CN109126863A - A kind of condensed-nuclei aromatics adds the preparation method of the porous Pd composite membrane of hydrogen production mononuclear aromatics - Google Patents
A kind of condensed-nuclei aromatics adds the preparation method of the porous Pd composite membrane of hydrogen production mononuclear aromatics Download PDFInfo
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- CN109126863A CN109126863A CN201811169060.0A CN201811169060A CN109126863A CN 109126863 A CN109126863 A CN 109126863A CN 201811169060 A CN201811169060 A CN 201811169060A CN 109126863 A CN109126863 A CN 109126863A
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- molecular sieve
- porous
- preparation
- transition zone
- auxiliary agent
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- 239000012528 membrane Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 13
- 239000001257 hydrogen Substances 0.000 title claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000002808 molecular sieve Substances 0.000 claims abstract description 74
- 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 62
- 210000002469 basement membrane Anatomy 0.000 claims abstract description 37
- 230000007704 transition Effects 0.000 claims abstract description 33
- 210000004379 membrane Anatomy 0.000 claims abstract description 25
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- 239000002905 metal composite material Substances 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052737 gold Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052709 silver Inorganic materials 0.000 claims abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 3
- 239000010935 stainless steel Substances 0.000 claims abstract description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 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 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005253 cladding Methods 0.000 claims description 4
- 238000001802 infusion Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000010899 nucleation Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000010944 silver (metal) Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 229910052681 coesite Inorganic materials 0.000 claims 3
- 229910052906 cristobalite Inorganic materials 0.000 claims 3
- 229910052682 stishovite Inorganic materials 0.000 claims 3
- 229910052905 tridymite Inorganic materials 0.000 claims 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 125000002619 bicyclic group Chemical group 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 34
- 239000003292 glue Substances 0.000 description 24
- 229910052594 sapphire Inorganic materials 0.000 description 20
- 239000000243 solution Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910002666 PdCl2 Inorganic materials 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 3
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- 206010068150 Acoustic shock Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102100035959 Cationic amino acid transporter 2 Human genes 0.000 description 1
- 102100021391 Cationic amino acid transporter 3 Human genes 0.000 description 1
- 102100021392 Cationic amino acid transporter 4 Human genes 0.000 description 1
- 101710195194 Cationic amino acid transporter 4 Proteins 0.000 description 1
- 229910002530 Cu-Y Inorganic materials 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
- 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 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 108091006231 SLC7A2 Proteins 0.000 description 1
- 108091006230 SLC7A3 Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000004062 acenaphthenyl group Chemical class C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 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
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018109 developmental process Effects 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
- 238000005516 engineering process Methods 0.000 description 1
- 230000009647 facial growth Effects 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
- 239000002010 green coke Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 238000005221 zone crystallization 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
- B01J29/04—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
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/14—Iron group metals or copper
- B01J29/146—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0234—Impregnation and coating simultaneously
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/18—Crystalline alumino-silicate carriers the catalyst 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- Chemical & Material Sciences (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention provides the preparation methods that a kind of condensed-nuclei aromatics adds the porous Pd composite membrane of hydrogen production mononuclear aromatics, wherein composite membrane is made of basement membrane, molecular sieve transition zone and metal composite layer three parts, wherein basement membrane includes one of porous aluminas, porous zirconia, porous titanium oxide, porous silica or porous stainless steel, molecular sieve transition zone is at least one of FAU, MFI, BEA, MWW topological structure molecular sieve, and molecular sieve transition region thickness is 10~200 μm；Active component includes main active component Pd layers and auxiliary agent layer, and at least one of auxiliary agent Co, Ni, Fe, Cu, V, Pt, Pd, Ag or Au, auxiliary agent/Pd molar ratio is 0.5~5.The porous Pd composite membrane is to the hydrogenation activity with higher of condensed-nuclei aromatics in heavy aromatics and selectivity, it has the function of that highly effective hydrogenation is converted into mononuclear aromatics to bicyclic and thrcylic aromatic hydrocarbon, the two conversion ratio is respectively up to 75% and 55% or more, mononuclear aromatics selectively up to 98%, catalyst stabilization performance is good.
Description
Technical field
The present invention relates to Membrane catalysis and field of membrane preparation, and in particular to a kind of condensed-nuclei aromatics adds the more of hydrogen production mononuclear aromatics
The preparation method of hole Pd composite membrane.
