CN114749206B - C5-C10 alkane dehydrogenation catalyst and preparation method and application thereof - Google Patents
C5-C10 alkane dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN114749206B CN114749206B CN202210658787.5A CN202210658787A CN114749206B CN 114749206 B CN114749206 B CN 114749206B CN 202210658787 A CN202210658787 A CN 202210658787A CN 114749206 B CN114749206 B CN 114749206B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 112
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 74
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 57
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 150000005673 monoalkenes Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 120
- 239000000047 product Substances 0.000 claims description 73
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000003513 alkali Substances 0.000 claims description 47
- 229910052697 platinum Inorganic materials 0.000 claims description 45
- 239000002253 acid Substances 0.000 claims description 33
- 239000002243 precursor Substances 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- 238000005216 hydrothermal crystallization Methods 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 20
- 239000012018 catalyst precursor Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 16
- 238000010306 acid treatment Methods 0.000 claims description 14
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 239000012265 solid product Substances 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 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
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 claims description 3
- LMABILRJNNFCPG-UHFFFAOYSA-L ethane-1,2-diamine;platinum(2+);dichloride Chemical compound [Cl-].[Cl-].[Pt+2].NCCN LMABILRJNNFCPG-UHFFFAOYSA-L 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- SYKXNRFLNZUGAJ-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 SYKXNRFLNZUGAJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 24
- 239000004711 α-olefin Substances 0.000 abstract description 12
- 239000006185 dispersion Substances 0.000 abstract description 9
- 239000002245 particle Substances 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000009792 diffusion process Methods 0.000 abstract description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 150000001336 alkenes Chemical class 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010517 secondary reaction Methods 0.000 abstract 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 79
- 239000000243 solution Substances 0.000 description 79
- 239000000203 mixture Substances 0.000 description 23
- 238000001035 drying Methods 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910002846 Pt–Sn Inorganic materials 0.000 description 13
- 239000010413 mother solution Substances 0.000 description 13
- 230000009467 reduction Effects 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 238000011068 loading method Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000005538 encapsulation Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910002835 Pt–Ir Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical group CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/44—Noble metals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a compound C 5 ~C 10 An alkane dehydrogenation catalyst, a preparation method and application thereof, belonging to the technical field of catalysts. The method disclosed by the invention is adopted to realize the coating of the ZSM-5 molecular sieve on the Pt particles, so that the dispersion degree of Pt is obviously improved, the agglomeration of Pt in the reaction is inhibited, and the alkane dehydrogenation activity and stability are improved; meanwhile, the mesoporous structure of the ZSM-5 carrier accelerates the diffusion of reactants and products, inhibits the occurrence of secondary reaction and side reaction, and obtains higher selectivity of olefin products, especially alpha-olefin, beta-olefin and other mono-olefin. The catalyst prepared by the invention is used for catalyzing C 5 ~C 10 The service life of the catalyst is as long as more than 120h, the highest selectivity to mono-olefin is 93%, and the highest selectivity to alpha-olefin and beta-olefin in the mono-olefin product is 65%.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a catalyst C 5 ~C 10 Alkane dehydrogenation catalyst anda preparation method and application thereof.
Background
Naphtha is a mixed liquid containing a plurality of chemical raw materials, and C in the component 5 ~C 10 The alkane accounts for more than 55 percent. Naphtha has wide application, can be used for preparing bulk commodities such as ethylene, propylene and the like through catalytic cracking, and can also be used for preparing aromatic hydrocarbon products such as benzene, xylene and the like through catalytic reforming. However, a catalyst for directly producing alpha-olefins from naphtha has been rarely reported.
