro tetra-ammine platinum aqueous solution with the Pt weight percentage content of 1wt% by an isovolumetric immersion method, and the immersed carrier is dried for 10 hours at 120 ℃ and baked for 12 hours at 450 ℃ to obtain the isomerization dewaxing catalyst D1 with the Pt upper amount of 0.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.
Example 5
The titanium-aluminum composite oxide in example 1, the ZSM-22 molecular sieve in example 2 and amorphous silicon aluminum are adopted as carrier materials, 100g of ZSM-22 molecular sieve, 125g of amorphous silicon aluminum and 25g of titanium-aluminum composite oxide are uniformly mixed, a tablet press is adopted to press the mixture into tablets, and the formed product is dried at 120 ℃ for 10 hours and baked at 550 ℃ for 12 hours to obtain the carrier. The obtained carrier is immersed in a dichloro tetra-ammine platinum aqueous solution with the Pt weight percentage content of 1wt% by an isovolumetric immersion method, the immersed carrier is dried for 10 hours at 120 ℃, and the carrier is roasted for 12 hours at 450 ℃ to obtain the isodewaxing catalyst E1 with the Pt upper amount of 0.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.
Comparative example 1
The SAPO-11 molecular sieve is shown in example 1, 100g of the SAPO-11 molecular sieve and 6.4g of sesbania powder are uniformly mixed to obtain a mixture H3, 38.4g of 10% HNO 3 solution is added into 30g of SB powder in a dropwise manner to obtain aluminum gel I3, adding the aluminum gel I3 into the mixture H3, dropwise adding a proper amount of deionized water, uniformly mixing, adopting a clover-shaped template with the diameter of 1.6mm to extrude the mixture, drying the extrudate at 120 ℃ for 10H, and roasting at 550 ℃ for 12H to obtain the carrier. The obtained carrier is immersed in a dichloro tetra-ammine platinum aqueous solution with the Pt weight percentage content of 1wt% by an isovolumetric immersion method, and the immersed carrier is dried for 10 hours at 120 ℃ and baked for 12 hours at 450 ℃ to obtain the isomerization dewaxing catalyst A2 with the Pt upper amount of 0.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.
Catalyst evaluation was performed according to the evaluation procedure described in example 1, and the evaluation results are shown in tables 2, 3 and 4.
Comparative example 2
The ZSM-22 molecular sieve is shown in the example 2, 100g of ZSM-22 molecular sieve and 6.4g of sesbania powder are uniformly mixed to obtain a mixture H4, 104.5g of 10% HNO 3 solution is dropwise added into 81.8g of SB powder and stirred to obtain aluminum gel I4, the aluminum gel I4 is added into the mixture H4, a proper amount of deionized water is dropwise added and uniformly mixed, the mixture is extruded and molded by a clover template with the diameter of 1.6mm, and the extrudate is dried at 120 ℃ for 10H and baked at 550 ℃ for 12H to obtain the carrier. The obtained carrier is immersed in a dichloro tetra-ammine platinum aqueous solution with the Pt weight percentage content of 1wt% by an isovolumetric immersion method, the immersed carrier is dried for 10 hours at 120 ℃, and the carrier is roasted for 12 hours at 450 ℃ to obtain the isomerization dewaxing catalyst B2 with the Pt upper amount of 0.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.
Catalyst evaluation was performed according to the evaluation procedure described in example 1, and the evaluation results are shown in tables 2, 3 and 4.
Comparative example 3
As shown in example 3, 100g of ZSM-23 molecular sieve and 6.4g of sesbania powder are uniformly mixed to obtain a mixture H5, 85.2g of 10% HNO 3 solution is dropwise added into 66.7g of SB powder and stirred to obtain aluminum gel I5, the aluminum gel I5 is added into the mixture H5, a proper amount of deionized water is dropwise added and uniformly mixed, the mixture is extruded and molded by a clover template with the diameter of 1.6mm, and the extrudate is dried at 120 ℃ for 10H and baked at 550 ℃ for 12H to obtain the carrier. The obtained carrier is immersed in a dichloro tetra-ammine platinum aqueous solution with the Pt weight percentage content of 1wt% by an isovolumetric immersion method, the immersed carrier is dried for 10 hours at 120 ℃, and the carrier is roasted for 12 hours at 450 ℃ to obtain the isodewaxing catalyst C2 with the Pt upper amount of 0.5 wt%. The physicochemical properties of the catalyst are shown in Table 1.
Catalyst evaluation was performed according to the evaluation procedure described in example 1, and the evaluation results are shown in tables 2, 3 and 4.
TABLE 1
Table 2 gives liquid yield data for the reaction process over the different catalysts.
TABLE 2
Table 3 gives the conversion and isomerization selectivity data for n-dodecane over different catalysts.
TABLE 3 Table 3
Table 4 shows the conversion and ring opening selectivity data for decalin over different catalysts.
TABLE 4 Table 4
As can be seen from the micro-inverse evaluation results of tables 2,3 and 4, the novel heterogeneous dewaxing catalysts A1, B1 and C1 prepared by compounding amorphous silicon aluminum, titanium aluminum composite oxides and mesoporous molecular sieves have higher liquid yield in the reaction process compared with the traditional heterogeneous dewaxing catalysts A2, B2 and C2, and the liquid yield is improved by 2-6 percent compared with the traditional heterogeneous dewaxing catalysts.