Background technique
Light aromatics (benzene, toluene or dimethylbenzene) or high-octane rating vapour are converted for Petroleum Aromatics using lighting technology
Oil ingredient is a kind of effective means for improving heavy aromatics utilization rate.But condensed-nuclei aromatics (PAHs) content in Petroleum Aromatics
Height, about 30~50% mainly include naphthalenes, acenaphthene class, acenaphthylene class, anthracene, phenanthrene etc., stable structure, this portion during lighting
Condensed-nuclei aromatics is divided to be not easy direct open loop cracking.In addition, easy dehydrogenative condensation generates coke to condensed-nuclei aromatics at high temperature, and it is attached to and urges
Agent surface makes catalyst lose activation H2Ability, cause catalyst activity and stability to decline.It is light to improve heavy aromatics oil
Matter efficiency inhibits green coke, converts mononuclear aromatics for condensed-nuclei aromatics elder generation pre-add hydrogen in heavy aromatics, then open loop cracking production again
Light aromatics (benzene, toluene or dimethylbenzene) or high-knock rating gasoline are a kind of efficient heavy aromatics lighting routes.Condensed-nuclei aromatics
Hydrogenation process is typical consecutive reaction, to realize the controllable selective hydrogenation of condensed-nuclei aromatics, and catalyst system is crucial.Ruthenium, rhodium
It is excellent aromatic hydrocarbon hydrogenation catalyst, but the excessively high selectivity for making product of its catalytic activity is difficult to control；The noble metals such as palladium, platinum add
Hydrogen activity is high, it is desirable that reaction condition is more mild, but noble metal price is more expensive, and catalyst is easy poisoning and deactivation, mainly sulphur
Poisoning；The base metals such as cobalt, nickel are mostly used with sulphided state, but non-precious metal catalyst reactivity is not high and requirement condition is severe
It carves.Therefore, it is crucial for developing cheap high activity and high stability condensed-nuclei aromatics hydrogenation catalyst.
Pd group compound film is due to hydrogen infiltration rate with higher and height hydrogen permeation selectivity, good anti-hydrogen embrittlement and antitoxin
Property and cost advantage, be widely used in hydrogen-involved reaction research in recent years.But about Pd group compound film in condensed ring
Aromatic hydrogenation produces mononuclear aromatics application study there is not yet document report.Currently, Pd group compound film research work is very active, but
The stability problem of composite membrane is the biggest obstacle for hindering its development.
Summary of the invention
The technical problem to be solved by the present invention is to Pd group compound film stability difference and condensed-nuclei aromatics conversion ratio it is not high and
The problem of catalyst easy coking deactivation, provides the system that a kind of new condensed-nuclei aromatics adds the porous Pd composite membrane of hydrogen production mononuclear aromatics
Preparation Method.The compound film properties of porous Pd of this method preparation are stablized, good etc. with high conversion rate and selectivity to condensed-nuclei aromatics
Advantage.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: a kind of condensed-nuclei aromatics adds hydrogen production list
The preparation method of the porous Pd composite membrane of cycloaromatics, mainly by basement membrane, molecular sieve transition zone and metal composite layer three parts group
At.Successively basement membrane is pre-processed respectively using acid solution, organic solvent at normal temperatures and pressures first, then again using czochralski method or
Molecular sieve gel containing seeding director is applied directly on pretreated basement membrane by cladding process, and in-situ crystallization is made later
Molecular sieve transition zone；Finally auxiliary agent and Pd are successively coated on molecular sieve transition zone using infusion process, porous Pd composite membrane is made
Catalyst；
The basement membrane includes porous aluminas, porous zirconia, porous titanium oxide, porous silica and porous stainless steel
One of, molecular sieve transition zone is at least one of FAU, MFI, BEA, MWW topological structure molecular sieve, and metal component includes
Main active component Pd layers and auxiliary agent layer, wherein auxiliary agent is at least one of Co, Ni, Cu, Fe, V, Pt, Ag or Au.The base
The preferred tubular porous aluminium oxide of film, more preferable 6~20mm of outer diameter, 4~18mm of internal diameter, porosity be greater than 30%, draw aperture 1~
10 μm of tubular porous aluminium oxide；Molecular sieve transition zone is at least one of Y molecular sieve and beta-molecular sieve, molecular sieve transition zone
With a thickness of 0~200 μm, preferably 20~50 μm；Pd film thickness is 50-200nm, preferably 50~100nm, auxiliary agent/Pd molar ratio
It is 0.5~5, preferably 1.5~3.0.
