CN106423226B - 具有接近优化位点的多金属催化剂的制备方法 - Google Patents
具有接近优化位点的多金属催化剂的制备方法 Download PDFInfo
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- CN106423226B CN106423226B CN201610819884.2A CN201610819884A CN106423226B CN 106423226 B CN106423226 B CN 106423226B CN 201610819884 A CN201610819884 A CN 201610819884A CN 106423226 B CN106423226 B CN 106423226B
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- catalyst
- tin
- metal
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- chlorine
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims description 26
- 238000005457 optimization Methods 0.000 title description 2
- 239000011135 tin Substances 0.000 claims abstract description 56
- 229910052718 tin Inorganic materials 0.000 claims abstract description 47
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 38
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000011574 phosphorus Substances 0.000 claims abstract description 34
- 229910052738 indium Inorganic materials 0.000 claims abstract description 26
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 70
- 239000000460 chlorine Substances 0.000 claims description 32
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 31
- 229910052801 chlorine Inorganic materials 0.000 claims description 31
- 229910052697 platinum Inorganic materials 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000002243 precursor Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 10
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- 230000008569 process Effects 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000001833 catalytic reforming Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 abstract description 8
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052716 thallium Inorganic materials 0.000 abstract description 7
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052797 bismuth Inorganic materials 0.000 abstract description 6
- 229910052787 antimony Inorganic materials 0.000 abstract description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052785 arsenic Inorganic materials 0.000 abstract description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004611 spectroscopical analysis Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 17
- 239000011324 bead Substances 0.000 description 9
