CN113968767A - Method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane - Google Patents
Method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane Download PDFInfo
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- CN113968767A CN113968767A CN202010720176.XA CN202010720176A CN113968767A CN 113968767 A CN113968767 A CN 113968767A CN 202010720176 A CN202010720176 A CN 202010720176A CN 113968767 A CN113968767 A CN 113968767A
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- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 107
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 94
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 208
- 239000001257 hydrogen Substances 0.000 claims abstract description 67
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 67
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 61
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 230000008569 process Effects 0.000 claims abstract description 39
- 239000003085 diluting agent Substances 0.000 claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 104
- 238000006243 chemical reaction Methods 0.000 claims description 96
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 48
- 238000010335 hydrothermal treatment Methods 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 36
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 30
- 230000009467 reduction Effects 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 14
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 230000002829 reductive effect Effects 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- -1 olefin hydrocarbon Chemical class 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 54
- 239000000243 solution Substances 0.000 description 51
- 239000003921 oil Substances 0.000 description 41
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 24
- 238000010438 heat treatment Methods 0.000 description 23
- 229910001220 stainless steel Inorganic materials 0.000 description 21
- 239000010935 stainless steel Substances 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 20
- 239000002994 raw material Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000010453 quartz Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 230000000536 complexating effect Effects 0.000 description 15
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical compound O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 238000004364 calculation method Methods 0.000 description 11
- 238000012512 characterization method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 11
- 229910052753 mercury Inorganic materials 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 239000008188 pellet Substances 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 238000005485 electric heating Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000005086 pumping Methods 0.000 description 8
- 150000004687 hexahydrates Chemical class 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- VXJIMUZIBHBWBV-UHFFFAOYSA-M lithium;chloride;hydrate Chemical compound [Li+].O.[Cl-] VXJIMUZIBHBWBV-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229910052680 mordenite Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- B01J35/615—
-
- B01J35/638—
-
- B01J35/647—
-
- 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
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/58—Platinum group metals with alkali- or alkaline earth metals or beryllium
-
- 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
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
Abstract
The invention provides a method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane, which comprises the steps of reacting the long-chain alkane with a dehydrogenation catalyst to prepare the long-chain olefin; wherein the long-chain alkane is reacted in the presence of a diluent which is a mixture of hydrogen and water vapor. The process can reduce the circulation amount of hydrogen and improve the safety of the process. The test result shows that the catalyst has higher activity and stability under the process condition at the same temperature.
Description
Technical Field
The invention relates to the technical field of catalytic dehydrogenation, and comprises a method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane.
Background
The long-chain alkane and the derivatives thereof have very important position in the petrochemical industry, and the product of the dehydrogenation reaction of the long-chain alkane can generate alkylbenzene sulfonate through the subsequent alkylation and sulfonation processes. Alkyl benzene sulfonate is the main component of anionic surfactant and is widely used in producing detergent, emulsifier and other products. Long-chain alpha olefin generated by dehydrogenation reaction of long-chain alkane can be used as lubricating oil base oil to generate poly-alpha olefin synthetic oil through oligomerization and hydrogenation saturation processes. The performance of the long-chain alkane dehydrogenation catalyst determines the yield and quality of the products to a certain extent, so that the research on the long-chain alkane dehydrogenation catalyst and the reaction process thereof has very important significance. The existing long-chain alkane dehydrogenation catalysts are mainly divided into platinum catalysts and chromium catalysts, and because the chromium catalysts are easy to generate heavy metal pollution in the using process of the chromium catalysts, the application of the chromium catalysts is strictly limited, people concentrate on the research of the long-chain alkane catalysts on the platinum catalysts, and the currently commercialized long-chain alkane dehydrogenation catalysts also mainly use the platinum catalysts.
At present, the long-chain alkane dehydrogenation catalysts which are more applied at home mainly comprise DEH type catalysts of UOP company and domestic NDC and DF type catalysts. The catalysts take alumina as a carrier and Pt as a main active component, and have better activity and stability. On the basis, people improve the catalyst in many aspects, so that the performance of the catalyst is improved, and a plurality of related reports are provided at home and abroad.
CN 104248982A discloses a preparation method of a long-chain alkane dehydrogenation catalyst carrier, wherein a lanthanum nitrate solution is added in the process of preparing an alumina pellet by a sol-gel method, the obtained alumina has the advantages of large pore volume, proper surface area, high strength and the like, and the catalyst prepared by using the carrier has higher activity and stability in an evaluation experiment; CN 104492407A improves the process of preparing alumina carrier by sol-gel method, ammonia water containing surfactant is added in the forming process, the catalyst prepared by the carrier can obviously improve the conversion rate of alkane when applied to dehydrogenation reaction of long-chain alkane; US400021 uses cationic mordenite as a carrier, Pt is loaded on the cationic mordenite, and organic base is used as a modifier to improve the selectivity of a target product; US 3903191 discloses a method for preparing a catalyst, which changes the type of a supported component, wherein the components comprise platinum, rhenium and alkali metal or alkaline earth metal elements, and the catalyst prepared by the method can improve the selectivity of long-chain alpha olefin. The prior art mentioned above covers various aspects of the carrier, the active component, the catalyst preparation method, etc., which all improve the performance of the long-chain alkane dehydrogenation catalyst to some extent, but because the influence factors of the performance of the long-chain alkane dehydrogenation catalyst are numerous and cannot be met, the existing long-chain alkane dehydrogenation catalyst still has room for improvement.
In terms of production process, the UOP company designs and develops a complete set of processes, including kerosene fractionation, dehydrogenation of long-chain alkanes, separation of aromatic hydrocarbons, and alkylation processes, most typically. The alkylbenzene produced by applying the technology can reach 70% of the total production worldwide, the Pacol technology is adopted in the dehydrogenation process of the long-chain alkane, the technology adopts hydrogen as a diluent, and a part of products enter the reactor again through a circulating unit to react to obtain higher olefin yield. In the dehydrogenation process of the long-chain alkane, hydrogen is used as a diluent, so that the conversion rate of reactants can be controlled within an ideal range, side reactions such as carbon deposit and the like are inhibited, and the service life of the catalyst is obviously prolonged. However, the recycling of hydrogen needs the support of matching equipment such as a compressor, and a large amount of hydrogen will increase the load of the equipment.
Disclosure of Invention
The invention mainly aims to provide a method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane, which is suitable for the long-chain alkane of C2-C30, in particular for the straight-chain alkane of C10-C14, and in the method, the catalyst can show higher activity and stability at the same temperature.
In order to achieve the purpose, the invention provides a method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane, wherein the long-chain alkane is reacted under the catalysis of a dehydrogenation catalyst to prepare the long-chain olefin; wherein the long-chain alkane is reacted in the presence of a diluent which is a mixture of hydrogen and water vapor.
