CN112569917A - Catalyst carrier, catalyst and method for producing unsaturated hydrocarbon by dehydrogenating saturated hydrocarbon - Google Patents
Catalyst carrier, catalyst and method for producing unsaturated hydrocarbon by dehydrogenating saturated hydrocarbon Download PDFInfo
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- CN112569917A CN112569917A CN201910926417.3A CN201910926417A CN112569917A CN 112569917 A CN112569917 A CN 112569917A CN 201910926417 A CN201910926417 A CN 201910926417A CN 112569917 A CN112569917 A CN 112569917A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 155
- 229930195734 saturated hydrocarbon Natural products 0.000 title claims abstract description 13
- 229930195735 unsaturated hydrocarbon Natural products 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000003223 protective agent Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 25
- 229910052697 platinum Inorganic materials 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 19
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 238000005507 spraying Methods 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000009828 non-uniform distribution Methods 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- IEIIMXZFDMTPNA-UHFFFAOYSA-H Cl[Os](Cl)(Cl)(Cl)(Cl)Cl.N Chemical compound Cl[Os](Cl)(Cl)(Cl)(Cl)Cl.N IEIIMXZFDMTPNA-UHFFFAOYSA-H 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 claims description 3
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 3
- SNPHNDVOPWUNON-UHFFFAOYSA-J platinum(4+);tetrabromide Chemical compound [Br-].[Br-].[Br-].[Br-].[Pt+4] SNPHNDVOPWUNON-UHFFFAOYSA-J 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 239000005456 alcohol based solvent Substances 0.000 claims description 2
- 239000004210 ether based solvent Substances 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- 229940084106 spermaceti Drugs 0.000 claims description 2
- 239000012177 spermaceti Substances 0.000 claims description 2
- 150000003626 triacylglycerols Chemical class 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 17
- 238000005299 abrasion Methods 0.000 abstract description 12
- 239000002344 surface layer Substances 0.000 abstract description 10
- 238000006356 dehydrogenation reaction Methods 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 19
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 18
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 15
- 239000000843 powder Substances 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 239000012876 carrier material Substances 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- -1 platinum group metals Chemical class 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical group [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- LTAJYXNAVRSSDS-UHFFFAOYSA-N ethanol;hexadecanoic acid Chemical compound CCO.CCCCCCCCCCCCCCCC(O)=O LTAJYXNAVRSSDS-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- VMDTXBZDEOAFQF-UHFFFAOYSA-N formaldehyde;ruthenium Chemical compound [Ru].O=C VMDTXBZDEOAFQF-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012694 precious metal precursor Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009495 sugar coating Methods 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J33/00—Protection of catalysts, e.g. by coating
-
- B01J35/51—
-
- 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
- B01J37/0201—Impregnation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
- C07C5/48—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor with oxygen as an acceptor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
- C07C2523/42—Platinum
Abstract
The invention discloses a catalyst carrier, which is internally provided with a straight channel, and the outer surface of the catalyst carrier is coated with a protective agent. The invention also discloses a catalyst with the active components distributed non-uniformly. In addition, the invention also discloses a method for preparing unsaturated hydrocarbon by dehydrogenating saturated hydrocarbon. The active components of the catalyst are distributed on the surface layer of the straight channel in the catalyst, and the platinum group metal active components are not contained on the outer surface of the catalyst sphere, so that the loss of noble metals caused by surface abrasion of the catalyst can be reduced.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst carrier and a catalyst containing the catalyst carrier. The invention also relates to a method for producing unsaturated hydrocarbons by dehydrogenating saturated hydrocarbons.
Background
Unsaturated hydrocarbons are a basic organic chemical raw material, and the catalytic dehydrogenation of saturated hydrocarbons is a main production method of unsaturated hydrocarbons in the petrochemical industry. The process of alkane dehydrogenation or aromatic dehydrogenation to produce unsaturated hydrocarbons is an equilibrium reaction in which the heat is absorbed and the number of molecules is increased. The catalyst bed temperature can be significantly reduced in adiabatic reactors, which in turn leads to a reduction in conversion. The single-pass conversion rate of alkane or aromatic hydrocarbon can be improved by increasing the reaction temperature and reducing the reaction pressure, but due to the limitation of thermodynamic equilibrium, the single-pass conversion rate of alkane or aromatic hydrocarbon is difficult to further improve under certain process conditions.
One method for solving the above problems is to introduce oxygen or a gas containing oxygen into the reaction system, and combust the hydrogen generated by dehydrogenation of alkane or aromatic hydrocarbon under the action of a hydrogen selective oxidation catalyst, thereby breaking the chemical equilibrium of the original system. After the hydrogen is combusted and consumed, the dehydrogenation reaction can be moved in a direction favorable for generating unsaturated hydrocarbon, and meanwhile, a large amount of heat released by the combustion of the hydrogen can supply heat for the dehydrogenation reaction, so that the energy consumption is reduced.