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000013256 coordination polymer Substances 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000002407 reforming Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- -1 extrudates Substances 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000002923 metal particle Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910002846 Pt–Sn Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910009038 Sn—P Inorganic materials 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005388 cross polarization Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 230000026030 halogenation Effects 0.000 description 2
- 238000005658 halogenation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 150000002823 nitrates Chemical class 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- VBWYZPGRKYRKNV-UHFFFAOYSA-N 3-propanoyl-1,3-benzoxazol-2-one Chemical compound C1=CC=C2OC(=O)N(C(=O)CC)C2=C1 VBWYZPGRKYRKNV-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LTDBRVSHYIAOOA-UHFFFAOYSA-L ClC(=O)[Pt](C(=O)Cl)(Cl)Cl Chemical compound ClC(=O)[Pt](C(=O)Cl)(Cl)Cl LTDBRVSHYIAOOA-UHFFFAOYSA-L 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
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- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- 125000000217 alkyl group Chemical group 0.000 description 1
- JRLDUDBQNVFTCA-UHFFFAOYSA-N antimony(3+);trinitrate Chemical class [Sb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JRLDUDBQNVFTCA-UHFFFAOYSA-N 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 229940095064 tartrate Drugs 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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Abstract
本发明涉及一种催化剂,其包括至少一种来自VIII族的金属M,锡,磷促进剂,卤化化合物,多孔载体和至少一种选自镓、铟、铊、砷、锑和铋的促进剂X1。在119Sn Mössbauer光谱学中,还原形式的催化剂具有0至0.45 mm/s的四极分岐值信号,和相对于CaSnO3的1.5至2.4 mm/s的异构体位移IS,所述信号相当于信号总面积的1%至30%。
Description
本申请是以下申请的分案申请:申请日2010年6月15日,申请号201080030122.5,发明名称“具有接近优化位点的多金属催化剂的制备方法”。
技术领域
本发明涉及烃类转化领域,更具体地涉及在催化剂存在下重整烃类进料产生汽油馏分。本发明还涉及用于所述转化的基于至少一种来自铂族的金属的改进催化配制料,以及涉及其制备方法。
现有技术
许多专利描述向铂族催化剂中添加促进剂,以改善其关于烃类进料重整的性能。因此,专利US 2 814 599描述向基于铂或钯的催化剂中添加例如镓、铟、钪、钇、镧、铊或锕的促进剂。
专利US 4 522 935描述包括沉积在载体上铂、锡铟和卤化化合物的重整催化剂,其中铟/铂原子比超过1.14。
专利FR 2 840 548描述均匀颗粒床形式的催化剂,包括无定形基体、至少一种贵金属、至少一种卤素和至少一种另外的金属。所述另外的金属优选选自锡、锗、铅、镓、铟、铊、铼、锰、铬、钼和钨。
磷也已知提高精确包含多于4个碳原子的烃类化合物(C5+),特别是芳族产物的产率。专利US 2 890 167、3 706 815、US 4 367 137、US 4 416 804、US 4 426 279和US 4463 104中请求保护该性能。近年来,专利US 2007/0215523描述添加小于1 wt%的稀释量的磷,使载体稳定化,在用于催化重整法期间允许更好地维持比表面积和氯。
专利US 6 864 212和US 6 667 270描述一种包含以均匀方式分布的铋和磷并用于制备催化重整加氢处理石脑油的催化剂的载体。根据那些专利,向载体中单独添加铋可以减缓形成焦炭并降低活性,但是同时降低了C5+产率,而单独添加磷提高产率,但不改善催化剂稳定性。这两种元素的组合可以进一步减缓焦炭形成,同时对0.10 wt%至0.06 wt%的Bi含量,和0.3 wt%的P含量具有更好的选择性。这两个专利没有请求保护其它元素。