In the preparation method of the porous Pd composite membrane of the present invention, basement membrane pre-treatment step includes: successively to use under normal temperature and pressure
Acid solution, organic solvent and deionized water rinse basement membrane, it is air-dried 5 in 100~170 DEG C~for 24 hours, in 500 in Muffle furnace
3~12h is roasted at~950 DEG C, is put into after being cooled to room temperature spare in drier.
In the preparation method of the porous Pd composite membrane of the present invention, molecular sieve transition zone preparation step includes: that preparation contains crystal seed
The Zeolite synthesis glue of directed agents, the aging process 3~for 24 hours at 25~100 DEG C, obtains required molecular sieve gel；Using
Czochralski method or cladding process coat molecular sieve gel to basement membrane, dry at room temperature, repeat 1~3 time；It is dried at 60~120 DEG C,
3~12h is roasted at 350~550 DEG C；The basement membrane for coating molecular sieve precursor is placed in crystallizing kettle, is passed through containing alkali, template
With the saturated vapor of water, then 12~72h of crystallization under 100~200 DEG C of self-generated pressures is down to room temperature, dry, roasting.
In the preparation method of the porous Pd composite membrane of the present invention, the auxiliary agent and Pd are coated on molecule using infusion process and are sieved through
Cross the step on layer are as follows: by the basement membrane with molecular sieve transition zone in the aqueous metal salt of auxiliary agent after rapid impregnation, 100~
150 DEG C of drying, 500~650 DEG C of roasting 3~10h, 2~4 times repeatedly；Then it repeats the above steps to coat Pd to cladding and help
On the basement membrane of agent and molecular sieve transition zone.
Compared with prior art, preparation method of the present invention passes through in basement membrane table the preparation method of the porous Pd composite membrane of the present invention
Face growth in situ molecular sieve transition zone, can be effectively controlled the performance of molecular sieve transitionality, while improve active component and basement membrane
Binding force, and then improve the compound membrane stability of Pd；And by introducing adjuvant component in molecular sieve surface, and then improve Pd composite membrane
Activity and stability, and precious metals pd dosage is reduced, achieve the purpose that improve Pd utilization rate.
Detailed description of the invention
Fig. 1 is that different catalysts stability compares figure.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Comparative example 1
Using equi-volume impregnating by 100g macroporous aluminium oxide (BET surface area 320m2/ g, hole hold 0.7cm3/ g, average hole
Diameter 12nm) it is immersed in the Pt (NH that mass fraction is 0.08%3)4Cl2(in terms of Pt) and 0.12% PdCl2In mixed solution
(in terms of Pd) stands 3h, 120 DEG C of drying 10h, 500 DEG C of roasting 5h.Pd+Pt total load amount 1% (in terms of matrix 100%), catalysis
Agent is denoted as contrast medium -1.
Embodiment 1
With α-Al2O3Membrane tube is basement membrane (membrane tube outer diameter 12mm, internal diameter 10mm, average pore size 50nm, porosity 50%),
Basement membrane is successively in the HNO of 0.5mol/L3It is each super in the ethanol solution of acid solution, 0.5mol/L acetone soln and mass fraction 95%
1h is swung in acoustic shock, except the impurity and dirt of attachment removal, is then washed with deionized water to neutrality, in 120 DEG C of dry 5h.By basement membrane both ends
Surface at 20mm is sealed with high-temperature glaze, roasts 6h at 600 DEG C in Muffle furnace, is put into after being cooled to room temperature standby in drier
With.
The preparation of beta-molecular sieve transition zone: 1) NaOH and sodium aluminate are successively dissolved in 25% tetraethyl ammonium hydroxide
(TEAOH) in aqueous solution, a certain amount of white carbon black and Beta molecular sieve powder is added wait be completely dissolved, stirs 2h, is then charged into
In hydrothermal synthesis kettle, stir lower aging for 24 hours at 100 DEG C, cool to obtain required molecular sieve glue, wherein in glue at
The molar ratio divided is 4.5NaO:1Al2O3: 22.5TEAOH:45SiO2: 1350H2O, crystal seed amount are the 6% of silicon species quality；2)
Above-mentioned glue is coated to pretreated basement membrane outer surface, 80 DEG C of dry 3h using czochralski method.It repeats aforesaid operations 3 times；3)
By the α-Al of precoating crystal seed2O3Membrane tube is placed in the synthesis reactor containing molecular sieve glue, and it is 0.05mol/L that concentration is added in kettle
Then TEAOH aqueous solution, crystallization 48h under 140 DEG C of self-generated pressures are down to room temperature, dry, roasting is obtained with molecular sieve transition zone
α-Al2O3Membrane tube.By pretreated α-Al before precoating crystal seed2O3Membrane tube both ends emit sealing with polytetrafluoroethylene (PTFE), simultaneously
Basement membrane outer surface is encased with polytetrafluoro band grows molecular sieve in basement membrane inner surface.