The key of the process method is the hydrogen selective oxidation catalyst which has various types, wherein the thin-shell type hydrogen selective oxidation catalyst with active components distributed on the catalyst in a non-uniform way has obvious effect. The structure ensures that the raw materials and the products have shorter diffusion paths, shortens the retention time of alkane or aromatic hydrocarbon on the catalyst, reduces the occurrence of side reactions, and improves the selectivity of oxygen for oxidizing hydrogen; meanwhile, the structure is beneficial to the rapid diffusion of heat released by hydrogen combustion.
Patent CN200380101578.6 discloses a catalyst for selective oxidation of hydrogen, which is based on an inert material as core, such as cordierite, and on lithium aluminate bonded to the outer layer of the inert material as carrier. The lithium aluminate support has dispersed therein a platinum group metal such as platinum and a promoter metal such as tin. The catalyst has good effect on selective oxidation of hydrogen in the dehydrogenation process.
The patent CN200810032914.0 is based on the adsorption theory, and by modulating the adsorption capacity and adsorption speed of the layered composite carrier to the catalyst precursor, the active component of the catalyst is dispersed on the outer surface of the catalyst, so that the active component is in an eggshell-shaped structure in the catalyst, thereby increasing the utilization rate of the noble metal and reducing the amount of the noble metal. Coating slurry of a coating porous material on an inner core of an inert carrier, drying, roasting for 0.5-10 hours at 700-1200 ℃ to obtain a layered composite carrier, impregnating the layered composite carrier with a solution containing noble metal and a cocatalyst component, drying, roasting for 1-24 hours in air at 200-700 ℃ to obtain a thin-shell catalyst precursor, and finally reducing the thin-shell catalyst precursor for 1-24 hours at 300-800 ℃ in a reducing atmosphere to obtain the thin-shell noble metal catalyst.
In patent CN 200910201626.8, a catalyst in which platinum group metals, alkali metals, alkaline earth metals and lanthanide series auxiliaries are loaded on a layered composite carrier is applied in the industrial production of styrene by catalytic dehydrogenation of ethylbenzene. The method comprises the steps of taking a product of ethylbenzene catalytic dehydrogenation and oxygen or gas containing oxygen as raw materials, and reacting at the temperature of 400-800 ℃, the reaction pressure of 1-1000 kPa and the liquid reaction space velocity of 0.01-100 hours-1Under the condition, the reaction raw material contacts with an oxidation catalyst to combust hydrogen and promote the balance of the moving material, thereby improving the conversion rate of the ethylbenzene. However, the thin-shell type composite carrier catalyst has the technical problems of high abrasion rate and insufficient catalyst stability.
In this respect, patent CN201010552838.3 discloses a method for controlling the base carrier material and the coating material of the composite carrierThe specific surface area of the material and the specific surface area of the material improve the bonding firmness of the coating and the substrate, and the specific surface area of the substrate carrier is controlled to be 2m2G, preferably 1-2 m2(ii)/g; the specific surface area of the coating material is more than 150m2The concentration of the water is controlled to be 150-300 m2The prepared carrier and the catalyst have low abrasion rate, and the obtained thin-shell noble metal catalyst has the advantages of high selectivity and good stability.
The catalytic active components of the catalysts described in the above patents are all distributed on the surface layer of the whole catalyst, and are exposed outside. During the transportation, filling and use of the catalyst, the mutual friction among catalyst particles, the collision friction between the catalyst and equipment and the long-term scouring of the catalyst by reaction gas inevitably cause the abrasion of the outer surface layer of the catalyst. The abrasion of the outer surface layer of the catalyst can cause the loss of active components, especially the loss of expensive platinum metals such as platinum, which not only affects the use effect of the catalyst, but also causes resource and economic losses.
Disclosure of Invention
In view of the problems of the prior art, the first object of the present invention is to provide a catalyst carrier, the second object is to provide a method for preparing the catalyst carrier, the third object is to provide a catalyst with a non-uniform distribution of active components, the fourth object is to provide a method for preparing a catalyst with a non-uniform distribution of active components, and the fifth object is to provide a method for producing unsaturated hydrocarbons by dehydrogenating saturated hydrocarbons.
The catalyst carrier provided by the invention is internally provided with a straight channel, and the outer surface of the catalyst carrier is coated with a protective agent. Preferably, the catalyst support is spherical or spheroidal.
According to some embodiments of the catalyst support of the present invention, the protective agent is selected from one or more of paraffin, palmitic acid, stearic acid, eicosanoic acid, lignitic acid, spermaceti acid, dodecanol and triglycerides.
According to some embodiments of the catalyst support of the present invention, the protective agent is present in an amount of 0.5 to 5% by mass of the support.