固态NMR谱,特别是魔角旋转(MAS) 31P NMR,已被广泛用于表征磷酸铝型材料中磷原子的环境。这种类型的材料具有0至-30 ppm的化学位移,如Sayari等人(Chem Mater 8,1996, 2080-2088)或Blackwell等人(J Phys Chem 92, 1988, 3965-3970; J Phys Chem88, 1984, 6135-6139)的文章中所披露。在该位移范围中,氧化铝中磷的完全缩合(fullcondensed)的位点能够与不完全缩合的位点区分开来,如Huang等人(J Am Chem Soc, 127(8), 2005, 2731-2740)的文章所表明的那样。但是,为了更精确地确定磷环境的性质,这种单系列的实验是不足够的。偶合该系列,如1H → 31P 交叉极化魔角旋转(CP MAS) NMR,例如能够区分磷的质子化环境并因此将表面原子与基体中的原子区分开来。
此外,使用红外光谱监测一氧化碳到负载的金属催化剂上的吸附是获取关于金属粒子电子密度或载体酸度的信息的一种方式,取决于所述吸附是否在环境温度或在液氮的温度发生。例如在负载有氧化铝上的基于铂的催化剂的情况下,在环境温度,一氧化碳优选吸附到铂上。该吸附通过两种键发生:
•CO的p轨道和金属的未占d轨道之间的σ键;
•满d轨道和CO的空反键轨道之间的π反馈键(π back-bongding)。
后一种键的强度取决于金属给予电子的能力。因此,在富含电子的金属粒子的情况下,反馈供给作用(back-donation)较强而C-O键被弱化:C-O键的波数降低。
在金属粒子的情况下,观察到C-O键的波数νCO随重合程度而变化。该现象通过由吸附的分子之间的偶极耦合引起的微扰(perturbation caused by dipolar coupling)来解释。为了补偿该微扰,C-O键的波数被外推到零重合程度(zero degree of overlap)。从而该值提供了关于粒子的电子密度的信息。
在实践中,使用Primet等人在 Journal of Catalysis 88, (1984), pp 273-282中描述的方法,对与一氧化碳到金属粒子的吸附相对应的区域中C-O键的振动波段的移位的分析可以用于获得在零重合程度时C-O键的波数。
发明内容
本发明涉及一种催化剂,其包括至少一种来自铂族的金属M,锡,磷促进剂,卤化化合物,多孔载体和至少一种选自镓、铟、铊、砷、锑和铋的促进剂X1。所述催化剂的31P魔角旋转NMR信号相对于H3PO4的信号而言是-30ppm到-50ppm。该催化剂的零重合度时的CO键的波数是2077cm-1。本发明还涉及所述催化剂的制备及其在催化重整或芳香族化合物制备反应中的用途。
发明详述
本发明涉及一种催化剂,包括至少一种选自铂族的金属M、锡、磷促进剂、卤化化合物、多孔载体和至少一种选自镓、铟、铊、砷和锑,优选镓、铊和铟,高度优选镓和铟,的促进剂X1,所述催化剂具有相对于H3PO4信号的31P魔角旋转NMR信号为-30至-50ppm。
本发明的催化剂产生改善的催化性能。特别地,所述催化剂对C5+化合物(即包括至少5个碳原子的化合物)的选择性提高,同时焦炭形成显著降低。
催化剂制备方法包括在载体制备步骤期间引入磷和一种或多种促进剂X1的步骤。如果在载体的合成过程中或成型过程中将磷和元素X1(一种或多种)一起引入,那么将获得在31P MAS NMR中所观察到的本发明催化剂的特征信号。
Sn/M原子比通常为0.5至4.0,更优选为1.0至3.5,和高度优选为1.3至3.2。X1/M比通常为0.1至5.0,更优选为0.2至3.0,和高度优选为0.4至2.2。P/M比通常为0.2至30.0,更优选为0.5至20.0,和高度优选为1.0至15.0。金属M的量通常为0.01 wt%至5 wt%,更优选为0.01 wt%至2 wt%,和更优选为0.1 wt%至1 wt%。
金属M通常为铂或钯,高度优选为铂。卤化化合物通常选自氟、氯、溴和碘。卤化化合物的量通常为0.1 wt%至15.0 wt%,更优选为0.1 wt%至8.0 wt%,和更优选为0.2 wt%至5wt%。如果卤化化合物为氯,则氯的量通常为0.0至5.0 wt%,优选为0.5 wt%至2.0 wt%。
将31P MAS NMR和1H →31P CP MAS技术应用于本发明的各种样品。这些技术首先用于揭示具有最佳催化性能的催化剂存在着如下信号:相对于作为参比样的H3PO4,在31P MASNMR谱中化学位移为-30ppm至-50ppm的信号。其次,MAS和CP MAS分析的组合也用于证明这些催化剂在化学位移为0ppm至-7ppm的31P MAS NMR信号中获得大的增益。这种信号对应于经过质子化的并且表征载体制备方式的表面磷的一部分。
使用Bruker DSX 400 MHz分光光度计使用4mm的MAS探针获得所述谱图。样品以经氧化的形式进行分析。将所述两种实验(31P MAS和1H → 31P CP MAS)的旋转频率都固定为10-12kHz,通过使质子上的磁化旋转π/2达2-5微秒来获得1H → 31P CP MAS谱图。所用的CP接触时间经过最优化以满足Hartmann Hahn条件。化学位移是相对于作为参比样的H3PO4的化学位移而给出的。
红外光谱分析在Nexus 1分光光度计上进行。在吸附CO之前,将样品进行如下预处理:在4h内从25℃升温到450℃(其中在150℃时恒温1h),然后在高真空下在450℃保温10h。然后将样品在过量H2中在450℃还原30分钟。接下来,施加高真空15分钟。所述还原程序进行4次。
CO脉冲吸附在环境温度下进行,随后一氧化碳在25°C、50°C、75°C、100°C和150°C解吸。在每一温度处记录红外光谱。接下来,采用Primet等在Journal of Catalysis 88,(1984), pp 273-282中描述的方法来将C-O键的波数外推到零重合度的情况(ν0 CO)。
这些测量结果表明,在石脑油(naphtha)催化重整反应中获得的最优化的芳族化合物收率归因于其中金属M上的电子密度减少了的催化剂,所述电子密度使得零重合度的ν0 CO严格大于2077 cm-1。