The method for preparing the long-chain olefin by catalytic dehydrogenation of the long-chain alkane, disclosed by the invention, is characterized in that the long-chain alkane has 2-30 carbons; the reaction temperature is 400-600 ℃, and the reaction pressure is 0.1-1 MPa; and/or the total space velocity of the long-chain alkane and the diluent is 1000-15000 h-1。
The method for preparing the long-chain olefin by catalytic dehydrogenation of the long-chain alkane, disclosed by the invention, is characterized in that the volume ratio of hydrogen to the long-chain alkane in the diluent is 10-150: 1, the molar ratio of water vapor to long-chain alkane in the diluent is 2-15.
The method for preparing the long-chain olefin by catalytic dehydrogenation of the long-chain alkane, disclosed by the invention, is characterized in that the dehydrogenation catalyst needs to be reduced before participating in the reaction, the reduction temperature is 400-600 ℃, and the reduction time is 2-8 hours.
The invention relates to a method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane, wherein, the dehydrogenation catalyst takes alumina as a carrier, precious metal as an active component and one or more of IVA group elements and alkali metal elements as an auxiliary agent; based on the total mass of the dehydrogenation catalyst, the content of the active component in terms of metal is 0.1-5%, and the content of the auxiliary agent in terms of elements is 0.1-8.0%; the specific surface area of the dehydrogenation catalyst is 100-200 m2The pore volume is 0.5-1.5 mL/g.
The method for preparing the long-chain olefin by catalytic dehydrogenation of the long-chain alkane comprises the following steps of (1) preparing an active component, wherein the active component is one or more of platinum, palladium and rhodium, and the content of the active component is 0.1-3% in terms of metal; the IVA group elements are one or more of germanium, tin and lead, and the content of the IVA group elements is 0.3 to 5 percent in terms of metal; the alkali metal elements are one or more of lithium, sodium, potassium and rubidium, and the content of the alkali metal elements is 0.1-3% in terms of metal; and/or the molar ratio of the group IVA element to the active component is 1:1 to 5:1 in terms of metal.
The invention relates to a method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane, wherein the preparation method of the dehydrogenation catalyst comprises the following steps: preparing an active component precursor into impregnation liquid, impregnating the alumina carrier in vacuum, and then drying and roasting to obtain the dehydrogenation catalyst.
The method for preparing the long-chain olefin by catalytic dehydrogenation of the long-chain alkane, disclosed by the invention, comprises the following hydrothermal treatment step before the alumina carrier is impregnated, wherein the hydrothermal treatment conditions are as follows: the hydrothermal treatment temperature is 500-1000 ℃, the hydrothermal treatment time is 1-30 h, and the total gas space velocity in the hydrothermal treatment process is 200-5000 h-1(ii) a The volume content of water vapor in the gas is 10-100%, and the balance is air or nitrogen.
The long-chain alkane catalysis of the inventionThe method for preparing the long-chain olefin by dehydrogenation comprises the following steps of roasting the impregnated and dried dehydrogenation catalyst under the condition of introducing air at a certain space velocity; the air airspeed is 600-5000 h-1The roasting temperature is 400-1000 ℃, and the roasting time is 1-20 h.
The method for preparing the long-chain olefin by catalytic dehydrogenation of the long-chain alkane further comprises the step of adding an auxiliary agent, wherein the auxiliary agent is impregnated with the precursor of the active component in a precursor form.
The invention has the beneficial effects that:
the invention provides a method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane, which uses a mixture of hydrogen and steam as a diluent, can inhibit the generation of catalyst carbon deposit, improve the activity and stability of the catalyst, and simultaneously can reduce the usage amount of hydrogen. The water vapor is easy to obtain, so that accidents such as explosion and the like can not occur in the using process, and the safety in the chemical production process is greatly improved; the dehydrogenation method disclosed by the invention has the advantage that the dehydrogenation process disclosed by the invention can maximally show unique action effect by cooperating with the preferred catalyst and the preparation method.
Detailed Description
The following examples of the present invention are described in detail, and the present invention is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and procedures are given, but the scope of the present invention is not limited to the following examples, and the following examples are experimental methods without specific conditions noted, and generally follow conventional conditions.
The invention provides a method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane, in particular to a method for preparing long-chain alpha monoolefin by catalytic dehydrogenation of long-chain normal alkane, which comprises the following steps: reacting long-chain alkane with a dehydrogenation catalyst to prepare long-chain alkene; wherein the long-chain alkane is reacted in the presence of a diluent which is a mixture of hydrogen and water vapor.
The dehydrogenation reaction is limited by thermodynamic equilibrium, generally is carried out at high temperature and low pressure, and the catalyst is easy to coke, so that the conversion rate of reactants is controlled in an ideal range by adopting hydrogen as a diluent in the dehydrogenation process of the long-chain alkane, side reactions such as carbon deposit generation and the like are inhibited, and the service life of the catalyst is obviously prolonged.
However, the product of the dehydrogenation reaction contains hydrogen, and the addition of hydrogen during the reaction is not favorable for the dehydrogenation reaction in terms of chemical reaction balance. Meanwhile, the recycling of hydrogen needs the support of matching equipment such as a compressor and the like, and a large amount of hydrogen will increase the load of the equipment.
The present inventors have found that the use of a mixture of hydrogen and water vapor as a diluent can suppress the generation of carbon deposit, improve the activity and stability of the catalyst, and reduce the amount of hydrogen used. The steam is easy to obtain, accidents such as explosion and the like can not occur in the using process, and the safety in the chemical production process is greatly improved.
In detail, water vapor is used as a diluent instead of part of hydrogen, so that the partial pressure of hydrogen can be reduced, and the conversion rate of alkane catalytic dehydrogenation reaction can be improved. Under the condition of hydrogen-steam dilution, the water steam can remove Cl in the catalyst-And the acidity of the carrier is reduced, and the generation of carbon deposited on the surface of the catalyst is reduced; in addition, the steam can react with partial coke under high temperature condition to gasify the coke, thereby eliminating partial carbon deposit and improving the stability of the catalyst. Moreover, the steam has an inhibiting effect on the dehydrocyclization reaction of the alkane, and the side reaction can be reduced.
In one embodiment, the long-chain alkane of the present invention uses a mixture of hydrogen and water vapor as a diluent during feeding, and provides an optimal ratio relationship, i.e., a hydrogen-oil volume ratio (volume ratio of hydrogen to long-chain alkane) is 10 to 150, preferably 20 to 60, and a water-oil molar ratio (mole ratio of water vapor to long-chain alkane) is 2 to 15, preferably 3 to 10. If the steam amount is lower, the reduction amount of hydrogen is not obvious, and the dehydrogenation reaction activity is not obviously improved; too high a water vapor amount causes the crystal grains of the active component of the catalyst to grow due to the coagulation, resulting in a decrease in activity.