According to some embodiments of the catalyst support of the present invention, the material of the support is a porous oxide material, preferably comprising at least one selected from the group consisting of gamma-alumina, delta-alumina, theta-alumina and molecular sieves.
According to some embodiments of the catalyst support of the present invention, the diameter of the support is in the range of 2mm to 2cm, preferably 2mm to 1.5cm, more preferably 2mm to 1.2cm, for example 2 to 8mm, such as 3mm, 4mm, 5mm, 6mm or 7 mm.
According to some embodiments of the catalyst carrier of the present invention, the number of straight channels is preferably 2 or more, more preferably 2 to 10, such as 3, 4, 5, 6 or 7, parallel to the sphere axis of the carrier.
According to some embodiments of the catalyst support of the present invention, the diameter of the straight channels is 0.1mm to 3mm, preferably 0.2 to 2mm, such as 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.8mm, 1.0mm, 1.2mm, 1.3mm, 1.5mm, etc.
According to some embodiments of the catalyst carrier according to the present invention, the straight channels are all parallel to the sphere axis and are evenly distributed between the straight channels within the spherical carrier.
The straight channels are in the largest cross section of the ball perpendicular to the straight channels, and the sum of the cross sections of the straight channels accounts for 5% -50%, preferably 10-50%, such as 11%, 15% or 20% of the largest cross section area of the ball.
According to some preferred embodiments, the carrier is: a delta-alumina support of 2 to 5mm, e.g. 4mm, diameter having straight channels 5 to 10, e.g. 7, of 0.2 to 1.0mm, e.g. 0.5mm diameter, the sum of the cross-sectional areas of the straight channels representing 5 to 15%, e.g. 11%, of the maximum cross-sectional area of the sphere.
According to some other preferred embodiments, the carrier is: the molecular sieve carrier with diameter of 5-10mm has 2-5 straight channels (e.g. 3) with diameter of 1.5-2.0mm (e.g. 1.83 mm), and the sum of the cross-sectional areas of the straight channels accounts for 5-15%, e.g. 10%, of the maximum cross-sectional area of the ball.
The preparation method of the catalyst carrier provided by the invention comprises the following steps:
1) extruding, molding and dicing the carrier preparation material to obtain a carrier I with a straight channel inside;
2) spraying a protective agent or a solution formed by the protective agent and a solvent on the outer surface of the carrier I, and then drying.
According to some embodiments of the catalyst carrier of the present invention, the carrier preparation material comprises carrier material powder and a binder material and water.
In the step 1), the carrier I having the straight channels therein can be produced by known extrusion molding and pelletizing. According to some embodiments, the carrier material powder is thoroughly mixed with the binder material and water, kneaded to form a plastic mass of carrier material, and the mass of carrier material is formed into a strip with a straight channel using an extrusion apparatus equipped with a corresponding die. And according to different number distributions of the straight channels of the carrier, corresponding dies are adopted during extrusion molding. And then, making the strip-shaped carrier material into a pill shape by using a granulator, and finally, rotationally shaping and rounding the pill-shaped particles to obtain a carrier blank. And drying and roasting the carrier embryo at high temperature to obtain the carrier I.
According to some embodiments of the catalyst support of the present invention, the solvent is a benign solvent of the protecting agent, preferably selected from alcohol solvents, ether solvents and halogenated hydrocarbon solvents, more preferably selected from ethanol, diethyl ether and chloroform.
According to some embodiments, the protective agent which is solid at room temperature needs to be dissolved by using a solvent such as ethanol, ether, chloroform, etc., and then sprayed after forming a protective agent solution. The spraying process can be completed by known spraying technology, the carrier I is put into a spraying cylinder, such as a sugar coating pan and a rotary pan, the carrier I is driven to continuously and slowly roll by the rotation of a round tube, the protective agent solution is sprayed on the surface of the carrier I by a spray gun, and simultaneously, hot air at 50-120 ℃ is introduced or the carrier I is heated by a heating cylinder, so that the solvent of the protective agent solution sprayed on the carrier I is heated and volatilized, and the protective agent is left on the outer surface of the carrier I to form a protective layer. Continuously spraying the protective agent solution until the required dosage of the protective agent is reached. And drying after the protective agent is sprayed, and further removing the solvent for dissolving the protective agent, thereby obtaining the catalyst carrier.
By using the catalyst carrier provided by the invention, a catalyst with non-uniform distribution of active components, which comprises a carrier with straight channels inside and platinum group metal active components distributed on the surfaces of the straight channels, can be prepared.
The catalyst with the active components distributed non-uniformly comprises a carrier with a straight channel inside and the platinum group metal active components, wherein the platinum group metal active components are preferably distributed on the surface of the straight channel in a thin layer mode, and the outer surface of the carrier does not contain the platinum group metal active components. The active components of the catalyst are distributed on the surface layer of the straight channel in the catalyst, and the platinum group metal active components are not contained on the outer surface of the catalyst sphere, so that the loss of noble metals caused by surface abrasion of the catalyst can be reduced.