载体通常包括选自镁、钛、锆、铝和硅的氧化物的至少一种氧化物。优选,其为二氧化硅、氧化铝或二氧化硅-氧化铝,和高度优选为氧化铝。根据本发明,所述多孔载体有利地为珠粒、挤出物、颗粒或粉末形式。高度有利地,所述载体为珠粒或挤出物形式。载体的孔容优选为0.1至1.5 cm3/g,更优选为0.4至0.8 cm3/g。此外,所述多孔载体具有有利地为50至600 m2/g,优选为100至400 m2/g,或甚至为150至300 m2/g的比表面积。
本发明还涉及制备本发明催化剂的方法通常包括以下步骤:
a) 在子步骤a1)或a2)之一期间,引入一种或多种促进剂X1和磷,所述子步骤a1)对应于主氧化物的前体的合成,所述子步骤a2)对应于载体的成型;
b) 在子步骤a1)和a2)的至少一个期间引入锡,步骤a)和b)可是连续或同时的;
c) 干燥步骤b)末尾获得的产物;
d) 在350℃至650℃下煅烧步骤c)中获得的产物;
e) 沉积至少一种来自铂族的金属M;
f) 在中性气体流或含氧气体流中,在不超过150℃温和温度下干燥;
g) 在350℃至650℃下煅烧步骤f)中获得的产物。
锡可以仅在成型载体时部分引入,该方法因此包括在载体上沉积互补部分(fraction)的锡的步骤,该步骤在步骤d)和e)之间,之后为干燥和煅烧或者相反,或在步骤e)和f)之间,或在步骤g)之后,之后为干燥和煅烧。
步骤g)的煅烧通常在任选富氧或富氮的空气存在下进行。
可以使用本领域技术人员已知的任何技术引入促进剂X1、P和Sn。引入载体期间,促进剂X1、P和Sn可以通过混合、共沉淀或溶解来添加;这些方法没有限制。
因此,锡可以与前体X1和P同时引入,或者可以在前体X1和P之前或之后单独引入。
在引入一种或多种促进剂X1和磷,即在合成氧化物前体期间的情况下,根据本发明的优选制备方法,锡、磷和一种或多种前体X1在使用溶胶-凝胶型技术合成主氧化物的前体期间引入。
根据另一个优选的方法,前体加入到制得的主氧化物前体的溶胶中。使用现有技术的载体成型技术,例如包括挤出或油滴凝聚的成型步骤,来成型载体。
X1前体具有多个类型,取决于X1的性质,并且可以单独使用或以混合物的形式使用。在铟的情况下,铟卤化物、硝酸盐、硫酸盐、过氯酸盐、氰化物或氢氧化物是合适的。可以使用镓卤化物、硝酸盐、硫酸盐、氰化物、氢氧化物和卤氧化物类型的前体。铊可以以铊硝酸盐、硫酸盐和氢氧化物的形式引入。在锑的情况下,锑硝酸盐、硫酸盐和氢氧化物是合适的。可以使用砷卤化物和卤氧化物的前体。铋可以以铋卤化物、硝酸盐、氢氧化物、卤氧化物或碳酸盐,或铋酸的形式引入。
在类型方面,锡前体可以是矿物的或者可以是有机金属,可以属于水溶性有机金属类型。可以单独或以混合物形式使用各种前体。特别地,可以选择锡;以非限制方式,锡可以选自卤代、氢氧化物、碳酸盐、羧酸盐、硫酸盐、酒石酸盐和硝酸盐化合物。当它们原位产生或可被原位产生(例如通过引入锡和羧酸)时,锡的这些形式可以引入催化剂制备介质中。有机金属锡基类型前体的实例为SnR4,其中R表示烷基,例如丁基,Me3SnCl,Me2SnCl2,Et3SnCl,Et2SnCl2,EtSnCl3,iPrSnCl2族,和氢氧化物Me3SnOH,Me2Sn(OH)2,Et3SnOH,Et2Sn(OH)2,氧化物(Bu3Sn)2O,乙酸盐Bu3SnOC(O)Me。优选使用锡的卤代形式,特别是氯化形式。特别有利地使用SnCl2或SnCl4。
在锡的情况下已经将促进剂Sn、X1和P引入已经成型的载体之中或之上,制备本发明催化剂的规程要求在沉积来自铂族的金属M之前进行煅烧(步骤d)。所述煅烧优选在350℃至650℃,优选400℃至600℃,和更优选400℃至550℃下进行。升温可以是规则的,或可以包括中间恒温阶段,利用固定或可变的温度分布曲线达到所述阶段。温度的升高因此可以速率相同或不同(以每分钟或每小时的度数计)。煅烧期间使用的气氛包含优选2体积%至50体积%和更优选5体积%至25体积%的氧气。该煅烧步骤期间因此也可以使用空气。
获得载体之后,沉积至少一种来自铂族的金属M (步骤e)。在该步骤中,可以通过干燥浸渍或过量溶液浸渍,使用包含来自铂族的金属M的前体或前体混合物引入金属M。浸渍可以在基于金属M前体和载体之间的相互作用有效的物质存在下进行。在非限制方式中,所述物质可以为矿物酸(HCl、HNO3)或有机酸(羧酸或多羧酸类型),和有机络合型化合物。优选,使用本领域技术人员已知的任何技术进行浸渍,用于在催化剂内达到金属M的均匀分布。
金属M的前体形成以下组的一部分,但是该列表没有限制:六氯铂酸、溴铂酸、氯铂酸铵、氯化铂、二氯碳酰二氯化铂和四胺氯化铂。
在该阶段,在优选不超过250℃的适度温度下,在中性气氛或包含氧气(可以使用空气)的气氛中,干燥包含X1、Sn、P和铂的催化剂(步骤f)。优选,干燥在200℃或更低的温度下进行几分钟至几小时。
该步骤之后为煅烧步骤f)中获得的产物。所述煅烧优选在空气存在下进行。空气也可以富含氧气或氮气。优选,所述气体中的氧气含量达到0.5体积%至30.0体积%,更优选为2体积%至25体积%。
所述煅烧在350℃至650℃,优选400℃至650℃,和更优选450℃至550℃下进行。温度分布曲线可以任选包含恒温阶段。
当本发明催化剂的制备中使用的各种前体不包含卤素或包含不足量的卤素时,可能必要的是在制备期间添加卤化化合物。可以使用本领域技术人员已知的任何化合物,并将其引入本发明催化剂的制备的任一个步骤中。特别地,可以使用Friedel-Crafts型化合物,例如氯化铝或溴化铝。也可使用有机化合物,例如甲基或乙基卤化物,例如二氯甲烷、氯仿、二氯乙烷、甲基氯仿或四氯甲烷。
也可以使用氧氯化处理将氯加入到本发明的催化剂中。所述处理可以例如在空气流中在500℃进行4小时,所述空气流包含沉积所需氯量所需的气态氯量和H2O/Cl摩尔比接近例如20的水量。
也可以借助于用水性盐酸溶液浸渍来添加氯。典型的规程由浸渍固体组成,以引入所需氯量。催化剂与水溶液保持接触足够长的时间,以沉积氯量,然后排出催化剂并在80℃至150℃下干燥,然后最后在450℃至650℃下在空气中煅烧。
本发明还涉及催化剂在催化重整反应或芳族化合物生产反应中通过使所述催化剂与烃进料接触而实现的用途。例如,重整工艺可用来提高得自原油蒸馏和/或其它精炼工艺如催化裂化或热裂解的汽油级分的辛烷值。