In one embodiment, the above dehydrogenation reactionThe method is carried out in a fixed bed reactor, the reaction temperature is 400-600 ℃, the reaction pressure is 0.1-1 MPa, and the total gas space velocity is 1000-15000 h-1Preferably 5000 to 10000h-1。
In one embodiment, the long-chain alkane of the present invention is a normal alkane having 2 to 30 carbons, particularly a normal alkane having 10 to 14 carbons.
The dehydrogenation catalyst of the present invention needs to be reduced before participating in the reaction, and the reduction can be in-situ reduction or ex-situ reduction, and an in-situ reduction method is recommended. The reducing conditions are related to the specific composition of the catalyst, the invention is not particularly limited, and the recommended reducing conditions are: the reduction temperature is 400-600 ℃, and the reduction time is 2-8 h.
The catalyst used in the present invention is a dehydrogenating catalyst capable of being hydrogenated, such as a noble metal catalyst which is generally used, particularly a noble metal catalyst using alumina as a carrier.
In order to have a better synergistic effect with the above process conditions, the invention particularly recommends a dehydrogenation catalyst composition: the dehydrogenation catalyst takes alumina as a carrier, precious metal as an active component and one or more of IVA group elements and alkali metal elements as an auxiliary agent; based on the total mass of the dehydrogenation catalyst, the content of the active component is 0.1-5%, and the content of the auxiliary agent is 0.1-8.0%.
In one embodiment, the noble metal as the active component in the catalyst of the invention is one or more of platinum, palladium and rhodium, preferably platinum; based on the total mass of the dehydrogenation catalyst, the content of the active component is 0.1-3%. The IVA group element is one or more of germanium, tin and lead, preferably tin; based on the total mass of the dehydrogenation catalyst, the content of the IVA group elements is 0.3-5%. The alkali metal element is one or more of lithium, sodium, potassium and rubidium, preferably lithium; the content of alkali metal is 0.1-3% based on the total mass of the dehydrogenation catalyst.
In another embodiment, the active component of the present invention is platinum, the content of which is 0.2% to 0.5%, preferably 0.3% to 0.5%, calculated as metal, the promoter includes Sn, the content of which is 0.1% to 1.0%, preferably 0.5% to 0.7%, calculated as metal, and the promoter further includes alkali metal, the content of which is 0.1% to 2.0%, preferably 0.5% to 0.7%, calculated as metal, based on the total mass of the dehydrogenation catalyst.
In another embodiment, the mole ratio of the group IVA element to the active component in the dehydrogenation catalyst of the present invention, calculated as the metal, is from 1:1 to 5: 1.
In one embodiment, the present invention provides a method for preparing the above dehydrogenation catalyst, which comprises a catalyst support and an active component, and can be prepared by a general impregnation method. The preparation of the catalyst carrier by the vacuum impregnation method is characterized in that the impregnation liquid prepared from a precursor containing an active component is loaded on the catalyst carrier by impregnation or equal-volume impregnation.
In one embodiment, the catalyst support of the present invention is alumina, more preferably modified alumina. Modified alumina refers to hydrothermal treatment of an alumina carrier. The conditions recommended for the hydrothermal treatment were: the hydrothermal treatment temperature is 500-1000 ℃, and preferably 600-800 ℃; the time of the hydrothermal treatment is 1-30 h, preferably 2-10 h; the total air speed of the gas in the hydrothermal treatment process is 200-5000 h-1Preferably 1000 to 2000 hours-1. Wherein the volume content of water vapor in the gas is 10-100%, preferably 30-70%, and the balance is air or nitrogen, preferably nitrogen.
The specific surface area of the alumina carrier after the hydrothermal treatment by adopting the hydrothermal treatment method is 100-200 m2The pore volume is 0.5-1.5 mL/g. The alumina carrier subjected to hydrothermal treatment has the advantages that the specific surface area is reduced, the pore volume and the pore diameter are increased, more places can be provided for carbon deposition migration, and the stability of the catalyst can be further improved by combining the recommended catalyst composition; in addition, the catalyst of the present invention can be promoted to act synergistically with the dehydrogenation process of the present invention, making the catalyst more suitable for the specific dehydrogenation process of the present invention.
The method for adding the auxiliary to the catalyst is not particularly limited in the method for preparing the catalyst of the present invention. The precursor of the auxiliary agent can be simultaneously impregnated with the precursor of the active component, or can be separately and independently impregnated, or the auxiliary agent can be added into the carrier.
The catalyst carrier loaded with the active component is dried at the temperature of 80-200 ℃, preferably 110-150 ℃, and the drying time is 5-24 hours, preferably 6-15 hours. And then roasting at the roasting temperature of 400-1000 ℃, preferably 500-650 ℃, for 1-20 h, preferably 3-10 h.
In one embodiment, the present invention provides a firing method comprising: roasting the impregnated and dried catalyst under the condition of introducing air at a certain airspeed, wherein the airspeed of the air is 600-5000 h-1Preferably 1500 to 3000 hours-1The roasting temperature is 400-1000 ℃, preferably 500-650 ℃, and the roasting time is 1-20 hours, preferably 3-10 hours.
In the prior art, the impregnated catalyst is usually calcined in a closed or normal air environment. The inventors have surprisingly found that the introduction of air during the firing process at a certain space velocity gives unexpected results. Firstly, the oxygen content is different when static air roasting and flowing air roasting are carried out, and the content of oxidation state metal is influenced; secondly, the flow rate of gas generated by decomposing water vapor, volatile components and the catalyst active component precursor in static air is low, and the gas and the volatile components such as the water vapor generated by decomposing the catalyst active component precursor in flowing atmosphere are quickly taken away, so that the decomposition of the active component precursor is facilitated; in addition, the heat dissipation effect in the flowing air atmosphere is better.
The technical solution of the present invention is further illustrated by the following specific examples. The following examples and comparative examples use platinum as the active component, tin and alkali metal as the auxiliary agent, and alumina as the carrier, but the invention is not limited thereto, and other noble metal catalysts in the prior art can be used in the method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane.
Example 1
100ml of alumina pellets prepared by an oil ammonia column molding process were placed in a quartz tube reactor. HeadFirstly heating to 700 ℃ in nitrogen atmosphere at a heating rate of 10 ℃/min, wherein the space velocity of nitrogen is 1500h-1. Then, introducing water vapor into the quartz tube reactor, and reducing the flow of nitrogen gas to ensure that the volume content of the water vapor reaches 50 percent and the total gas space velocity is 1500h-1. Under the condition, after the alumina carrier is treated for 5 hours, the water vapor is stopped from being added, and the alumina carrier is enabled to have space velocity of 750 hours-1Naturally cooling the mixture to room temperature in nitrogen for later use.