According to some embodiments of the catalyst of the present invention, the platinum group metal active component is one or more selected from ruthenium, rhodium, osmium, platinum and palladium.
According to some embodiments of the catalyst of the present invention, the platinum group metal active component is present in an amount of 0.01 to 5.0%, preferably 0.05 to 3.0%, more preferably 0.05 to 1.0% by weight of the catalyst.
The preparation method of the catalyst with the active components distributed non-uniformly comprises the following steps:
the catalyst carrier according to the above or the catalyst carrier obtained by the above production method is impregnated in an aqueous solution of a compound containing a platinum-group metal element, followed by drying and calcination.
In the invention, the active component can be uniformly distributed in the catalyst due to the long impregnation time, which has little influence on the loss of the active component but can influence the reaction effect of the catalyst. According to some embodiments of the method for preparing a catalyst of the present invention, the impregnation time is 0.5 to 30 minutes, preferably 0.5 to 20 minutes, more preferably 0.5 to 15 minutes, and further preferably 1 to 10 minutes.
According to some embodiments of the process for preparing the catalyst of the present invention, the temperature of the impregnation is 15 to 90 ℃, preferably 40 to 90 ℃.
According to some embodiments of the method of preparing a catalyst of the present invention, the temperature of the drying is 90 to 150 ℃.
According to some embodiments of the method of preparing a catalyst of the present invention, the drying time is 1 to 24 hours.
According to some embodiments of the method of preparing a catalyst of the present invention, the calcination temperature is 300-800 ℃.
According to some embodiments of the method of preparing a catalyst of the present invention, the calcination time is 0.5 to 24 hours.
According to some embodiments of the method of preparing a catalyst of the present invention, the platinum group metal element-containing compound is selected from one or more of chloroplatinic acid, ammonium chloroplatinate, potassium chloroplatinate, platinum tetrabromide, platinum oxide, palladium chloride, palladium bromide, tetraamminepalladium dichloride, triruthenium dodecacarbonyl, rhodium trichloride, and ammonium hexachloroosmium.
According to some embodiments, the resulting catalyst support is impregnated in an aqueous solution containing a compound of a platinum-group metal element. The platinum group metal element compound may be any decomposable platinum group compound, for example, chloroplatinic acid, ammonium chloroplatinate, potassium chloroplatinate, platinum tetrabromide, platinum oxide, palladium chloride, palladium bromide, tetraamminepalladium dichloride, triruthenium dodecacarbonyl, rhodium trichloride, ammonium hexachloroosmium, and the like. The aqueous solution containing the platinum group metal may be an aqueous solution of one platinum group metal precursor, or a mixed aqueous solution of several platinum group metal precursors. The amount of the platinum group metal-containing aqueous solution is 1 to 2 times the bulk volume of the carrier. The impregnation may be carried out under a static condition or in a rotating vessel, and is preferably carried out under a static condition. The catalyst carrier is soaked in the water solution containing the platinum group metal for 0.5 to 10 minutes. The temperature of the dipping solution is between room temperature and 90 ℃. Due to the existence of the protective agent on the outer surface of the catalyst carrier, the precursor of the platinum group metal is not adsorbed on the outer surface of the carrier, but is adsorbed on the channel walls of the straight channels in the carrier. And then the selection of carrier materials and the control of the time for soaking the carrier in the platinum group metal aqueous solution are carried out, thereby controlling the active components to be distributed on the straight channel wall in the carrier in a thin layer. Taking out the catalyst carrier impregnated with the platinum group metal precursor, drying at 90-150 ℃ for 1-24 hours, and roasting at 300-800 ℃ for 0.5-24 hours to obtain the catalyst of which the outer surface does not contain platinum group metal and the straight channel in the spherical carrier is provided with the platinum group metal in a thin layer distribution.
Promoters or modifiers such as group IIIA-VA metals (e.g., tin) to improve the dispersion of the platinum group metal on the catalyst, and alkali and alkaline earth metals (e.g., lithium) to modulate the acidity of the support may be supported as desired. The cocatalyst or modifier for adjusting the acidity of the support can be added to the powder of the support material during the production of the spherical support I in step a). A promoter or modifier for improving the dispersion of the platinum group metal on the catalyst may be added to the aqueous platinum group metal solution in step c), and loaded onto the inner straight channel of the catalyst carrier together with the platinum group metal precursor.
The invention provides a method for producing unsaturated hydrocarbon by dehydrogenating saturated hydrocarbon, which comprises the step of carrying out selective oxidation reaction on hydrogen generated by dehydrogenating the saturated hydrocarbon in the presence of the catalyst with the active components distributed unevenly.