By beta-molecular sieve/α-Al2O3Membrane tube is totally submerged in the nickel nitrate solution that mass fraction is 12% (in terms of Ni), quiet
Set 6h, 120 DEG C of drying 10h, 500 DEG C of roasting 5h；Then by Ni- beta-molecular sieve/α-Al2O3Membrane tube is totally submerged is in mass fraction
0.12% PdCl2In mixed solution (in terms of Pd), 6h, 120 DEG C of drying 10h, 500 DEG C of roasting 5h, catalyst obtained are stood
It is denoted as CAT-1.The basement membrane outer surface with molecular sieve is encased with polytetrafluoro band in interior area load before load active component
Active component.
Embodiment 2
α-Al2O3Membrane tube specification and preprocess method are the same as embodiment 1.
The preparation of Y molecular sieve glue: waterglass, aluminum sulfate are added sequentially in water, are stirred to complete hydrolysis, are obtained molten
Liquid a；NaOH and sodium metaaluminate are added in aqueous solution, stirred at 60 DEG C to being completely dissolved, room temperature is cooled to and obtains solution b；Room
Solution b is added in solution a under temperature stirring, 30min is stirred, is subsequently placed in aging in 35 DEG C of baking ovens and for 24 hours, obtains required glue
Liquid.Wherein, the molar ratio of each component is 2Na in glue2O:1Al2O3: 8SiO2: 1440H2O。
The preparation of molecular sieve transition zone: molecular sieve glue is coated on to the inner surface of basement membrane using czochralski method, is dried in the air at room temperature
It is dry；It repeatedly aforesaid operations 3 times, is subsequently placed in 100 DEG C of baking ovens and dries for 24 hours；The basement membrane of precoating crystal seed is placed in containing concentration
For crystallization in the crystallizing kettle of tetramethylammonium hydroxide (TMAOH) aqueous solution of 0.06mol/L, water-soluble liquid measure is to be slightly above crystallization temperature
Spend lower saturated vapor amount；Crystallization 48h, cooling, drying and roasting obtain Y molecular sieve/α-Al2O3Membrane tube；
By Y molecular sieve/α-Al2O3Membrane tube is totally submerged in the nickel nitrate solution that mass fraction is 12% (in terms of Ni), quiet
Set 6h, 120 DEG C of drying 10h, 500 DEG C of roasting 5h；Then by Ni- beta-molecular sieve/α-Al2O3Membrane tube is completely soaked is in mass fraction
0.12% PdCl2In mixed solution (in terms of Pd), 6h, 120 DEG C of drying 10h, 500 DEG C of roasting 5h, catalyst obtained are stood
It is denoted as CAT-2.Before load active component, including the film support outer surface with molecular sieve is encased with polytetrafluoro band first
Area load active component.
Embodiment 3
α-Al2O3Membrane tube specification and preprocess method are the same as embodiment 1.
Y molecular sieve transition zone preparation method in situ is the same as embodiment 2.Before growing molecular sieve in situ, first by basement membrane appearance
Face is encased with polytetrafluoro band grows molecular sieve transition zone in inner surface.
By Y molecular sieve/α-Al2O3Membrane tube is completely soaked in the copper nitrate solution that mass fraction is 12% (in terms of Cu), quiet
Set 6h, 120 DEG C of drying 10h, 500 DEG C of roasting 5h；Then by Cu-Y molecular sieve/α-Al2O3Membrane tube is completely soaked is in mass fraction
0.12% PdCl2In mixed solution (in terms of Pd), 6h, 120 DEG C of drying 10h, 500 DEG C of roasting 5h, catalyst obtained are stood
It is denoted as CAT-3.Before load active component, the basement membrane outer surface with molecular sieve is encased with polytetrafluoro band in inner surface first
Load active component.
Embodiment 4
α-Al2O3Membrane tube specification and preprocess method are the same as embodiment 1.