0.204g of stannous chloride dihydrate was weighed into a 100ml beaker, and then dissolved by adding 1ml of 37% concentrated hydrochloric acid. Then, 0.161g of chloroplatinic acid hexahydrate was added to the above solution containing Sn, and stirred to dissolve the chloroplatinic acid and form a uniform complex solution with Sn. The above complexing solution was diluted to 20ml with deionized water. 0.864g of lithium chloride monohydrate was weighed out and added to the above solution, and stirred to dissolve it. 20g of the alumina carrier treated by the water vapor is weighed and placed in a vacuum impregnator, and the vacuum degree is up to 50mbar by starting a vacuum pump for vacuum pumping. Adding the complexing solution into a vacuum impregnator, and stirring to ensure that the solution is fully absorbed by an alumina carrier. The composition of the obtained catalyst is 0.3% of platinum, 0.53% of tin, 0.49% of lithium and the balance of alumina carrier (the catalyst composition is calculated by weight percent).
The alumina absorbing the active components is dried in an electric heating air blast drying oven. The drying temperature is 120 ℃, and the drying time is 10 h.
20ml of alumina which is impregnated with active components and dried is placed in the middle of a stainless steel reactor at a space velocity of 2000h-1Heating the mixture to 550 ℃ in air flow, and keeping the temperature for 5 hours to decompose the active component precursor to obtain the finished catalyst.
2ml of the calcined catalyst is placed in a stainless steel reactor, and the temperature and the hydrogen airspeed are controlled at 500 ℃ for 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Dodecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material dodecane to contact with a catalyst, and the total space velocity of gas is kept at 7500h in the reaction process-1Hydrogen oil bodyThe volume ratio is 50, and the water-oil molar ratio is 4. The evaluation results are shown in table 1. The sample characterization data are shown in Table 2, wherein the specific surface is represented by N2The pore volume and the pore diameter are measured by a mercury intrusion method through a BET calculation method by a low-temperature physical adsorption method.
Example 2
100ml of alumina pellets prepared by an oil ammonia column molding process were placed in a quartz tube reactor. Firstly, heating to 600 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, wherein the airspeed of nitrogen is 1500h-1. Then, introducing water vapor into the quartz tube reactor, and reducing the flow of nitrogen gas to ensure that the volume content of the water vapor reaches 70 percent and the total gas space velocity is 1500h-1. Under the condition, after the alumina carrier is treated for 10 hours, the water vapor is stopped from being added, and the alumina carrier is enabled to have space velocity of 750 hours-1Naturally cooling the mixture to room temperature in nitrogen for later use.
0.205g of stannous chloride dihydrate was weighed into a 100ml beaker, and then dissolved by adding 1ml of 37% concentrated hydrochloric acid. Then, 0.269g of chloroplatinic acid hexahydrate was added to the above solution containing Sn, and stirred to dissolve the chloroplatinic acid and form a uniform complex solution with Sn. The above complexing solution was diluted to 20ml with deionized water. 0.866g of lithium chloride monohydrate was weighed out and added to the above solution, followed by stirring to dissolve it. 20g of the alumina carrier treated by the water vapor is weighed and placed in a vacuum impregnator, and the vacuum degree is up to 50mbar by starting a vacuum pump for vacuum pumping. Adding the complexing solution into a vacuum impregnator, and stirring to ensure that the solution is fully absorbed by an alumina carrier. The composition of the obtained catalyst is 0.5% of platinum, 0.53% of tin, 0.49% of lithium and the balance of alumina carrier (the catalyst composition is calculated by weight percent).
The alumina absorbing the active components is dried in an electric heating air blast drying oven. The drying temperature is 120 ℃, and the drying time is 10 h.
20ml of alumina which is impregnated with active components and dried is placed in the middle of a stainless steel reactor at a space velocity of 2000h-1Heating to 650 ℃ in the air flow, and keeping for 3h to decompose the active component precursor to obtain the finished catalyst.
2ml of the calcined catalyst is placed in a stainless steel reactor500 ℃ and the hydrogen space velocity of 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Dodecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material dodecane to contact with a catalyst, and the total space velocity of gas is kept at 5000h in the reaction process-1The hydrogen-oil volume ratio was 20 and the water-oil molar ratio was 8. The evaluation results are shown in table 1. The sample characterization data are shown in Table 2, wherein the specific surface is represented by N2The pore volume and the pore diameter are measured by a mercury intrusion method through a BET calculation method by a low-temperature physical adsorption method.
Example 3
100ml of alumina pellets prepared by an oil ammonia column molding process were placed in a quartz tube reactor. Firstly, heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, wherein the airspeed of nitrogen is 1500h-1. Then, introducing water vapor into the quartz tube reactor, and reducing the flow of nitrogen gas to ensure that the volume content of the water vapor reaches 50 percent and the total gas space velocity is 1500h-1. Under the condition, after the alumina carrier is treated for 2 hours, the water vapor is stopped from being added, and the alumina carrier is enabled to have space velocity of 750 hours-1Naturally cooling the mixture to room temperature in nitrogen for later use.
0.251g of stannous chloride dihydrate was weighed into a 100ml beaker, and then dissolved by adding 1ml of 37% concentrated hydrochloric acid. Then, 0.162g of chloroplatinic acid hexahydrate is added into the Sn-containing solution, and the mixture is stirred to dissolve the chloroplatinic acid and form a uniform complex solution with Sn. The above complexing solution was diluted to 20ml with deionized water. 0.232g of potassium chloride was weighed out and added to the above solution, followed by stirring to dissolve it. 20g of the alumina carrier treated by the water vapor is weighed and placed in a vacuum impregnator, and the vacuum degree is up to 50mbar by starting a vacuum pump for vacuum pumping. Adding the complexing solution into a vacuum impregnator, and stirring to ensure that the solution is fully absorbed by an alumina carrier. The composition of the obtained catalyst was 0.3% of platinum, 0.65% of tin and 0.6% of potassium (the composition of the catalyst is in weight percent).
The alumina absorbing the active components is dried in an electric heating air blast drying oven. The drying temperature is 120 ℃, and the drying time is 10 h.
20ml of alumina which is impregnated with active components and dried is placed in the middle of a stainless steel reactor at a space velocity of 3000h-1Heating the mixture to 550 ℃ in air flow, and keeping the temperature for 5 hours to decompose the active component precursor to obtain the finished catalyst.
2ml of the calcined catalyst is placed in a stainless steel reactor, and the temperature and the hydrogen airspeed are controlled at 500 ℃ for 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Dodecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material dodecane to contact with a catalyst, and the total space velocity of gas is kept at 7500h in the reaction process-1The hydrogen-oil volume ratio was 80 and the water-oil molar ratio was 3. The evaluation results are shown in table 1. The sample characterization data are shown in Table 2, wherein the specific surface is represented by N2The pore volume and the pore diameter are measured by a mercury intrusion method through a BET calculation method by a low-temperature physical adsorption method.