According to some embodiments of the method for producing unsaturated hydrocarbons by dehydrogenation of saturated hydrocarbons, the conditions of the selective oxidation reaction include a reaction temperature of 520--1。
According to some embodiments of the process for the dehydrogenation of a saturated hydrocarbon to produce an unsaturated hydrocarbon according to the present invention, the saturated hydrocarbon is selected from the group consisting of saturated aliphatic hydrocarbons and saturated aromatic hydrocarbons. The aromatic hydrocarbon may be ethylbenzene, diethylbenzene, methylethylbenzene, propylbenzene, etc., preferably ethylbenzene. The alkane may be C2-C16Of (2) a paraffin.
According to some embodiments, the present invention provides a catalyst for use in which a gas comprising dehydrogenated hydrocarbon, non-dehydrogenated hydrocarbon, hydrogen and steam from a dehydrogenation zone is passed into an oxidation zone, an oxygen-containing gas is passed into the oxidation zone to mix with the dehydrogenation zone effluent gas, and the two gases are mixed and contacted with the above-described catalyst having active components on the inner surface layer in the oxidation zone. The oxygen-containing gas includes oxygen, air, and oxygen diluted with an inert gas (e.g., water vapor, carbon dioxide, nitrogen, helium, argon, etc.) that does not react with oxygen or the aromatic hydrocarbon. The molar content of oxygen in the introduced oxygen-containing gas and the molar content of hydrogen flowing out of the dehydrogenation area are the molar ratio of hydrogen and oxygen in the hydrogen-oxygen reaction. In the oxidation zone, hydrogen is oxidatively combusted to produce water, while dehydrogenated hydrocarbons, non-dehydrogenated hydrocarbons are unaffected. The hydrogen-depleted gas exiting the oxidation zone may be passed to the next dehydrogenation zone for further dehydrogenation. The reactant gas may be passed repeatedly and alternately through the dehydrogenation zone and the oxidation zone as needed to achieve the desired ratio of dehydrogenated to non-dehydrogenated hydrocarbon.
The catalyst provided by the invention can be used for dehydrogenation and hydro-oxidation reactions of hydrocarbons, and can also be used for combustion purification reactions of waste gases containing hydrogen, carbon monoxide and low-carbon alkanes (such as methane and ethane). The catalyst can also be used for hydrogenation reaction, cracking reaction, dehydrogenation reaction and the like.
In the present invention, the term "normal temperature" or "room temperature" refers to a temperature within 10 to 30 ℃.
The invention changes the traditional non-uniformly distributed catalyst noble metal active component distribution on the outer surface of the catalyst into the active component concentrated distribution on the surface layer of the straight channel in the catalyst. The method comprises the steps of manufacturing a spherical carrier with a straight channel structure parallel to the axis of the sphere inside, preventing noble metal active component precursors from being adsorbed to the outer surface of the carrier to be loaded on the straight channel inside the carrier by spraying a protective agent on the outer surface of the carrier, and enabling the active components to be distributed on the straight channel wall in the carrier in a thin layer by controlling the time for soaking the noble metal aqueous solution. The catalyst with the outer surface free of platinum metals and the platinum metals distributed in a thin layer on the straight channel in the spherical carrier is obtained by the technical scheme, so that the problem of active component precious metal loss caused by catalyst surface abrasion possibly occurring in the transportation and use processes of the heterogeneous catalyst is solved.
Detailed Description
The present invention is further illustrated in detail by the following examples, which are not to be construed as limiting the invention.
Unless otherwise specified, each operation in examples and comparative examples was performed at room temperature.
Example 1
The gamma-alumina carrier Ai with the diameter of 4mm is internally provided with 3 straight channels with the diameter of 1mm, and the sum of the cross sections of the straight channels accounts for 19 percent of the maximum cross section area of the ball. 2 g of stearic acid is dissolved in 50 ml of ethanol to prepare a stearic acid solution, 100 g of the carrier Ai is put into a spraying rotary cylinder, and the stearic acid solution is sprayed on the surface of the tumbling carrier by a spray gun. And drying at 100 ℃ overnight after the protective agent is sprayed, thus obtaining the carrier Aii with the protective agent content accounting for 2% of the carrier mass.
Dissolving chloroplatinic acid in water to prepare a solution. The carrier Aii with the surface sprayed with the protective agent is put into a chloroplatinic acid solution with the same volume as the carrier at 40 ℃ for dipping, and is taken out after 5 minutes. Then drying at 120 deg.C for 4 hr, calcining at 600 deg.C for 6 hr, and cooling to obtain catalyst A whose external surface does not contain platinum and whose internal straight channel has platinum distributed in thin layer. Elemental analysis showed that the mass fraction of platinum in the catalyst was 0.20%.
The catalyst A was tested for attrition rate of 0.31% by the method of Standard HG/T2976-1999, and the powder abraded by the attrition rate test was collected and the mass fraction of platinum in the powder was determined to be 0.067% by elemental analysis. The loss rate of the active component platinum was 0.10%.