The preparation of Y- β composite molecular screen transition zone:
1) preparation of Y- β composite molecular screen glue: the preparation method is the same as that of Example 1 for beta-molecular sieve glue, and wherein each component rubs
That ratio are as follows: 4.5NaO:1Al2O3: 22.5TEAOH:45SiO2: 2700H2O；The preparation of Y molecular sieve glue with embodiment 2, wherein
The molar ratio of each component are as follows: 2Na2O:1Al2O3: 8SiO2: 144H2O；By Y and beta-molecular sieve glue, 3:1 is mixed by volume, room temperature
30min is stirred, required composite molecular screen glue is obtained；
2) transition zone coating is the same as embodiment 1；
3) Y- β composite molecular screen/α-Al is made with embodiment 2 in transition zone crystallization condition2O3Membrane tube.
By Y- β composite molecular screen/α-Al2O3Pt (the NH that it is 0.08% in mass fraction that membrane tube, which is totally submerged,3)4Cl2(with Pt
Meter) in, stand 6h, 120 DEG C of drying 10h, 500 DEG C of roasting 5h；Then by Pt-Y- beta-molecular sieve/α-Al2O3Be totally submerged in
0.12% PdCl2In mixed solution (in terms of Pd), 6h, 120 DEG C of drying 10h, 500 DEG C of roasting 5h, catalyst obtained are stood
It is denoted as CAT-4.Before load active component, including the film support outer surface with molecular sieve is encased with polytetrafluoro band first
Area load active component.
Embodiment 5
α-Al2O3Membrane tube specification and preprocess method are the same as embodiment 1.
The preparation of Y- β composite molecular screen transition zone:
1) preparation of Y- β composite molecular screen glue: the preparation method is the same as that of Example 1 for beta-molecular sieve glue, and wherein each component rubs
That ratio are as follows: 1.5NaO:1Al2O3: 10TEAOH:30SiO2: 1350H2O；The preparation of Y molecular sieve glue is with embodiment 3, wherein respectively
The molar ratio of component are as follows: 2Na2O:1Al2O3: 8SiO2: 1440H2O；By Y and beta-molecular sieve glue, 1:3 is mixed by volume, room temperature
30min is stirred, required composite molecular screen glue is obtained；
2) coating coating step is the same as embodiment 1；
3) Y- β composite molecular screen/α-Al is made with embodiment 4 in coating crystallization condition2O3Membrane tube.
By Y- β composite molecular screen/α-Al2O3Membrane tube is totally submerged in the nickel nitrate solution that mass fraction is 12% (with Ni
Meter), stand 6h, 120 DEG C of drying 10h, 500 DEG C of roasting 5h；Then by Ni-Y molecular sieve/α-Al2O3Membrane tube is totally submerged in quality
The PdCl that score is 0.12%2(in terms of Pd) and 0.08% Pt (NH3)4Cl2In (in terms of Pt) mixed solution, stand 6h, 120
DEG C drying 10h, 500 DEG C of roasting 5h, catalyst obtained is denoted as CAT-5.It, first will be with molecular sieve before load active component
Basement membrane outer surface encased with polytetrafluoro band in interior area load active component.
Embodiment 6
α-Al2O3Membrane tube specification and preprocess method are the same as embodiment 1.
The preparation of Y- β composite molecular screen transition zone:
1) preparation of Y- β composite molecular screen glue: the preparation method is the same as that of Example 1 for beta-molecular sieve glue, and wherein each component rubs
That ratio are as follows: 1.5NaO:1Al2O3: 10TEAOH:30SiO2: 1350H2O；The preparation of Y molecular sieve glue is with embodiment 3, wherein respectively
The molar ratio of component are as follows: 2Na2O:1Al2O3: 8SiO2: 1440H2O；By Y and beta-molecular sieve glue, 1:3 is mixed by volume, room temperature
30min is stirred, required composite molecular screen glue is obtained；
2) coating coating is with embodiment 1, wherein by pretreated basement membrane inner surface polytetrafluoro before precoating crystal seed
Band, which is encased, coats crystal seed in outer surface；
3) Y- β composite molecular screen/α-Al is made with embodiment 4 in coating crystallization condition2O3Membrane tube.
By Y- β composite molecular screen/α-Al2O3Membrane tube is totally submerged in the nickel nitrate solution that mass fraction is 12% (with Ni
Meter), stand 6h, 120 DEG C of drying 10h, 500 DEG C of roasting 5h；Then by Ni-Y molecular sieve/α-Al2O3Membrane tube is totally submerged in quality
The PdCl that score is 0.12%2(in terms of Pd) and 0.08% Pt (NH3)4Cl2In (in terms of Pt) mixed solution, stand 6h, 120
DEG C drying 10h, 500 DEG C of roasting 5h, catalyst obtained is denoted as CAT-6.It will be with molecular sieve basement membrane before load active component
Inner surface encased with polytetrafluoro band in outer area load active component.