Example 4
100ml of alumina pellets prepared by an oil ammonia column molding process were placed in a quartz tube reactor. Firstly, heating to 900 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, wherein the space velocity of nitrogen is 1500h-1. Then, introducing water vapor into the quartz tube reactor, and reducing the flow of nitrogen gas to ensure that the volume content of the water vapor reaches 30 percent and the total gas space velocity is 1500h-1. Under the condition, after the alumina carrier is treated for 8 hours, the water vapor is stopped from being added, and the alumina carrier is enabled to have space velocity of 750 hours-1Naturally cooling the mixture to room temperature in nitrogen for later use.
0.309g of stannous chloride dihydrate was weighed into a 100ml beaker, and then dissolved by adding 1ml of 37% concentrated hydrochloric acid. Then, 0.162g of chloroplatinic acid hexahydrate is added into the Sn-containing solution, and the mixture is stirred to dissolve the chloroplatinic acid and form a uniform complex solution with Sn. The above complexing solution was diluted to 20ml with deionized water. 0.258g of sodium chloride was weighed, added to the above solution, and stirred to dissolve it. 20g of the alumina carrier treated by the water vapor is weighed and placed in a vacuum impregnator, and the vacuum degree is up to 50mbar by starting a vacuum pump for vacuum pumping. Adding the complexing solution into a vacuum impregnator, and stirring to ensure that the solution is fully absorbed by an alumina carrier. The composition of the obtained catalyst was 0.3% of platinum, 0.8% of tin and 0.5% of sodium (the composition of the catalyst is in weight percent).
The alumina absorbing the active components is dried in an electric heating air blast drying oven. The drying temperature is 120 ℃, and the drying time is 10 h.
20ml of alumina which is impregnated with active components and dried is placed in the middle of a stainless steel reactor at a space velocity of 2500h-1Heating the mixture to 700 ℃ in air flow, and keeping the temperature for 5 hours to decompose the active component precursor to obtain the finished catalyst.
2ml of the calcined catalyst is placed in a stainless steel reactor, and the temperature and the hydrogen airspeed are controlled at 500 ℃ for 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Dodecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material dodecane to contact with a catalyst, and the total gas space velocity is kept to be 6500h in the reaction process-1The hydrogen-oil volume ratio was 20, and the water-oil molar ratio was 5. The evaluation results are shown in table 1. The sample characterization data are shown in Table 2, wherein the specific surface is represented by N2The pore volume and the pore diameter are measured by a mercury intrusion method through a BET calculation method by a low-temperature physical adsorption method.
Example 5
100ml of alumina pellets prepared by an oil ammonia column molding process were placed in a quartz tube reactor. Firstly, heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, wherein the airspeed of nitrogen is 1000h-1. Then, introducing water vapor into the quartz tube reactor, and reducing the flow of nitrogen gas to ensure that the volume content of the water vapor reaches 60 percent and the total gas space velocity is 1000h-1. Under the condition, after the alumina carrier is treated for 8 hours, the water vapor is stopped from being added, and the alumina carrier is enabled to have space velocity of 750 hours-1Naturally cooling the mixture to room temperature in nitrogen for later use.
0.252g of stannous chloride dihydrate was weighed into a 100ml beaker, and then dissolved by adding 1ml of 37% concentrated hydrochloric acid. Then 0.17g of palladium chloride is added into the Sn-containing solution, and the palladium chloride is dissolved by stirring to form a uniform complex solution with Sn. The above complexing solution was diluted to 20ml with deionized water. 0.519 sodium chloride was weighed out and added to the above solution, and dissolved by stirring. 20g of the alumina carrier treated by the water vapor is weighed and placed in a vacuum impregnator, and the vacuum degree is up to 50mbar by starting a vacuum pump for vacuum pumping. Adding the complexing solution into a vacuum impregnator, and stirring to ensure that the solution is fully absorbed by an alumina carrier. The composition of the obtained catalyst is 0.5 percent of palladium, 0.65 percent of tin, 1.0 percent of sodium and the balance of alumina carrier (the composition of the catalyst is calculated by weight percentage).
The alumina absorbing the active components is dried in an electric heating air blast drying oven. The drying temperature is 120 ℃, and the drying time is 10 h.
20ml of alumina which is impregnated with active components and dried is placed in the middle of a stainless steel reactor at a space velocity of 1500h-1Heating to 600 ℃ in the air flow, and keeping for 8h to decompose the active component precursor to obtain the finished catalyst.
2ml of the calcined catalyst is placed in a stainless steel reactor, and the temperature and the hydrogen airspeed are controlled at 500 ℃ for 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Dodecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material dodecane to contact with a catalyst, and the total space velocity of gas is kept 8000h in the reaction process-1The hydrogen-oil volume ratio was 50, and the water-oil molar ratio was 10. The evaluation results are shown in table 1. The sample characterization data are shown in Table 2, wherein the specific surface is represented by N2The pore volume and the pore diameter are measured by a mercury intrusion method through a BET calculation method by a low-temperature physical adsorption method.
Example 6
100ml of alumina pellets prepared by an oil ammonia column molding process were placed in a quartz tube reactor. Firstly, heating to 700 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, wherein the space velocity of nitrogen is 2000h-1. Then, introducing water vapor into the quartz tube reactor, and reducing the flow of nitrogen gas to ensure that the volume content of the water vapor reaches 30 percent and the total gas space velocity is 2000h-1. Under the condition, the alumina is addedAfter the carrier is treated for 10h, the water vapor is stopped adding, and the alumina carrier is led to have space velocity of 750h-1Naturally cooling the mixture to room temperature in nitrogen for later use.
0.253g of stannous chloride dihydrate is weighed into a 100ml beaker and then dissolved by adding 1ml of 37% concentrated hydrochloric acid. Then, 0.163g of chloroplatinic acid hexahydrate was added to the above solution containing Sn, and stirred to dissolve the chloroplatinic acid and form a uniform complex solution with Sn. The above complexing solution was diluted to 20ml with deionized water. 0.586g of potassium chloride was weighed, added to the above solution, and stirred to dissolve it. 20g of the alumina carrier treated by the water vapor is weighed and placed in a vacuum impregnator, and the vacuum degree is up to 50mbar by starting a vacuum pump for vacuum pumping. Adding the complexing solution into a vacuum impregnator, and stirring to ensure that the solution is fully absorbed by an alumina carrier. The composition of the obtained catalyst is 0.3% of platinum, 0.65% of tin, 1.5% of potassium and the balance of alumina carrier (the catalyst composition is calculated by weight percentage).
The alumina absorbing the active components is dried in an electric heating air blast drying oven. The drying temperature is 120 ℃, and the drying time is 10 h.