The alkane dehydrogenation process is one of the main synthesis processes of long-chain alpha-olefin, and the conventional long-chain alkane dehydrogenation catalyst is a Pacol process developed by U.S. UOP company, and adopts Pt-Sn/gamma-Al 2 O 3 A catalyst. However, in the using process of the catalyst, side reactions such as isomerization, aromatization and the like occur at an acid site on the oxide carrier, the mono-olefin selectivity, particularly alpha-olefin and beta-olefin, needs to be improved, and the service life of the catalyst is short. In order to improve the mono-olefin selectivity and the service life of the catalyst, He Sonbo discloses Pt-Sn-K/gamma-Al 2 O 3 Catalyst adopts auxiliary agent K to Pt-Sn/gamma-Al 2 O 3 The catalyst is modified, and the modified catalyst is used for catalyzing C 16 Although the selectivity of alkane dehydrogenation reaction to mono-olefin is improved, the catalyst has poor stability and short service life, and the catalyst is inactivated for 24 hours by 15 percent (He Sonbo, Biwenjun, Liyulong, and the like 2 O 3 Effect of dehydrogenation of C16 Normal paraffins on catalyst [ J]The journal of fuel chemistry 2010, 038(004): 452-. At present, alkane dehydrogenation catalysts which can combine high mono-olefin selectivity and long catalytic life are lacked.
Disclosure of Invention
The invention aims to improve the selectivity of the mono-olefin product on the basis of improving the yield of the mono-olefin, namely C in naphtha 5 ~C 10 The alkane is selectively dehydrogenated to raise the selectivity of monoolefin product, especially alpha-olefin and beta-olefin, and prolong the service life of the catalyst.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a compound C 5 ~C 10 A method for preparing an alkane dehydrogenation catalyst comprising the steps of:
mixing a platinum source solution and a ligand to obtain a precursor solution; the ligand is ethylenediamine, cyclohexylamine or cyclohexanediamine;
mixing the precursor solution and a ZSM-5 molecular sieve synthesis matrix solution, carrying out hydrothermal crystallization, and carrying out solid-liquid separation on the obtained crystallization product to obtain a solid product;
performing first roasting on the solid product to obtain a roasted product;
mixing the roasted product with an alkali solution, carrying out alkali treatment, and carrying out second roasting on the obtained product to obtain a catalyst precursor; or mixing the roasted product with an acid solution, carrying out acid treatment, and carrying out second roasting on the obtained product to obtain a catalyst precursor;
reducing the catalyst precursor to obtain C 5 ~C 10 An alkane dehydrogenation catalyst.
Preferably, the platinum source in the platinum source solution is chloroplatinic acid, tetraammineplatinum chloride, ethylenediamine platinum chloride, sodium hexachloroplatinate or tetrakis (triphenylphosphine) platinum; the molar ratio of the platinum source to the ligand in the precursor solution is 1 (30-200).
Preferably, the precursor solution further comprises an auxiliary salt; the auxiliary metal element In the auxiliary salt is one or more of Sn, Ir, La, Ga, Ce, In and Zn; the molar ratio of the auxiliary metal element in the auxiliary salt to the platinum element in the platinum source is below 10.
Preferably, the concentration of the acid solution is 0.005-1 mol/L; the acid in the acid solution comprises hydrochloric acid, nitric acid or carbonic acid; the acid treatment time is 15-60 min; the temperature of the acid treatment is 60-90 ℃;
the concentration of the alkali solution is 0.005-1 mol/L, and the alkali in the alkali solution comprises sodium hydroxide, potassium carbonate or sodium carbonate; the alkali treatment time is 15-240 min; the temperature of the alkali treatment is 60-90 ℃.
Preferably, the temperature of the second roasting is 350-600 ℃, and the heat preservation time is 3-10 h; the second firing is performed in an air atmosphere.
Preferably, the temperature of the first roasting is 400-700 ℃, and the heat preservation time is 4-14 h.
The invention provides C prepared by the preparation method in the scheme 5 ~C 10 The alkane dehydrogenation catalyst comprises a ZSM-5 molecular sieve and an active component loaded on the ZSM-5 molecular sieve, wherein the active component comprises platinum, and the ZSM-5 molecular sieve is in a mesoporous structure.
Preferably, the molecular sieve further comprises an auxiliary agent loaded on the ZSM-5 molecular sieve, wherein the auxiliary agent is one or more of Sn, Ir, La, Ga, Ce, In and Zn.
The invention provides the scheme C 5 ~C 10 Application of alkane dehydrogenation catalyst in preparation of mono-olefin by catalyzing alkane dehydrogenation, wherein alkane is C 5 ~C 10 Of (a) an alkane.