用于生产芳族化合物的工艺产生基料产物(base products)(苯、甲苯、二甲苯),其能够在石油化学中使用。
这两种工艺由于它们有助于产生大量氢而格外引人注意,所述氢对精炼厂实施的氢化和加氢处理工艺是不可缺少的。这两种类型的工艺能够因操作条件和进料组成的选择而不同;这些是本领域技术人员熟知的。
用于重整工艺的进料通常含有链烷的、环烷的和芳族的烃,其每分子含有5-12个碳原子。所述进料尤其由其密度和其按重量计的组成所限定。这些进料可具有40℃-70℃的初沸点和160℃-220℃的终点。它们还可以由初沸点和终点为40℃-220℃的级分或汽油级分混合物构成。所述进料还可以由沸点为160℃-200℃的重石脑油构成。
典型地,重整催化剂被供给设施(unit)中并经历在先的还原处理。还原步骤通常在稀释的或纯的氢气气氛中,有利地在400℃至600℃,优选450℃至550℃下进行。
所述进料然后在氢存在下引入,并且其中氢/进料烃摩尔比通常为0.1-10,优选1-8。用于重整的操作条件通常如下:温度优选为400℃-600℃,更优选为450℃-540℃,和压力优选为0.1 MPa-4 MPa,更优选为0.25 MPa-3.0 MPa。所产生氢中的全部或一部分可以再循环至重整反应器的入口。
实施例
以下实施例说明本发明。
实施例1 (对比)
催化剂A的制备:Pt/(Al
2
O
3
-Sn)-Cl
通过使二氯化锡与由氯化铝水解获得的氧化铝水溶胶接触,制备氧化铝珠粒形式的载体,其包含0.3 wt%的锡并具有1.2 mm的平均直径。由此获得的氧化铝水溶胶然后进入充满添加剂油的垂直柱。在至多600℃下热处理由此获得的球体,以获得具有优良机械强度的珠粒。由此获得的载体具有205 m2/g的BET表面。
通过在最终的催化剂上沉积0.3 wt%的铂和1 wt%的氯,在该载体上制备催化剂A。向100 g包含锡的氧化铝载体中添加400 cm3的六氯铂酸和盐酸的水溶液。使其保持接触4小时,然后排出。在120℃使其干燥,然后在每小时100升的空气流中在500℃煅烧2小时,温度陡升为每分钟7℃。选择四氯化锡的量使得获得在煅烧产品上总重量为0.3wt%锡。煅烧之后获得的催化剂A包含0.29 wt%的铂,0.30 wt%的锡和1.02 wt%的氯。
实施例2 (对比)
催化剂B的制备:Pt/(Al
2
O
3
-Sn-In)-Cl
通过使二氯化锡和硝酸铟与由氯化铝水解获得的氧化铝水溶胶接触,制备氧化铝珠粒形式的载体,其包含0.3 wt%的锡和0.3 wt%的铟,具有1.2 mm的平均直径。由此获得的氧化铝水溶胶然后进入充满添加剂油的垂直柱。在至多600℃下热处理由此获得的球体,以获得具有优良机械强度的珠粒。由此获得的载体具有201 m2/g的BET表面。
在该载体上制备催化剂B,目标为与实施例1中的铂和氯含量相同。煅烧之后获得的催化剂B包含0.29 wt%的铂,0.29 wt%的锡,0.30 wt%的铟和1.05 wt%的氯。
实施例3 (对比)
催化剂C的制备:Pt/(Al
2
O
3
-Sn-P)-Cl
通过使二氯化锡和磷酸与氧化铝水溶胶接触,以类似于实施例1中所述的方式获得氧化铝珠粒形式的载体,其包含0.3 wt%的锡和0.4 wt%的磷,具有1.2 mm的平均直径。由此获得的载体具有198 m2/g的BET表面。
在该载体上制备催化剂C,目标为与实施例1中的铂和氯含量相同。煅烧之后获得的催化剂C包含0.30 wt%的铂,0.31 wt%的锡,0.39 wt%的磷和1.00 wt%的氯。
实施例4 (本发明)
催化剂D的制备:Pt/(Al
2
O
3
-Sn-In-P)-Cl
通过使二氯化锡、硝酸铟和磷酸与氧化铝水溶胶接触,以类似于实施例1中所述的方式获得氧化铝珠粒形式的载体,其包含0.3 wt%的锡,0.3 wt%的铟和0.4 wt%的磷,具有1.2 mm的平均直径。由此获得的载体具有196 m2/g的BET表面。
在该载体上制备催化剂D,目标为与实施例1中的铂和氯含量相同。煅烧之后获得的催化剂D包含0.30 wt%的铂,0.31 wt%的锡,0.32 wt%的铟,0.38 wt%的磷和1.00 wt%的氯。
实施例5 (本发明)
催化剂E的制备:Pt/(Al
2
O
3
-Sn-In-P)-Cl
用和实施例4一样的方法制备氧化铝珠粒形式的载体,具有相同的锡和磷量,但是仅引入0.2 wt%的铟。由此获得的载体具有210 m2/g的BET表面。
在该载体上制备催化剂E,目标为与实施例1中的铂和氯含量相同。煅烧之后获得的催化剂E包含0.31 wt%的铂,0.31 wt%的锡,0.22 wt%的铟,0.40 wt%的磷和1.02 wt%的氯。
实施例6 (对比)
催化剂F的制备:Pt-In/(Al
2
O
3
-Sn-P)-Cl
制备载体,目标为与实施例3中的锡和磷量相同。由此获得的载体具有180 m2/g的BET表面。
在该载体上制备催化剂F,目标为最终催化剂上的0.3 wt%的铂,0.3 wt%的铟和1wt%的氯。
向100 g包含锡和磷的氧化铝载体中添加400 cm3的六氯铂酸和盐酸的水溶液。使其保持接触4小时,然后排出。在90℃将其干燥,然后在盐酸存在下使其与200 cm3的硝酸铟水溶液接触。使其保持接触4小时,排出,在120℃干燥,然后在每小时100升的空气流中在500℃煅烧2小时,温度陡升为每分钟7℃。煅烧之后获得的催化剂F包含0.30 wt%的铂,0.32wt%的锡,0.29 wt%的铟,0.41 wt%的磷和1.04 wt%的氯。
实施例7 (对比)
催化剂G的制备:Pt-In-P/(Al
2
O
3
-Sn)-Cl
制备载体,目标为与实施例1中的锡量相同。
在该载体上制备催化剂G,目标为最终催化剂上的0.3 wt%的铂,0.3 wt%的铟,0.4wt%的磷和1 wt%的氯。由此获得的载体具有209 m2/g的BET表面。