The hydrogen in the process of producing unsaturated aromatic styrene by selective oxidation of saturated aromatic ethylbenzene and dehydrogenation by using the catalyst A is carried out in a stainless steel reaction tube, and the filling amount is 30 mL. The molar contents of the raw materials for reaction are 2.4% of styrene, 5.4% of ethylbenzene, 0.08% of benzene and toluene, 2.4% of hydrogen, 1.1% of oxygen, 0.11% of nitrogen and 88.51% of water. The reaction temperature is 580 ℃, the reaction pressure is 100kPa, and the space velocity is 3h-1. The evaluation results are shown in Table 1.
Comparative example 1
Dissolving chloroplatinic acid in water to prepare a solution. 100 g of spherical gamma-alumina carrier A' i with the diameter of 4 is put into chloroplatinic acid solution with the same volume as the carrier at the temperature of 40 ℃ for dipping, and is taken out after 5 minutes. Then, the catalyst A ' is dried and calcined under the same conditions as the catalyst A, namely, the catalyst A ' is dried at 120 ℃ for 4 hours and then calcined at 600 ℃ for 6 hours to obtain the catalyst A '.
Analysis tests showed that the platinum content of catalyst A' was 0.20%, the attrition rate was 0.22%, and the platinum content in the attrited powder was 0.82%. The loss rate of the active component platinum was 0.90%.
The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 1.
Examples 2 to 6
The following five vectors exist:
the gamma-alumina carrier A-1i with the diameter of 2mm is internally provided with 1 straight channel with the diameter of 1.41mm, and the sectional area of the straight channel accounts for 50 percent of the maximum sectional area of the ball;
the delta-alumina carrier A-2i with the diameter of 4mm is internally provided with 7 straight channels with the diameter of 0.5mm, and the sum of the sectional areas of the straight channels accounts for 11 percent of the maximum sectional area of the sphere;
the delta-alumina and theta-alumina mixture carrier A-3i with the diameter of 6mm is internally provided with 4 straight channels with the diameter of 2mm, and the sum of the sectional areas of the straight channels accounts for 44 percent of the maximum sectional area of the ball;
the theta-alumina carrier A-4i with the diameter of 8mm is internally provided with 2 straight channels with the diameter of 2mm, and the sum of the sectional areas of the straight channels accounts for 13 percent of the maximum sectional area of the ball;
the molecular sieve carrier A-5i with the diameter of 10mm is internally provided with 3 straight channels with the diameter of 1.83mm, and the sum of the sectional areas of the straight channels accounts for 10 percent of the maximum sectional area of the ball.
Catalysts A-1, A-2, A-3, A-4 and A-5, each having an outer surface free from platinum and an inner straight channel in which platinum is distributed in a thin layer, were prepared in the same manner as in example 1.
Analysis tests show that the platinum contents of the catalysts A-1, A-2, A-3, A-4 and A-5 are respectively 0.21%, 0.22%, 0.18% and 0.20%; the abrasion rates are respectively 1.32%, 0.12%, 0.44%, 1.07% and 0.08%; the platinum content in the milled powder was 0.066%, 0.065%, 0.067%, 0.060%, respectively. The loss rates of the active component platinum were 0.41%, 0.04%, 0.13%, 0.40%, 0.02%, respectively.
The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 1.
Comparative example 2
Catalyst A-1' was prepared in the same manner as in comparative example 1, except that the carrier was changed to spherical gamma-alumina having a diameter of 2 mm.
The analysis test showed that the platinum content of catalyst A-1' was 0.20%, the attrition rate was 1.03%, and the platinum content in the abraded powder was 3.30%. The loss rate of the active component platinum was 17.0%.
The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 1.
Examples 7 to 10
The preparation method is the same as that of the example 1, except that the mass of the stearic acid serving as the protective agent is changed into 0.5 g, 1 g, 3.5 g and 5 g, and finally the prepared catalysts are respectively marked as B-1, B-2, B-3 and B-4.
Analysis and test show that the platinum contents of the catalysts B-1, B-2, B-3 and B-4 are respectively 0.20%, 0.21% and 0.20%; the abrasion rates are all 1.31%; the platinum content in the milled powder was 0.066%, 0.064%, 0.068%, 0.066%, respectively. The loss rates of the active component platinum were 0.10%, 0.09%, 0.10%, respectively.
The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 1.
Examples 11 to 17
The preparation method is the same as that of example 1, except that the protective agent and the solvent are changed into paraffin-carbon tetrachloride, palmitic acid-ethanol, eicosanoic acid-chloroform, lignoic acid-acetone, cetyl ether, dodecanol-ethanol and triglyceride-acetone, and finally the prepared catalysts are respectively marked as C-1, C-2, C-3, C-4, C-5, C-6 and C-7.