Preferably, the conditions for preparing mono-olefin by catalytic alkane dehydrogenation comprise: the reaction conditions are normal pressure, the temperature is 320-500 ℃, and the mass space velocity is 0.2-12 h -1 (ii) a The reaction atmosphere comprises one or more of nitrogen, hydrogen, carbon monoxide and carbon dioxide, and the ratio of the molar amount of the gas providing the reaction atmosphere to the molar amount of the alkane is below 5.
The invention provides a compound C 5 ~C 10 A method of preparing an alkane dehydrogenation catalyst comprising the steps of: mixing a platinum source solution and a ligand to obtain a precursor solution; the ligand is ethylenediamine, cyclohexylamine or cyclohexanediamine; mixing the precursor solution and a ZSM-5 molecular sieve synthesis matrix solution, and performing hydrothermal crystallization to obtain a solid product; carrying out first roasting on the solid product to obtain a roasted product; mixing the roasted product with an acid solution, carrying out acid treatment, and carrying out second roasting on the obtained product to obtain a catalyst precursor; or mixing the roasted product with an alkali solution, carrying out alkali treatment, and carrying out secondary roasting on the obtained product to obtain a catalyst precursor; reducing the catalyst precursor to obtain C 5 ~C 10 An alkane dehydrogenation catalyst.
The conventional oxide carrier supports only the active component, and fails to sufficiently exert the functions of the carrier and the active component. The invention adopts a ZSM-5 molecular sieve carrier which is characterized by having a pore channel structure with molecular size, rich specific surface area and shape-selective catalytic characteristic, and the Pt supported on the carrier can control the dispersion and C of Pt compared with the traditional oxide carrier 5 ~C 10 The accessibility of alkane molecules leads to selective adsorption and dehydrogenation of alkane molecule terminals, and can improve the selectivity of alpha-olefin and beta-olefin; the alkali/acid treated ZSM-5 molecular sieve carrier provided by the invention has a mesoporous structure, can slow down the carbon deposition rate, improves the stability of the catalyst, prolongs the service life, and can promote the diffusion of products such as alpha-olefin and beta-olefin, reduce the occurrence of side reactions such as isomerization and cyclization, and improve the selectivity of a target product; according to the loading preparation method provided by the invention, the ligand can be used as a template of the ZSM-5 molecular sieve and can be coordinated with metal ions, so that platinum participates in hydrothermal crystallization of the ZSM-5 molecular sieve, the active component is stably introduced into the molecular sieve, the ZSM-5 molecular sieve is used for coating Pt particles, the dispersion degree of Pt is remarkably improved, the agglomeration of Pt in the reaction is inhibited, and the alkane dehydrogenation activity and stability are improved.
The results of the examples show that the catalyst of the invention is applied to naphtha C 5 ~C 10 In the alkane dehydrogenation reaction, the service life of the catalyst is as long as over 120h, the highest selectivity of the catalyst to mono-olefin is 93%, and the highest selectivity of alpha-olefin and beta-olefin in the mono-olefin product is 65%.