向100 g包含锡和磷的氧化铝载体中添加400 cm3的六氯铂酸和盐酸的水溶液。使其保持接触4小时,然后排出。在90℃将其干燥,然后在盐酸存在下使其与200 cm3的硝酸铟和磷酸水溶液接触。使其保持接触4小时,排出,在120℃干燥,然后在每小时100升的空气流中在500℃煅烧2小时,温度陡升为每分钟7℃。煅烧之后获得的催化剂G包含0.30 wt%的铂,0.31 wt%的锡,0.33 wt%的铟,0.38 wt%的磷和1.05 wt%的氯。
实施例8 (本发明)
催化剂H的制备:Pt-Sn/(Al
2
O
3
-Sn-In-P)-Cl
制备载体,目标为与实施例4中的铟和磷量相同,但具有0.2 wt%的铟。由此获得的载体具有182 m2/g的BET表面。
通过沉积0.35 wt%的铂,补足的0.2 wt%的锡,以在最终催化剂上获得0.4 wt%的锡和1 wt%的氯,在该载体上制备催化剂H。
向100 g包含锡和铟的氧化铝载体中添加400 cm3的六氯铂酸和盐酸的水溶液。使其保持接触4小时,然后排出。在90℃将其干燥,然后在盐酸存在下使其与200 cm3的四氯化锡水溶液接触。使其保持接触4小时,排出,在120℃干燥,然后在每小时100升的空气流中在500℃煅烧2小时,温度陡升为每分钟7℃。煅烧之后获得的催化剂H包含0.36 wt%的铂,0.41wt%的锡,0.29 wt%的铟,0.41 wt%的磷和0.99 wt%的氯。
实施例9 (本发明)
催化剂I的制备:Pt-Sn/(Al
2
O
3
-Sn-Sb-P)-Cl
以类似于实施例4中所述的方式,使用二氯化锡、硝酸镓和磷酸,制备包含0.1 wt%的锡,0.4 wt%的锑和0.4 wt%的磷并具有1.2 mm平均直径的氧化铝珠粒载体。由此获得的载体具有191 m2/g的BET表面。
由所述载体制备催化剂I,具有与实施例7相同的铂、锡和氯量。煅烧之后获得的催化剂G包含0.29 wt%的铂,0.30 wt%的锡,0.32 wt%的铟,0.42 wt%的磷和1.10 wt%的氯。
实施例10催化剂A至I的红外和NMR特征
催化剂C至I的31P NMR信号数值,使用在说明书中所描述的方法测定,以及在表1中详细描述的{1H - 31P} CP MAS 系列中多种信号的面积增长。该增长以在交叉极化 (CPMAS)中获得的信号的面积与在直接极化(direct polarization) (MAS)中具有相同化学位移的信号的面积之间的比例计算。
在此表中报告了9种催化剂的ν0 CO数值。
催化剂A和B不包含P,磷NMR没有在它们上实施。
表1:催化剂A至I的红外和NMR表征。
实施例11:催化剂A至I在催化重整中的表现评价
将如实施例1至9所述制备的催化剂试样放入反应床中,该反应床适合于转化衍生自油蒸馏的石脑油型烃类进料。该石脑油具有以下组成(按重量计):
● 52.6%的链烷烃化合物;
● 31.6%的环烷烃;
● 15.8%的芳族分子;
总密度为0.759 g/cm3。
进料的研究辛烷值接近55。
加入到反应器中之后,通过在490℃下在纯氢气气氛中热处理2小时活化该催化剂。
在上述氢气和石脑油存在下,在重整反应条件下评价催化表现。特别地,使用的条件和催化剂对比如下:
● 反应器压力保持在8 bar g (0.8 MPa g);
● 每千克催化剂,进料流速为2.0 kg/h;
● 进料的氢气/烃类摩尔比:4。
对比由进料的催化转化产生的液体排放物(也称作重整产品)的研究辛烷值的异构-性能(iso-quality)。对比104的研究辛烷值。
表2:催化剂性能。
图1显示了随着C-O键的振动频率位移,芳香族化合物收率的变化,显示了当铂颗粒电子密度在IR图谱记录条件下减小时所获得的芳香族产物收率的增长。
零重合度ν0 CO严格大于2077 cm-1使得改进待获得的芳香族化合物的收率。
Claims (4)
1.一种催化剂在催化重整或芳族化合物制备反应中以减少焦炭形成的用途,其中所述催化剂包含选自铂的金属M、锡、磷促进剂、选自氯的卤化化合物、选自氧化铝的多孔载体和选自铟的促进剂X1,并且该催化剂具有相对于H3PO4的信号为-30ppm到-50ppm的31P魔角旋转NMR信号,并且在该催化剂金属M上的减少的电子密度使得在零重合度的ν0 CO严格大于2077 cm-1;其中该催化剂通过包括下述步骤的方法进行制备:
a) 在子步骤a1)或a2)之一期间,引入一种或多种促进剂X1,锡和磷,所述子步骤a1)对应于主氧化物的前体的合成,所述子步骤a2)对应于载体的成型;
b) 干燥在步骤a)结束时获得的产物;
c) 在350℃至650℃温度下煅烧在步骤b)中获得的产物;
d) 沉积至少一种来自铂族的金属M;
e) 在中性气体流或含氧气体流中,在不超过150℃的温和温度下干燥;
f) 在350℃至650℃的温度下煅烧在步骤e)中获得的产物,
其中Sn/M原子比为0.5至4.0,X1/M比为0.1至5.0,和P/M比为1至15。
2.根据权利要求1的用途,其中金属M的量为0.01 wt%至5 wt%。
3.根据权利要求1至2任一项的用途,其中卤化化合物的量为0.1 wt%至15.0 wt%。
4.根据权利要求1至2任一项的用途,其中卤化化合物为氯,氯含量为0.1 wt%至5.0wt%。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR09/03.226 | 2009-07-01 | ||
FR0903226A FR2947465B1 (fr) | 2009-07-01 | 2009-07-01 | Catalyseur multi-metallique presentant une proximite de sites optimisee |
PCT/FR2010/000443 WO2011012776A2 (fr) | 2009-07-01 | 2010-06-15 | Procede de preparation d'un catalyseur multi-métallique présentant une proximité de sites optimisée |
CN2010800301225A CN102665897A (zh) | 2009-07-01 | 2010-06-15 | 具有接近优化位点的多金属催化剂的制备方法 |