The calcination of the catalyst impregnated with the active component and dried is carried out in a muffle furnace commonly used in laboratories, the calcination temperature is 500 ℃, and the calcination time is 5 hours. Calcination in a muffle furnace differs from calcination in a tubular reactor in that the air is static and does not flow significantly.
2ml of the calcined catalyst is placed in a stainless steel reactor, and the temperature and the hydrogen airspeed are controlled at 500 ℃ for 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Dodecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material dodecane to contact with a catalyst, and the total space velocity of gas is kept at 7500h in the reaction process-1The hydrogen-oil volume ratio is 100, and the water-oil molar ratio is 3. The evaluation results are shown in table 1. The sample characterization data are shown in Table 2, wherein the specific surface is represented by N2The pore volume and the pore diameter are measured by a mercury intrusion method through a BET calculation method by a low-temperature physical adsorption method.
Example 7
The catalyst was prepared using an alumina carrier that was not subjected to hydrothermal treatment, i.e., the alumina carrier was directly impregnated with an impregnation solution containing an active component without being subjected to hydrothermal treatment, and the composition and preparation method of the catalyst, drying conditions, calcination conditions, and the like were the same as in example 2.
2ml of the calcined catalyst is placed in a stainless steel reactor, and the temperature and the hydrogen airspeed are controlled at 500 ℃ for 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Dodecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material dodecane to contact with a catalyst, and the total space velocity of gas is kept at 5000h in the reaction process-1The hydrogen-oil volume ratio was 20 and the water-oil molar ratio was 8. The evaluation results are shown in table 1. The sample characterization data are shown in Table 2, wherein the specific surface is represented by N2The pore volume and the pore diameter are measured by a mercury intrusion method through a BET calculation method by a low-temperature physical adsorption method.
Example 8
100ml of alumina pellets prepared by an oil ammonia column molding process were placed in a quartz tube reactor. Firstly, heating to 700 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, wherein the airspeed of nitrogen is 1000h-1. Then, introducing water vapor into the quartz tube reactor, and reducing the flow of nitrogen gas to ensure that the volume content of the water vapor reaches 40 percent and the total gas space velocity is 1000h-1. Under the condition, after the alumina carrier is treated for 4 hours, the water vapor is stopped from being added, and the alumina carrier is enabled to have space velocity of 750 hours-1Naturally cooling the mixture to room temperature in nitrogen for later use.
0.115g of stannous chloride dihydrate was weighed into a 100ml beaker, and then dissolved by adding 1ml of 37% concentrated hydrochloric acid. Then, 0.214g of chloroplatinic acid hexahydrate is added into the Sn-containing solution, and the mixture is stirred to dissolve the chloroplatinic acid and form a uniform complex solution with Sn. The above complexing solution was diluted to 20ml with deionized water. 20g of the alumina carrier treated by the water vapor is weighed and placed in a vacuum impregnator, and the vacuum degree is up to 50mbar by starting a vacuum pump for vacuum pumping. Adding the complexing solution into a vacuum impregnator, and stirring to ensure that the solution is fully absorbed by an alumina carrier. The composition of the obtained catalyst is 0.4 percent of platinum, 0.3 percent of tin and the balance of alumina carrier (the catalyst composition is calculated by weight percentage).
The alumina absorbing the active components is dried in an electric heating air blast drying oven. The drying temperature is 120 ℃, and the drying time is 10 h.
20ml of alumina which is impregnated with active components and dried is placed in the middle of a stainless steel reactor at a space velocity of 1500h-1Heating the mixture to 550 ℃ in air flow, and keeping the temperature for 7 hours to decompose the active component precursor to obtain the finished catalyst.
2ml of the calcined catalyst is placed in a stainless steel reactor, and the temperature and the hydrogen airspeed are controlled at 500 ℃ for 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Tetradecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material tetradecane to contact with a catalyst, and the total space velocity of gas is kept to be 9000h in the reaction process-1The hydrogen-oil volume ratio was 40 and the water-oil molar ratio was 10. The evaluation results are shown in table 1. The sample characterization data are shown in Table 2, wherein the specific surface is represented by N2The pore volume and the pore diameter are measured by a mercury intrusion method through a BET calculation method by a low-temperature physical adsorption method.
Example 9
The catalyst was prepared using an alumina carrier that was not subjected to hydrothermal treatment, i.e., the alumina carrier was directly impregnated with an impregnation solution containing the active ingredient without being subjected to hydrothermal treatment, and the catalyst preparation method and drying conditions were the same as in example 8. However, the calcination of the catalyst impregnated with the active component and dried was carried out in a muffle furnace commonly used in laboratories, at a calcination temperature of 550 ℃ for a calcination time of 7 hours. Calcination in a muffle furnace differs from calcination in a tubular reactor in that the air is static and does not flow significantly.
2ml of the calcined catalyst is placed in a stainless steel reactor, and the temperature and the hydrogen airspeed are controlled at 500 ℃ for 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Tetradecane as model compound participating in dehydrogenation reaction of long-chain alkaneHydrogen and steam are used as diluents and are introduced into a reaction system together with raw material tetradecane to contact with a catalyst, and the total space velocity of gas is kept at 9000h in the reaction process-1The hydrogen-oil volume ratio was 40 and the water-oil molar ratio was 10. The evaluation results are shown in table 1. The sample characterization data are shown in Table 2, wherein the specific surface is represented by N2The pore volume and the pore diameter are measured by a mercury intrusion method through a BET calculation method by a low-temperature physical adsorption method.
Example 10
100ml of alumina pellets prepared by an oil ammonia column molding process were placed in a quartz tube reactor. Firstly, heating to 800 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, wherein the airspeed of nitrogen is 1500h-1. Then, introducing water vapor into the quartz tube reactor, and reducing the flow of nitrogen gas to ensure that the volume content of the water vapor reaches 70 percent and the total gas space velocity is 1500h-1. Under the condition, after the alumina carrier is treated for 6 hours, the water vapor is stopped from being added, and the alumina carrier is enabled to have space velocity of 750 hours-1Naturally cooling the mixture to room temperature in nitrogen for later use.
0.16g of chloroplatinic acid hexahydrate was weighed into a 100ml beaker, and then dissolved by adding 1ml of 37% concentrated hydrochloric acid, and the solution was diluted to 20ml with deionized water. 0.860g of lithium chloride was weighed out and added to the above solution, and dissolved by stirring. 20g of the alumina carrier treated by the water vapor is weighed and placed in a vacuum impregnator, and the vacuum degree is up to 50mbar by starting a vacuum pump for vacuum pumping. Adding the complexing solution into a vacuum impregnator, and stirring to ensure that the solution is fully absorbed by an alumina carrier. The composition of the obtained catalyst is 0.3% of platinum, 0.49% of lithium and the balance of alumina carrier (the catalyst composition is calculated by weight percentage).