Drawings
FIG. 1 is a graph showing the results of the evaluation of the dehydrogenation reaction of n-octane over the #1 catalyst (Pt-Sn/ZSM-5 catalyst) in example 1;
FIG. 2 is a graph showing the results of evaluation of the dehydrogenation reaction of n-octane catalyzed by the #2 catalyst (Pt-La/ZSM-5 catalyst) in example 2;
FIG. 3 is a graph showing the results of the evaluation of the dehydrogenation reaction of n-octane catalyzed by the #3 catalyst (Pt-Ce/ZSM-5 catalyst) in example 3;
FIG. 4 is a graph showing the results of evaluating the n-octane dehydrogenation reaction catalyzed by #4 catalyst (Pt-Ir/ZSM-5 catalyst) in example 4;
FIG. 5 is a graph showing the results of evaluation of the dehydrogenation reaction of n-octane catalyzed by #5 catalyst (Pt-In/ZSM-5 catalyst) In example 5;
FIG. 6 is a graph showing the results of evaluating the n-octane dehydrogenation reaction catalyzed by #6 catalyst (Pt-Zn/ZSM-5 catalyst) in example 6;
FIG. 7 is a graph showing the results of evaluating the n-octane dehydrogenation reaction catalyzed by #7 catalyst (Pt-Ga/ZSM-5 catalyst) in example 7;
FIG. 8 is a graph showing the results of evaluating the dehydrogenation reaction of n-octane catalyzed by #8 catalyst (Pt/ZSM-5 catalyst) in example 8;
FIG. 9 is a graph showing the evaluation results of the #9 catalyst in comparative example 1 for catalyzing the dehydrogenation reaction of n-octane;
FIG. 10 is a graph showing the results of the evaluation of the #10 catalyst in comparative example 2 for catalyzing the dehydrogenation reaction of n-octane;
FIG. 11 is a graph showing the evaluation results of the dehydrogenation reaction of n-octane catalyzed by the #11 catalyst in comparative example 3;
FIG. 12 is a graph showing the results of evaluation of the dehydrogenation reaction of n-pentane catalyzed by the #1 catalyst (Pt-Sn/ZSM-5 catalyst) in example 1;
FIG. 13 is a graph showing the results of evaluation of dehydrogenation reaction of n-hexane catalyzed by #1 catalyst (Pt-Sn/ZSM-5 catalyst) in example 1;
FIG. 14 is a graph showing the evaluation results of the dehydrogenation reaction of n-heptane catalyzed by the #1 catalyst (Pt-Sn/ZSM-5 catalyst) in example 1;
FIG. 15 is a graph showing the results of evaluation of dehydrogenation reaction of n-nonane catalyzed by the #1 catalyst (Pt-Sn/ZSM-5 catalyst) in example 1;
FIG. 16 is a graph showing the evaluation results of the dehydrogenation reaction of n-decane catalyzed by the #1 catalyst (Pt-Sn/ZSM-5 catalyst) in example 1;
FIG. 17 is a graph showing the selectivity of 1-octene and 2-octene to total olefin product as a function of reaction time as a result of evaluating the n-octane dehydrogenation reaction over #1 catalyst (Pt-Sn/ZSM-5 catalyst) in example 1;
FIG. 18 is a transmission electron micrograph of catalyst # 1;
FIG. 19 is a BET adsorption curve for catalyst #1 and catalyst # 11.
Detailed Description
The invention provides a compound C 5 ~C 10 A method for preparing an alkane dehydrogenation catalyst comprising the steps of:
mixing a platinum source solution and a ligand to obtain a precursor solution; the ligand is ethylenediamine, cyclohexylamine or cyclohexanediamine;
mixing the precursor solution and a ZSM-5 molecular sieve synthesis matrix solution, performing hydrothermal crystallization, and performing solid-liquid separation on the obtained crystallization product to obtain a solid product;
carrying out first roasting on the solid product to obtain a roasted product;
mixing the roasted product with an alkali solution, carrying out alkali treatment, and carrying out second roasting on the obtained product to obtain a catalyst precursor; or mixing the roasted product with an acid solution, carrying out acid treatment, and carrying out secondary roasting on the obtained product to obtain a catalyst precursor;
reducing the catalyst precursor to obtain C 5 ~C 10 An alkane dehydrogenation catalyst.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
According to the invention, a platinum source solution and a ligand are mixed to obtain a precursor solution.
In the present invention, the platinum source in the platinum source solution is preferably chloroplatinic acid, tetraammineplatinum chloride, ethylenediamine platinum chloride, sodium hexachloroplatinate or tetrakis (triphenylphosphine) platinum; the ligand is ethylenediamine, cyclohexylamine or cyclohexanediamine. In the invention, the molar ratio of the platinum source to the ligand in the precursor solution is preferably 1 (30-200), and more preferably 1 (60-100). In the present invention, platinum in the platinum source is used as an active component; the ligand can be used as a template of the ZSM-5 molecular sieve and can be coordinated with metal ions, so that platinum participates in hydrothermal crystallization of the ZSM-5 molecular sieve, and the dispersibility and stability of the platinum are improved.
The invention has no special requirement on the concentration of the platinum source solution as long as the platinum source can be dissolved; in the present invention, the platinum source solution is preferably obtained by dissolving a platinum source in water.