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CN201610819884.2A Active CN106423226B (zh) | 2009-07-01 | 2010-06-15 | 具有接近优化位点的多金属催化剂的制备方法 |
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EP (1) | EP2448670B1 (zh) |
JP (1) | JP5615917B2 (zh) |
CN (2) | CN102665897A (zh) |
DK (1) | DK2448670T3 (zh) |
FR (1) | FR2947465B1 (zh) |
RU (1) | RU2535206C2 (zh) |
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Families Citing this family (6)
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US20150133291A1 (en) * | 2012-05-08 | 2015-05-14 | Stc.Unm | Hydrothermal Stability of Oxides With Carbon Coatings |
CN104841425A (zh) * | 2014-02-18 | 2015-08-19 | 中国石油化工股份有限公司 | 一种半再生催化重整催化剂及其制备方法 |
FR3039082B1 (fr) | 2015-07-24 | 2017-07-21 | Ifp Energies Now | Catalyseur multi-metallique dope par du phosphore et un lanthanide |
FR3074063B1 (fr) * | 2017-11-30 | 2019-11-01 | IFP Energies Nouvelles | Catalyseur multi-metallique dope par du phosphore et de l'ytterbium |
FR3120076A1 (fr) | 2021-02-22 | 2022-08-26 | IFP Energies Nouvelles | Procédé de production de composés aromatiques et/ou d’essences à partir d’une charge hydrocarbonée de type naphta |
FR3123230A1 (fr) | 2021-05-28 | 2022-12-02 | IFP Energies Nouvelles | Procédé de traitement à régénération continue de catalyseur d’une charge hydrocarbonée |
Family Cites Families (19)
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US2814599A (en) | 1953-04-17 | 1957-11-26 | Kellogg M W Co | Group iii metal compound promoted platinum or palladium catalyst |
US2890167A (en) | 1953-11-16 | 1959-06-09 | Universal Oil Prod Co | Conversion process using a phosphoruscontaining platinum group metal catalyst |
US3706815A (en) | 1971-05-24 | 1972-12-19 | Union Oil Co | Chelated metal-polyphosphoric acid catalysts,method of preparation and isomerization process utilizing the same |
US4016068A (en) * | 1974-06-21 | 1977-04-05 | Uop Inc. | Catalytic reforming with an activated bimetallic catalytic composite |
US4367137A (en) | 1980-12-04 | 1983-01-04 | Uop Inc. | Hydrocarbon conversion with an acidic multimetallic catalytic composite |
US4416804A (en) * | 1981-11-23 | 1983-11-22 | Uop Inc. | Acidic multimetallic catalytic composite |
US4426279A (en) | 1981-11-23 | 1984-01-17 | Uop Inc. | Reforming hydrocarbons with a platinum group- and phosphorus-containing catalyst |
US4463104A (en) | 1981-11-23 | 1984-07-31 | Uop Inc. | Platinum group and phosphorus containing catalyst composition for hydrocarbon conversion |
US4487848A (en) * | 1983-06-02 | 1984-12-11 | Uop Inc. | Indium-containing catalyst for reforming hydrocarbons |