Analysis and test show that the platinum contents of the catalysts C-1, C-2, C-3, C-4, C-5, C-6 and C-7 are respectively 0.20%, 0.21%, 0.20%, 0.21% and 0.19%; the abrasion rates are all 0.31%; the platinum content in the milled powder was 0.066%, 0.064%, 0.068%, 0.066%, 0.067%, 0.065%, respectively. The loss rates of the active component platinum are respectively 0.10%, 0.09%, 0.10% and 0.11%.
The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 1.
Examples 18 to 23
The same preparation method as that of example 1, except that the precious metal precursor was changed to ammonium chloroplatinate, dodecacarbonyltriruthenium, hexachloroosmium ammonium, rhodium trichloride, potassium chloroplatinate, and palladium chloride, and the finally prepared precious metal catalysts were respectively labeled as platinum catalyst D-1, ruthenium catalyst D-2, osmium catalyst D-3, rhodium catalyst D-4, platinum catalyst D-5, and palladium catalyst D-6.
Analysis and test show that the noble metal contents of the catalysts D-1, D-2, D-3, D-4, D-5 and D-6 are respectively 0.21%, 0.20%, 0.21% and 0.19%; the abrasion rates are all 0.31%; the content of noble metal in the milled powder is 0.066%, 0.064%, 0.068%, 0.067% and 0.067% respectively. The loss rates of the active component platinum were 0.10%, 0.09%, 0.11%, 0.10%, 0.11%, respectively.
The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 1.
Examples 24 to 27
The preparation method of example 1 was used to obtain a protective agent-sprayed carrier Aii. And dissolving chloroplatinic acid in water to prepare a solution.
The carrier Aii was immersed in a chloroplatinic acid solution at a temperature of 1.5 times the volume of the carrier at room temperature for 0.5 minute and then taken out. Then drying at 150 ℃ for 1 hour, roasting at 550 ℃ for 12 hours, and cooling to obtain the catalyst E-1.
The carrier Aii was immersed in a chloroplatinic acid solution at 70 ℃ in an equal volume to the carrier for 2 minutes and then taken out. Then drying the catalyst at 90 ℃ for 24 hours, roasting the catalyst at 400 ℃ for 20 hours, and cooling the catalyst to obtain the catalyst E-2.
The carrier Aii was immersed in a chloroplatinic acid solution at 50 ℃ in a volume of 2 times the carrier volume, and taken out after 7 minutes. Then drying at 110 ℃ for 10 hours, roasting at 800 ℃ for 0.5 hour, and cooling to obtain the catalyst E-3.
The carrier Aii was immersed in a chloroplatinic acid solution at 90 ℃ in a volume 2 times that of the carrier, and taken out after 10 minutes. Then drying at 120 ℃ for 18 hours, roasting at 300 ℃ for 24 hours, and cooling to obtain the catalyst E-4.
Analysis and test show that the noble metal contents of the catalysts E-1, E-2, E-3 and E-4 are respectively 0.05%, 0.51%, 0.74% and 1.00%; the abrasion rates are all 0.31%; the content of noble metal in the milled powder is 0.017%, 0.161%, 0.225% and 0.323% respectively. The loss rates of the active component platinum were 0.11%, 0.10%, 0.09%, and 0.10%, respectively.
The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 1.
Example 28
Catalyst E' was prepared in the same manner as in example 1, except that the impregnation time of the chloroplatinic acid solution was changed to 30 minutes.
Analysis tests showed that the platinum content of catalyst E' was 0.20%, the attrition rate was 0.31%, and the platinum content in the attrited powder was 0.065%. The loss rate of the active component platinum was 0.10%.
The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 1.
Example 29
Catalyst E' was prepared in the same manner as in example 1 except that the impregnation time of the chloroplatinic acid solution was changed to 60 minutes.
Analytical tests showed that catalyst E "had a platinum content of 0.20%, an attrition rate of 0.31% and a platinum content of 0.063% in the attrited powder. The loss rate of the active component platinum was 0.10%.
The evaluation conditions were the same as in example 1, and the evaluation results are shown in Table 1.
TABLE 1
As can be seen from the results of the noble metal loss rates in the above examples and comparative examples, the catalyst having a non-uniform distribution of the active component according to the present invention in the inner surface layer structure is significantly superior to the catalyst having a non-uniform distribution of the conventional structure, and the noble metal loss can be controlled to a very low level. Therefore, compared with the traditional non-uniformly distributed catalyst, the catalyst with the active component in the inner surface layer structure has the characteristic of effectively reducing the loss rate of the noble metal.