The invention has no special requirements on the process of mixing the platinum source solution and the ligand, and can mix the platinum source solution and the ligand uniformly.
In the present invention, the precursor solution preferably further comprises an auxiliary salt; in the present invention, the promoter metal element In the promoter salt is preferably one or more of Sn, Ir, La, Ga, Ce, In, and Zn. The invention has no special requirement on the specific type of the auxiliary salt, and the salt of the metal which is well known in the field and can be dissolved in water can be any, and the specific type can be nitrate, chloride, carbonate, sulfate and the like. In the embodiment of the invention, the assistant salt is SnCl 4 ·5H 2 O、La(NO 3 ) 3 、Ce(NO 3 ) 3 、IrCl 3 、In(NO 3 ) 3 、Zn(NO 3 ) 2 Or Ga (NO) 3 ) 3 . In the invention, the molar ratio of the promoter metal element in the promoter salt to the platinum element in the platinum source is preferably 10 or less, and more preferably 1 to 10. In the invention, the metal in the auxiliary agent salt is used as an auxiliary agent and has an electronic effect with platinum, so that the dehydrogenation activity of the catalyst is improved, and the dispersibility of the platinum is improved.
In the present invention, when the precursor solution further includes an auxiliary salt, the preparation of the precursor solution preferably includes: and mixing the platinum source solution, the auxiliary agent salt solution and the ligand to obtain a precursor solution. The invention has no special requirement on the concentration of the auxiliary salt solution, as long as the auxiliary salt can be completely dissolved.
After the precursor solution is obtained, the precursor solution and a ZSM-5 molecular sieve synthesis matrix solution are mixed, hydrothermal crystallization is carried out, and the obtained crystallization product is subjected to solid-liquid separation to obtain a solid product.
In the present invention, the ZSM-5 molecular sieve synthesis precursor solution preferably has an initial gel molar composition of 40H 2 O：(0.00~0.10)Al 2 O 3 ：(0.05~0.1)Na 2 O: 0.5TPAOH (meaning tetrapropylammonium hydroxide): 1SiO 2 . In the present invention, theNa 2 The raw material corresponding to O is preferably sodium hydroxide; the SiO 2 The corresponding raw material is preferably tetraethoxysilane; the Al is 2 O 3 The corresponding raw material is preferably aluminum nitrate; the tetrapropylammonium hydroxide is preferably used in the form of an aqueous tetrapropylammonium hydroxide solution; the mass fraction of the tetrapropylammonium hydroxide aqueous solution is preferably 25%. The preparation method of the ZSM-5 molecular sieve synthesis matrix solution has no special requirements, and the preparation method can be obtained by directly mixing the corresponding raw materials according to the molar ratio and then aging the mixture. In the embodiment of the invention, the ZSM-5 molecular sieve mother solution is prepared by sequentially adding NaOH and TPAOH aqueous solution with the mass fraction of 25 percent into H 2 And (3) uniformly stirring the mixture in O at 500rpm until the mixture is clear, slowly dropwise adding TEOS (tetraethyl orthosilicate), and stirring and aging the mixture at room temperature for 2-6 hours to obtain the product.
In the invention, the dosage ratio of the platinum in the precursor solution to the ZSM-5 molecular sieve mother solution is preferably determined according to the loading amount of the platinum in the alkane dehydrogenation catalyst, and in the invention, the mass content of the platinum in the alkane dehydrogenation catalyst is preferably 0.05-2.00%.
The invention has no special requirement on the process of mixing the precursor solution and the ZSM-5 molecular sieve mother solution, and the precursor solution and the ZSM-5 molecular sieve mother solution can be uniformly mixed.
In the invention, the temperature of the hydrothermal crystallization is preferably 150-200 ℃, more preferably 160-190 ℃, and further preferably 170-180 ℃; the heat preservation time is preferably 2-4 days.
After the hydrothermal crystallization is finished, the method carries out solid-liquid separation on the obtained crystallization product. The invention has no special requirement on the solid-liquid separation mode, and the solid-liquid separation mode which is well known in the field, such as centrifugation, can be adopted. After the solid-liquid separation, the present invention preferably further comprises drying the solid product. The drying conditions of the present invention are not particularly limited, and those well known in the art may be used.