US4522935A (en) * | 1983-06-02 | 1985-06-11 | Uop Inc. | Platinum and indium-containing catalyst for reforming hydrocarbons |
US5858908A (en) * | 1997-04-17 | 1999-01-12 | Uop Llc | Selective multimetallic-multigradient reforming catalyst |
CN1384175A (zh) * | 2001-04-28 | 2002-12-11 | 中国石油化工股份有限公司 | 含铂、锡的多金属重整催化剂及其制备与应用 |
EP1507586A1 (en) * | 2002-05-22 | 2005-02-23 | Shell Internationale Research Maatschappij B.V. | Bismuth-and phosphorus-containing reforming catalysts, method of making and naphtha reforming process |
US6667270B2 (en) * | 2002-05-22 | 2003-12-23 | Shell Oil Company | Bismuth-and phosphorus-containing catalyst support, reforming catalysts made from same, method of making and naphtha reforming process |
FR2840548B1 (fr) | 2002-06-07 | 2005-03-18 | Inst Francais Du Petrole | Lit homogene de catalyseur et procede de transformation d'hydrocarbures en composes aromatiques avec ledit lit |
US20070215523A1 (en) | 2002-12-10 | 2007-09-20 | Moser Mark D | Dilute phosphorus incorporation into a naphtha reforming catalyst |
CN100338189C (zh) * | 2004-05-14 | 2007-09-19 | 中国石油化工股份有限公司 | 一种铂、锡系重整催化剂的制备方法 |
US7449423B2 (en) * | 2005-01-14 | 2008-11-11 | Headwaters Technology Innovation, Llc | Heat treatment of anchored nanocatalysts in a non-zero oxidation state and catalysts made by such method |
FR2910347B1 (fr) * | 2006-12-22 | 2009-12-04 | Inst Francais Du Petrole | Catalyseur bimetallique ou multi-metallique presentant un indice de bimetallicite et une capacite d'adsorption d'hydrogene optimises |
-
2009
- 2009-07-01 FR FR0903226A patent/FR2947465B1/fr active Active
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2010
- 2010-06-15 JP JP2012518103A patent/JP5615917B2/ja active Active
- 2010-06-15 US US13/381,281 patent/US20120178979A1/en not_active Abandoned
- 2010-06-15 WO PCT/FR2010/000443 patent/WO2011012776A2/fr active Application Filing
- 2010-06-15 EP EP10734170.3A patent/EP2448670B1/fr active Active
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RU2535206C2 (ru) | 2014-12-10 |
FR2947465B1 (fr) | 2012-05-11 |
EP2448670A2 (fr) | 2012-05-09 |
WO2011012776A3 (fr) | 2011-11-17 |
WO2011012776A2 (fr) | 2011-02-03 |
JP5615917B2 (ja) | 2014-10-29 |
EP2448670B1 (fr) | 2015-09-23 |
JP2012531306A (ja) | 2012-12-10 |
RU2012103328A (ru) | 2013-08-10 |
US20120178979A1 (en) | 2012-07-12 |
FR2947465A1 (fr) | 2011-01-07 |
CN106423226A (zh) | 2017-02-22 |
CN102665897A (zh) | 2012-09-12 |
DK2448670T3 (en) | 2016-01-11 |
US20170252726A1 (en) | 2017-09-07 |
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