Example 30
The hydrogen in the process of producing unsaturated aromatic styrene by dehydrogenating saturated aromatic ethylbenzene is carried out in a stainless steel reaction tube, and the catalyst A with 30mL of active components on the inner surface layer is filled. The molar contents of the raw materials for reaction are 2.4% of styrene, 5.4% of ethylbenzene, 0.08% of benzene and toluene, 2.4% of hydrogen, 1.1% of oxygen, 0.11% of nitrogen and 88.51% of water. The reaction conditions and the activity and selectivity results of the catalyst are listed in table 2.
TABLE 2
What has been described above is merely a preferred example of the present invention. It should be noted that other equivalent variations and modifications can be made by those skilled in the art based on the technical teaching provided by the present invention, and the protection scope of the present invention should be considered.
Claims (10)
1. A catalyst carrier having a straight channel in its interior and a protective agent coated on its outer surface, preferably, the catalyst carrier is spherical or spheroidal.
2. The catalyst carrier according to claim 1, wherein the protecting agent is selected from one or more of paraffin, palmitic acid, stearic acid, eicosanoic acid, lignitic acid, spermaceti, dodecanol and triglycerides; and/or the content of the protective agent accounts for 0.5-5% of the mass of the carrier; and/or the material of the support comprises at least one selected from gamma-alumina, delta-alumina, theta-alumina and molecular sieves.
3. The catalyst carrier according to claim 1 or 2, wherein the number of straight channels is preferably 2 or more, more preferably 2 to 10, parallel to the spherical axis of the carrier; and/or the diameter of the support is 2mm to 2cm, preferably 2mm to 1.5cm, more preferably 2mm to 1.2 cm; and/or the diameter of the straight channels is 0.1mm-3mm, preferably 0.5mm-2mm, and/or the sum of the cross-sectional areas of the straight channels in the largest cross-sectional area of the ball perpendicular to the straight channels is 5% -50%, preferably 10-50% of the largest cross-sectional area of the ball.
4. A method for producing a catalyst carrier according to any one of claims 1 to 3, comprising the steps of:
1) extruding, molding and dicing the carrier preparation material to obtain a carrier I with a straight channel inside;
2) spraying a protective agent or a solution formed by the protective agent and a solvent on the outer surface of the carrier I, and then drying.
5. The method according to claim 4, wherein the solvent is a benign solvent of the protecting agent, and is preferably selected from the group consisting of alcohol solvents, ether solvents and halogenated hydrocarbon solvents, and more preferably from the group consisting of ethanol, diethyl ether and chloroform.
6. A catalyst with non-uniform distribution of active components comprises a carrier with a straight channel inside and platinum group metal active components, wherein the platinum group metal active components are preferably distributed on the surface of the straight channel in a thin layer mode, the outer surface of the carrier does not contain the platinum group metal active components, and the carrier is preferably spherical or spheroidal.
7. A catalyst according to claim 6, wherein the platinum group metal active component is one or more selected from ruthenium, rhodium, osmium, platinum and palladium, preferably the platinum group metal active component is present in an amount of from 0.01 to 5.0%, preferably from 0.05 to 3.0%, more preferably from 0.05 to 1.0% by weight of the catalyst.
8. A preparation method of a catalyst with non-uniformly distributed active components comprises the following steps:
the catalyst carrier according to any one of claims 1 to 3 or the catalyst carrier obtained by the production method according to claim 4 or 5 is impregnated in an aqueous solution containing a platinum-group metal element compound, followed by drying and calcination.
9. The production method according to claim 8, wherein the time for the impregnation is 0.5 to 30 minutes, preferably 0.5 to 20 minutes, more preferably 0.5 to 15 minutes, further preferably 1 to 10 minutes; and/or the temperature of the impregnation is between 15 and 90 ℃, preferably between 40 and 90 ℃; and/or the drying temperature is 90-150 ℃, and the drying time is 1-24 hours; and/or the roasting temperature is 300-800 ℃, and the roasting time is 0.5-24 hours; and/or the platinum group metal element-containing compound is selected from one or more of chloroplatinic acid, ammonium chloroplatinate, potassium chloroplatinate, platinum tetrabromide, platinum oxide, palladium chloride, palladium bromide, palladium tetraammine dichloride, triruthenium dodecacarbonyl, rhodium trichloride and ammonium hexachloroosmium.
10. A method for producing unsaturated hydrocarbon by dehydrogenating saturated hydrocarbon, which comprises subjecting hydrogen generated by dehydrogenating saturated hydrocarbon to selective oxidation reaction in the presence of the catalyst of claim 6 or 7, preferably, the conditions of the selective oxidation reaction comprise reaction temperature of 520 ℃ and 650 ℃, reaction pressure of 20-200KPa and liquid reaction space velocity of 0.1-10h-1。
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| CN201910926417.3A CN112569917A (en) | 2019-09-27 | 2019-09-27 | Catalyst carrier, catalyst and method for producing unsaturated hydrocarbon by dehydrogenating saturated hydrocarbon |
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