After obtaining the solid product, the invention carries out the first roasting on the solid product to obtain a roasted product. In the present invention, the first firing is preferably performed in an air atmosphere; the first roasting temperature is preferably 400-700 ℃, and more preferably 500-600 ℃; the heat preservation time is preferably 4-14 h, more preferably 6-12 h, and further preferably 8-10 h. In the present invention, the templating agent (TPAOH) and the ligand are removed during the firing process while the metal component is oxidized to a metal oxide.
After a roasted product is obtained, the roasted product is mixed with an acid solution for acid treatment, and the obtained product is subjected to secondary roasting to obtain a catalyst precursor.
In the invention, the concentration of the acid solution is preferably 0.005-1 mol/L, more preferably 0.01-0.9 mol/L, and further preferably 0.1-0.8 mol/L; the acid in the acid solution comprises hydrochloric acid, nitric acid or carbonic acid. In the present invention, the acid solution is preferably obtained by dissolving an acid in water. In the invention, the solid-to-liquid ratio of the roasted product to the acid solution is preferably 1g (50-200) mL, and more preferably 1g (100-150) mL; the time of the acid treatment is preferably 15-60 min; the temperature of the acid treatment is preferably 60-90 ℃, and more preferably 70-80 ℃.
In the invention, the roasted product is mixed with an acid solution for acid treatment, and the second roasting of the obtained product can be replaced by: and mixing the roasted product with an alkali solution, carrying out alkali treatment, and carrying out secondary roasting on the obtained product to obtain a catalyst precursor.
In the invention, the concentration of the alkali solution is preferably 0.005-1 mol/L, more preferably 0.01-0.9 mol/L, and further preferably 0.1-0.8 mol/L; the alkali in the alkali solution preferably comprises sodium hydroxide, potassium carbonate or sodium carbonate, more preferably sodium hydroxide; the time of the alkali treatment is preferably 15-120 min; the temperature of the alkali treatment is preferably 60-90 ℃, and more preferably 70-80 ℃.
After the acid treatment or the alkali treatment, the present invention preferably further comprises subjecting the treated product to solid-liquid separation, solid drying, and then to second calcination. The solid-liquid separation mode is not particularly required in the invention, and the solid-liquid separation mode well known in the field, such as centrifugation, can be used. In the invention, the drying temperature is preferably 100 ℃, and the drying time is preferably 6-12 h.
In the invention, the temperature of the second roasting is preferably 350-600 ℃, and more preferably 400-500 ℃; the heat preservation time is preferably 3-10 h, and more preferably 4-8 h; in the present invention, the second baking is preferably performed in an air atmosphere. The second roasting of the present invention has the function of removing residual moisture on the surface.
In the invention, the processes of acid treatment (or alkali treatment) and second roasting are preferably carried out for 1-3 times.
After obtaining the catalyst precursor, the invention reduces the catalyst precursor to obtain C 5 ~C 10 An alkane dehydrogenation catalyst.
In the invention, the temperature of the reduction treatment is preferably 150-600 ℃, more preferably 200-500 ℃, and further preferably 300-400 ℃; the heat preservation time is preferably 1-5 h, and more preferably 2-4 h. In the present invention, the atmosphere of the reduction treatment is preferably an atmosphere of carbon monoxide, carbon dioxide or hydrogen. In the present invention, the reduction treatment functions to reduce the metal oxide to the elemental metal. In the reduction process, part of Pt and auxiliary metal forms alloy, so that an electronic effect and a geometric effect exist, the dispersion degree of Pt is improved by the geometric effect, and the Pt is prevented from agglomerating; electronic effects can promote the dehydrogenation process activated by C-H bonds.