Under the reaction conditions, the traditional isomerization dewaxing catalysts A2, B2 and C2 have lower decalin conversion rate, and only a small amount of ring-opened products exist in the converted products. Under the reaction conditions, the isomerization conversion rate and the isomerization selectivity of the novel isomerization dewaxing catalysts A1, B1 and C1 are equivalent to those of the traditional isomerization dewaxing catalysts, and meanwhile, the novel isomerization dewaxing catalysts A1, B1 and C1 have higher decalin conversion rate and higher ring opening selectivity.
In summary, the noble metal/amorphous silicon-aluminum and noble metal/titanium-aluminum composite oxide functional components with cycloparaffin ring opening function are compounded, a step diffusion channel is constructed for macromolecules such as polycyclic cycloparaffin, rapid diffusion of reactants and products is realized, isomerization and excessive residence of ring-opening reaction products on a catalyst are avoided, secondary cracking reaction is continued, and higher liquid yield in the reaction process is ensured. Compared with the traditional heterogeneous dewaxing catalyst, the novel heterogeneous dewaxing catalyst added with the amorphous silicon-aluminum and titanium-aluminum composite oxide can improve the liquid yield in the reaction process by 2-6 percent.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (12)
1. A process for preparing an isomerisation dewaxing catalyst comprising the steps of:
(1) Preparation of a catalyst carrier: mixing a mesoporous molecular sieve, amorphous silica-alumina and a titanium-aluminum composite oxide, adding an extrusion aid and a binder, kneading the mixture, extruding, forming, drying and roasting to obtain a catalyst carrier, wherein the drying condition is 100-130 ℃ for 1-24 h, and the roasting condition is 400-600 ℃ for 4-24 h;
(2) Putting the catalyst carrier into the impregnating solution for impregnation treatment, wherein the impregnation time is 2-24 hours;
(3) And drying and roasting the impregnated catalyst carrier to obtain a catalyst finished product.
2. The method according to claim 1, wherein step (1) further comprises mixing the mesoporous molecular sieve, amorphous silica alumina and titanium aluminum composite oxide and tabletting.
3. The method according to claim 2, wherein the medium pore molecular sieve is at least one selected from the group consisting of silicoaluminophosphate molecular sieves (SAPO-11, SAPO-31, SAPO-41), zeolite molecular sieves having an MTT framework structure (ZSM-23, SSZ-32, EU-13, ISI-4 and KZ-1), and zeolite molecular sieves having a TON framework structure (θ -1, ISI-1, KZ-2, NU-10 and ZSM-22).
4. The preparation method according to claim 2, wherein the amorphous silica-alumina has a silica content of 5-75 wt%, a pore volume of 0.5-1.6 mL/g, a specific surface area of 300-600 m 2/g, an average pore diameter of 8-14 nm, and an infrared acidity of generally 0.25-0.55 mmol/g.
5. The process according to claim 4, wherein the amorphous silica-alumina has a silica content of 15 to 50wt%, a pore volume of 1.0 to 1.4mL/g, a specific surface area of 350 to 500m 2/g, an average pore diameter of 10 to 13nm, and an infrared acidity of 0.35 to 0.45mmol/g.
6. The preparation method according to claim 2, wherein the titanium aluminum composite oxide has a titanium oxide content of 5 to 50wt%, a pore volume of 0.7 to 1.5mL/g, a specific surface area of 300 to 450m 2/g, and an average pore diameter of 8 to 16nm.
7. The method according to claim 6, wherein the titanium oxide content is 10 to 50wt%, the pore volume is 0.8 to 1.2mL/g, the specific surface area is 320 to 450m 2/g, and the average pore diameter is 13 to 15nm.
8. The method of claim 1, wherein in step (1), the binder comprises alumina, aluminum hydroxide, pseudo-boehmite, an alumina sol or a silica sol, preferably a small pore alumina or a small pore pseudo-boehmite material.
9. The method according to claim 1, wherein in the step (1), the drying temperature is 100 to 120 ℃ and the drying time is 1 to 12 hours; the roasting temperature is 500-550 ℃ and the roasting time is 4-12 h.
10. The method according to claim 1, wherein in the step (2), the dipping time is 4 to 16 hours; the impregnation method is selected from any one of ion exchange, isovolumetric impregnation and coprecipitation.
11. An isodewaxing catalyst prepared by the preparation method of claims 1-10, wherein the isodewaxing catalyst carrier comprises 5-90 wt% of mesoporous molecular sieve, 5-70 wt% of amorphous silicon aluminum, 0.2-20 wt% of titanium aluminum composite oxide and 0-30 wt% of binder; the active metal component of the isodewaxing catalyst at least contains one noble metal component of Pt, pd, ru, rh and Ni, the noble metal content is 0.1-2.0wt%, the metal salt is at least one of halide salt, amine complex salt, nitrate, carbonate, bicarbonate, carboxylate and formate, the specific surface area of the isodewaxing catalyst is 100-250 m 2/g, the pore volume is 0.25-0.65 mL/g, and the infrared acidity is generally 0.25-0.65 mmol/g.
12. The isomerization dewaxing catalyst according to claim 11, wherein the isomerization dewaxing catalyst carrier contains 40 to 80wt% of mesoporous molecular sieve, 10 to 50wt% of amorphous silicon aluminum, 1.0 to 10wt% of titanium aluminum composite oxide and 0 to 20wt% of binder; the content of noble metal is 0.2-0.8 wt%, the specific surface area of the isomerization dewaxing catalyst is preferably 120-200 m 2/g, the pore volume is preferably 0.30-0.50 mL/g, and the infrared acidity is preferably 0.35-0.60 mmol/g.
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