Embodiment 7
Under hydro condition, porous Pd composite membrane is fitted into specific reactor, Ф 3mm inertia porcelain is filled on the inside of membrane tube
Ball plays air flow method.Reaction pressure 4MPa, 170 DEG C of reaction temperature, weight space velocity 3.5h-1, hydrogen to oil volume ratio 600:1.Even
Continuous sample introduction, it is primary per sampling for 24 hours, and product is analyzed.In addition, being unified implementation example and comparative example as a result, by contrast medium-
1 is packed into the α-Al of blank2O3In membrane tube, process conditions are same as above.The results are shown in Table 1 for feedstock analysis, condensed-nuclei aromatics conversion ratio and list
Cyclophane hydrocarbon-selective (SMononuclear aromatics) be listed in Table 2 below.
1 raw material of table composition
2 different catalysts catalytic performance of table compares
Claims (10)
1. the preparation method that a kind of condensed-nuclei aromatics adds the porous Pd composite membrane of hydrogen production mononuclear aromatics, which is characterized in that described
Porous Pd composite membrane is made of basement membrane, molecular sieve transition zone and metal composite layer three parts；The basement membrane be porous aluminas,
One of porous zirconia, porous titanium oxide, porous silica and porous stainless steel；The molecular sieve transition zone be FAU,
At least one of MFI, BEA, MWW topological structure molecular sieve, the molecular sieve transition region thickness are 10~200 μm, preferably
20~50 μm；The metal composite layer includes main active component Pd layers and auxiliary agent layer, and wherein Pd layers with a thickness of 50~200nm；
Auxiliary agent layer is at least one of Co, Ni, Cu, Fe, V, Pt, Ag or Au, and auxiliary agent/Pd molar ratio is 0.5~5；
Successively basement membrane is pre-processed respectively using acid solution, organic solvent at normal temperatures and pressures first, using lifting after pretreatment
Molecular sieve gel containing seeding director is applied directly on pretreated basement membrane by method or cladding process, later in-situ crystallization
Molecular sieve transition zone is made；Finally auxiliary agent and Pd are successively coated on molecular sieve transition zone using infusion process, made in molecular sieve
The Pd layer on auxiliary agent layer and auxiliary agent layer is formed on transition zone, so that porous Pd film catalyst be made.
2. preparation method according to claim 1, which is characterized in that the basement membrane shape is tubulose, tabular, honeycomb
One of shape.
3. preparation method according to claim 1, which is characterized in that the auxiliary agent layer and Pd layers are coated using infusion process
Step on molecular sieve transition zone are as follows: quickly soak the basement membrane with molecular sieve transition zone in the aqueous metal salt of auxiliary agent
After stain, 100~150 DEG C of drying, 500~650 DEG C of roasting 3~10h, 2~4 times repeatedly；Then it repeats the above steps and wraps Pd layers
It overlays on the basement membrane for helping oxidant layer and molecular sieve transition zone.
4. preparation method according to claim 1, which is characterized in that the molecular sieve transition zone is FAU and/or BEA
The molecular sieve of structure.
5. preparation method according to claim 1, which is characterized in that acid solution described in basement membrane pre-treatment step is salt
At least one of acid, nitric acid, sulfuric acid or phosphoric acid solution, the concentration of acid solution are 0.05~3mol/L；The organic solvent
For at least one of methanol, ethyl alcohol, acetone, organic solvent concentration is 0.1~5mol/L.
6. preparation method according to claim 1, which is characterized in that Pd layers with a thickness of 50~100nm.
7. preparation method according to claim 1, which is characterized in that auxiliary agent/Pd molar ratio is 1.5~3.0.
8. preparation method according to claim 1, which is characterized in that the molecular sieve gel containing seeding director
Composition are as follows: SiO2/Al2O3=10~80, Na2O/SiO2=0.02~0.25, H2O/SiO2=8~100.
9. preparation method according to claim 1, which is characterized in that the basement membrane is porous aluminas membrane tube.
10. preparation method according to claim 9, which is characterized in that the multiaperture pellumina pipe outside diameter 6~
20mm, 4~18mm of internal diameter, porosity is greater than 30%, 1~10 μm of average pore size.
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