The invention provides C prepared by the preparation method in the scheme 5 ~C 10 An alkane dehydrogenation catalyst comprising a ZSM-5 molecular sieve and an active component supported on the ZSM-5 molecular sieve, the active component comprising platinum; the ZSM-5 molecular sieve is of a mesoporous structure. In the present invention, said C 5 ~C 10 The alkane dehydrogenation catalyst preferably further comprises an auxiliary agent loaded on the ZSM-5 molecular sieve, wherein the auxiliary agent is one or more of Sn, Ir, La, Ga, Ce, In and Zn. In the present invention, said C 5 ~C 10 The mass content of platinum in the alkane dehydrogenation catalyst is preferably 0.05-2.00%; the mass content of the metal element corresponding to the auxiliary agent is preferably 0.00-2.00%. In the present invention, said C 5 ~C 10 The preferred mesoporous aperture of the alkane dehydrogenation catalyst is 2-10 nm, and the preferred specific surface area is 300-400 m 2 (iv) g. In the present invention, the active ingredient and the auxiliary agentAnd (3) loading on the pore canal and/or the surface of the ZSM-5 molecular sieve.
The conventional oxide carrier supports only the active component, and fails to sufficiently exert the functions of the carrier and the active component. The invention adopts a ZSM-5 molecular sieve carrier which is characterized by having a pore channel structure with molecular size, rich specific surface area and shape-selective catalytic characteristic, and the Pt supported on the carrier can control the dispersion and C of Pt compared with the traditional oxide carrier 5 ~C 10 The accessibility of alkane molecules leads to selective adsorption and dehydrogenation of alkane molecule terminals, and can improve the selectivity of alpha-olefin and beta-olefin; the alkali/acid treated ZSM-5 molecular sieve carrier provided by the invention has a mesoporous structure, can slow down the carbon deposition rate, improves the stability of the catalyst, prolongs the service life, and can promote the diffusion of products such as alpha-olefin and beta-olefin, reduce the occurrence of side reactions such as isomerization and cyclization, and improve the selectivity of target products; according to the loading preparation method provided by the invention, the ligand can be used as a template of the ZSM-5 molecular sieve and can be coordinated with metal ions, so that platinum participates in hydrothermal crystallization of the ZSM-5 molecular sieve, the active component is stably introduced into the molecular sieve, the ZSM-5 molecular sieve is used for coating Pt particles, the dispersion degree of Pt is remarkably improved, the agglomeration of Pt in the reaction is inhibited, and the alkane dehydrogenation activity and stability are improved.
The invention provides application of the alkane dehydrogenation catalyst in the scheme in preparation of mono-olefin by catalyzing alkane dehydrogenation, wherein the alkane is C 5 ~C 10 Of an alkane.
In the present invention, the conditions for preparing mono-olefin by catalytic alkane dehydrogenation preferably include: the temperature is 320-500 ℃, and the mass space velocity is 0.2-12 h -1 (ii) a The reaction atmosphere comprises one or more of nitrogen, hydrogen, carbon monoxide and carbon dioxide, and the ratio of the molar amount of the gas providing the reaction atmosphere to the molar amount of the alkane is below 5. More preferably, the temperature is 350-450 ℃, and the mass space velocity is 3-10 h -1 (ii) a The ratio of the molar weight of the gas providing the reaction atmosphere to the molar weight of the alkane is 1-5.
The alkane dehydrogenation catalyst provided by the present invention, the preparation method and the application thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1.1 ZSM-5 molecular sieves parent solution Synthesis
0.202g of NaOH and 17.179g of TPAOH aqueous solution (25% by mass) were added to 25.362g H in this order 2 Stirring the mixture evenly in O at 500rpm until the mixture is clear, slowly dropwise adding 12.30g TEOS, stirring at room temperature and aging for 6 hours; corresponding to an initial gel molar composition of 40H 2 O：0.05Na 2 O：0.4TPAOH：1SiO 2 。
1.2 precursor preparation and encapsulation Synthesis catalyst Process
0.023g of SnCl 4 ·5H 2 Dissolving O in 1mL of water, uniformly mixing with 1mL of 0.0513mol/L chloroplatinic acid solution and 0.61g of ethylenediamine at normal temperature, adding the solution and ZSM-5 molecular sieve matrix solution in the 1.1 into a 100mL high-pressure reaction kettle, carrying out hydrothermal crystallization at 170 ℃ for 48 hours, taking the kettle, centrifuging a sample for 3 times, drying at 100 ℃ for 12 hours, roasting at 550 ℃ in a muffle furnace under air atmosphere for 10 hours to obtain a roasted product, and placing the roasted product in 0.01mol/L sodium hydroxide solution for alkali treatment for 2 hours (the solid-to-liquid ratio is 1g:100 mL), wherein the alkali treatment temperature is 80 ℃. The distilled water is centrifuged for 1 time, dried for 12h at 100 ℃ and calcined for 5h at 450 ℃ in a muffle furnace under air. The sample is tableted, crushed, sieved by 20-40 meshes, and then subjected to reduction treatment for 2 hours at 450 ℃ in a hydrogen atmosphere, and the sample is used for activity test and is marked as a #1 catalyst (the loading capacity of Pt is 0.35%, and the loading capacity of Sn is 0.35%).