The alumina absorbing the active components is dried in an electric heating air blast drying oven. The drying temperature is 120 ℃, and the drying time is 10 h.
20ml of alumina which is impregnated with active components and dried is placed in the middle of a stainless steel reactor at a space velocity of 2500h-1Heating to 500 ℃ in the air flow, and keeping for 4h to decompose the active component precursor to obtain the finished catalyst.
2ml of the calcined catalyst was placed in a stainless steel containerIn a steel reactor, at 500 ℃ and a hydrogen space velocity of 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Tetradecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material tetradecane to contact with a catalyst, and the total air speed of gas is kept at 6000h in the reaction process-1The hydrogen-oil volume ratio was 30 and the water-oil molar ratio was 7. The evaluation results are shown in table 1. The sample characterization data are shown in Table 2, wherein the specific surface is represented by N2The pore volume and the pore diameter are measured by a mercury intrusion method through a BET calculation method by a low-temperature physical adsorption method.
Example 11
The catalyst was prepared using an alumina carrier that was not subjected to hydrothermal treatment, i.e., the alumina carrier was directly impregnated with an impregnation solution containing an active component without being subjected to hydrothermal treatment, and the catalyst preparation method and drying conditions were the same as in example 10. However, the calcination of the catalyst impregnated with the active component and dried was carried out in a muffle furnace commonly used in laboratories, at a calcination temperature of 550 ℃ for 4 hours. Calcination in a muffle furnace differs from calcination in a tubular reactor in that the air is static and does not flow significantly.
2ml of the calcined catalyst is placed in a stainless steel reactor, and the temperature and the hydrogen airspeed are controlled at 500 ℃ for 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Tetradecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material tetradecane to contact with a catalyst, and the total air speed of gas is kept at 6000h in the reaction process-1The hydrogen-oil ratio was 30 and the water-oil ratio was 7. The evaluation results are shown in table 1. The sample characterization data are shown in Table 2, wherein the specific surface is represented by N2The pore volume and the pore diameter are measured by a mercury intrusion method through a BET calculation method by a low-temperature physical adsorption method.
Comparative example 1
The catalyst was prepared using the alumina carrier subjected to the hydrothermal treatment, the hydrothermal treatment conditions of the alumina carrier, the method of supporting the catalyst component, the drying conditions, and the calcination conditions were the same as in example 2.
2ml of the calcined catalyst is placed in a stainless steel reactor, and the temperature and the hydrogen airspeed are controlled at 500 ℃ for 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Dodecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and raw material dodecane are separately introduced into a reaction system to contact with a catalyst, and the total gas space velocity is kept at 7500h in the reaction process-1The volume ratio of hydrogen to oil was 600. The evaluation results are shown in table 1.
Comparative example 2
The catalyst was prepared using the alumina carrier subjected to the hydrothermal treatment, the hydrothermal treatment conditions of the alumina carrier, the method of supporting the catalyst component, the drying conditions, and the calcination conditions were the same as in example 8.
2ml of the calcined catalyst is placed in a stainless steel reactor, and the temperature and the hydrogen airspeed are controlled at 500 ℃ for 4000h-1Reducing for 4h under the condition of (1). After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Tetradecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and raw material tetradecane are separately introduced into a reaction system to contact with a catalyst, and the total space velocity of gas is kept at 7500h in the reaction process-1The volume ratio of hydrogen to oil was 600. The evaluation results are shown in table 1.
Comparative example 3
The catalyst was prepared using the alumina carrier subjected to the hydrothermal treatment, the hydrothermal treatment conditions of the alumina carrier, the method of supporting the catalyst component, the drying conditions, and the calcination conditions were the same as in example 10.
2ml of the calcined catalyst is placed in a stainless steel reactor and reduced for 4 hours at the temperature of 500 ℃ and the hydrogen airspeed of 4000h < -1 >. After the catalyst reduction, the reaction temperature was set at 420 ℃ and the reaction pressure was set at 0.14 MPa. Tetradecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and raw material tetradecane are separately introduced into a reaction system to contact with a catalyst, and the total space velocity of gas is kept at 7500h in the reaction process-1The volume ratio of hydrogen to oil was 600. The evaluation results are shown in table 1.
Example 12
The catalyst was prepared using the alumina carrier subjected to the hydrothermal treatment, the hydrothermal treatment conditions of the alumina carrier, the method of supporting the catalyst component, the drying conditions, and the calcination conditions were the same as in example 1.
After the reduction of the catalyst (the reducing conditions were as in example 1), the reaction pressure was set to 0.14 MPa. Dodecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material dodecane to contact with a catalyst, and the total space velocity of gas is kept at 7500h in the reaction process-1The hydrogen-oil volume ratio was 50, the water-oil molar ratio was 4, the reaction temperature was adjusted so that the dodecane conversion rate was kept around 12%, and the stability of the catalyst was evaluated within 200 hours. The evaluation results are shown in table 3.
Example 13
The catalyst was prepared using an alumina carrier that was not subjected to hydrothermal treatment, i.e., the alumina carrier was directly impregnated with an impregnation solution containing an active component without being subjected to hydrothermal treatment, and the catalyst preparation method and drying conditions were the same as in example 1. However, the calcination of the catalyst impregnated with the active component and dried was carried out in a muffle furnace commonly used in laboratories, at a calcination temperature of 550 ℃ for 5 hours. Calcination in a muffle furnace differs from calcination in a tubular reactor in that the air is static and does not flow significantly.
After the catalyst reduction, the reaction pressure was set to 0.14 MPa. Dodecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and steam are taken as diluents and are introduced into a reaction system together with raw material dodecane to contact with a catalyst, and the total space velocity of gas is kept at 7500h in the reaction process-1The hydrogen-oil volume ratio was 50, the water-oil molar ratio was 4, the reaction temperature was adjusted so that the dodecane conversion rate was kept around 12%, and the stability of the catalyst was evaluated within 200 hours. The evaluation results are shown in table 3.
Comparative example 4
The catalyst was prepared using the alumina carrier subjected to the hydrothermal treatment, the hydrothermal treatment conditions of the alumina carrier, the method of supporting the catalyst component, the drying conditions, and the calcination conditions were the same as in example 1.
After the catalyst reduction, the reaction pressure was set to 0.14 MPa. Dodecane is taken as a model compound to participate in dehydrogenation reaction of long-chain alkane, hydrogen and raw material dodecane are independently introduced into a reaction system to contact with a catalyst, and the total gas space velocity is kept at 7500h in the reaction process-1The hydrogen-oil ratio was 600, the reaction temperature was adjusted to maintain the dodecane conversion at about 12%, and the stability of the catalyst was evaluated within 200 hours. The evaluation results are shown in table 3.
TABLE 1 evaluation results of catalyst for dehydrogenation of long-chain alkane
TABLE 1 evaluation results of catalyst for dehydrogenation of long-chain alkane
TABLE 2 data of the physical properties of the specific surface and pores of the support after hydrothermal treatment
TABLE 3 catalyst stability test results for dodecane dehydrogenation
As can be seen from the experimental results shown in table 1, in examples 1 to 5, 8 and 10 of the present application, the catalyst prepared by impregnating the active component with the hydrothermally treated alumina support and then calcining the impregnated alumina support in an atmosphere of air at a certain space velocity, example 6 was calcined in a muffle furnace, example 7 was impregnated with the active component without the hydrothermal treatment, and examples 9 and 11 were prepared by impregnating the active component with the hydrothermally treated alumina support and calcining the impregnated alumina support in a muffle furnace, and all of the reaction processes were carried out using hydrogen and steam as diluents, and the initial activity was significantly higher than that of the catalysts of comparative examples 1 to 3 (comparative examples 1 to 3 only use hydrogen as a diluent).
In the application, the alumina carrier after hydrothermal treatment is used for impregnating the active component in example 12 and comparative example 4, the catalyst after the active component impregnation is calcined in the atmosphere of introducing air with certain space velocity, the alumina carrier without hydrothermal treatment is used for impregnating the active component in example 13, the catalyst after the active component impregnation is calcined in a muffle furnace, the reaction processes of hydrogen and water vapor as diluents are matched in example 12 and example 13, and the hydrogen and raw materials are independently used for feeding in comparative example 4, as can be seen from the experimental results of the table 3, the reaction temperature of example 12 is increased by 2 ℃ in the reaction time of 200 hours, the reaction temperature of example 13 is increased by 4 ℃ in the reaction time of example 13, the reaction temperature of comparative example 4 is increased by 5 ℃ in the reaction time of 200 hours, and the reaction temperature required for maintaining the dodecane conversion rate to be about 12% in the comparative example 4 is higher, which shows that the catalyst stability is better under the process conditions of example 12 and example 13, and the catalytic activity of the catalyst is higher.
From the experimental results, the catalyst for preparing long-chain mono-olefin by dehydrogenation of long-chain alkane has better activity and stability when used in the dehydrogenation process. The mixture of hydrogen and steam is used as diluent, so that the use amount of hydrogen can be reduced, and the purposes of inhibiting carbon deposition of the catalyst and improving the activity and stability of the catalyst are achieved. Further, the hydrothermal treatment is carried out on the catalyst carrier, so that the pore structure performance of the catalyst carrier can be improved, more places are provided for carbon deposit migration, and the mixture of hydrogen and water vapor is more suitable to be used as a diluent, so that the stability of the catalyst is improved. When the catalyst is roasted, roasting atmosphere is also a key factor influencing the catalytic performance of the catalyst, compared with the roasting in static state and general condition in which air flows, the roasting in the atmosphere with a certain space velocity promotes precursor decomposition, improves the heat dispersion of the catalyst and other reasons because the oxygen content in the gas flowing through the catalyst is higher and the volatile components in the catalyst are taken away by the flowing gas flow at any time, influences the state and distribution of active metals on the catalyst, further influences the reaction performance of the catalyst, and is also more suitable for the process of preparing long-chain mono-olefin by using the mixture of hydrogen and water vapor as the diluent for the dehydrogenation of long-chain alkane.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane is characterized in that the long-chain alkane is reacted under the catalysis of a dehydrogenation catalyst to prepare the long-chain olefin; wherein the long-chain alkane is reacted in the presence of a diluent which is a mixture of hydrogen and water vapor.
2. The method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane according to claim 1, wherein the long-chain alkane has 2 to 30 carbons; the reaction temperature is 400-600 ℃, and the reaction pressure is 0.1-1 MPa; and/or the total space velocity of the long-chain alkane and the diluent is 1000-15000 h-1。
3. The method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane according to claim 1, wherein the volume ratio of hydrogen to long-chain alkane in the diluent is 10-150: 1, and the molar ratio of water vapor to long-chain alkane in the diluent is 2-15: 1.
4. The method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane according to claim 1, wherein the dehydrogenation catalyst is reduced before participating in the reaction, wherein the reduction temperature is 400-600 ℃ and the reduction time is 2-8 h.
5. The process for the catalytic dehydrogenation of long chain alkanes to long chain alkenes of claim 1, wherein the dehydrogenation catalyst isTaking alumina as a carrier, precious metal as an active component and one or more of IVA group elements and alkali metal elements as an auxiliary agent; based on the total mass of the dehydrogenation catalyst, the content of the active component in terms of metal is 0.1-5%, and the content of the auxiliary agent in terms of elements is 0.1-8.0%; the specific surface area of the dehydrogenation catalyst is 100-200 m2The pore volume is 0.5-1.5 mL/g.
6. The method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane according to claim 5, wherein the active component is one or more of platinum, palladium and rhodium, and the content of the active component in terms of metal is 0.1-3%; the IVA group elements are one or more of germanium, tin and lead, and the content of the IVA group elements is 0.3 to 5 percent in terms of metal; the alkali metal elements are one or more of lithium, sodium, potassium and rubidium, and the content of the alkali metal elements is 0.1-3% in terms of metal; and/or the molar ratio of the group IVA element to the active component is 1:1 to 5:1 in terms of metal.
7. The method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane according to claim 1, wherein the dehydrogenation catalyst is prepared by: preparing an active component precursor into impregnation liquid, impregnating the alumina carrier in vacuum, and then drying and roasting to obtain the dehydrogenation catalyst.
8. The method for preparing long-chain olefin hydrocarbon through catalytic dehydrogenation of long-chain alkane as claimed in claim 7, wherein the alumina carrier further comprises a hydrothermal treatment step before impregnation, and the hydrothermal treatment conditions are as follows: the hydrothermal treatment temperature is 500-1000 ℃, the hydrothermal treatment time is 1-30 h, and the total gas space velocity in the hydrothermal treatment process is 200-5000 h-1(ii) a The volume content of water vapor in the gas is 10-100%, and the balance is air or nitrogen.
9. The method for preparing long-chain olefin by catalytic dehydrogenation of long-chain alkane according to claim 7, wherein the calcination is carried out as a strip for introducing the impregnated and dried dehydrogenation catalyst into air at a certain space velocityRoasting under the condition of a workpiece; the air airspeed is 600-5000 h-1The roasting temperature is 400-1000 ℃, and the roasting time is 1-20 h.
10. The process for the catalytic dehydrogenation of long-chain alkanes to long-chain alkenes of claim 7, further comprising the step of adding an auxiliary agent to the process for the preparation of said dehydrogenation catalyst, said auxiliary agent being co-impregnated in precursor form with the precursor of said active component.
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