Example 2
0.01894 g La (NO) 3 ) 3 Mixing 1g of cyclohexylamine and 1mL of 0.0513mol/L chloroplatinic acid to obtain a precursor solution; adding the obtained product and a ZSM-5 molecular sieve mother solution in the 1.1 into a 100mL high-pressure reaction kettle, performing hydrothermal crystallization at 170 ℃ for 48 hours, taking the kettle, centrifuging a sample for 3 times, drying at 100 ℃ for 12 hours, drying, roasting at 550 ℃ for 10 hours in a muffle furnace under the air atmosphere to obtain a roasted product, and placing the roasted product in a 0.01mol/L sodium hydroxide solution for alkali treatment for 2 hours (the solid-liquid ratio is 1g:100 mL), wherein the alkali treatment temperature is 80 ℃. Centrifuging with distilled water for 1 time at 100 deg.CDrying for 12h, and calcining for 5h at 450 ℃ under the air of a muffle furnace. The sample is tableted, crushed, sieved by 20-40 meshes, and then subjected to reduction treatment at 450 ℃ for 2 hours in a hydrogen atmosphere, and the sample is used for activity test and is marked as a #2 catalyst (the mass content of Pt is 0.35%, and the mass content of La is 0.35%).
Example 3
0.02522 g Ce (NO) 3 ) 3 1.81g of cyclohexanediamine and 1mL of chloroplatinic acid with the concentration of 0.0513mol/L to obtain a precursor solution; adding the solution and the ZSM-5 molecular sieve mother solution in the 1.1 into a 100mL high-pressure reaction kettle, performing hydrothermal crystallization at 170 ℃ for 48 hours, taking the kettle, centrifuging the sample for 3 times, drying the sample at 100 ℃ for 12 hours, roasting the dried sample at 550 ℃ for 10 hours in a muffle furnace under the air atmosphere to obtain a roasted product, and placing the roasted product into a 0.01mol/L sodium hydroxide solution for alkali treatment for 2 hours (the solid-liquid ratio is 1g:100 mL), wherein the alkali treatment temperature is 80 ℃. The distilled water is centrifuged for 1 time, dried for 12h at 100 ℃, and calcined for 5h at 450 ℃ under the air of a muffle furnace. The sample is tableted, crushed, sieved by 20-40 meshes, and then subjected to reduction treatment for 2 hours at 450 ℃ in a hydrogen atmosphere, and the sample is used for activity test and is marked as a #3 catalyst (the mass content of Pt is 0.35%, and the mass content of Ce is 0.35%).
Example 4
0.06233 g of IrCl 3 1mL of 0.0513mol/L chloroplatinic acid solution and 0.61g of ethylenediamine are mixed uniformly at normal temperature, the mixture and ZSM-5 molecular sieve mother solution in the 1.1 are added into a 100mL high-pressure reaction kettle together, the kettle is taken after hydrothermal crystallization is carried out for 48 hours at the temperature of 170 ℃, a sample is centrifuged for 3 times, dried for 12 hours at the temperature of 100 ℃, then roasted for 10 hours at the temperature of 550 ℃ in a muffle furnace under the air atmosphere to obtain a roasted product, and the roasted product is placed in 0.01mol/L sodium hydroxide solution for alkali treatment for 2 hours (the solid-to-liquid ratio is 1g:100 mL), and the alkali treatment temperature is 80 ℃. The distilled water is centrifuged for 1 time, dried for 12h at 100 ℃ and calcined for 5h at 450 ℃ in a muffle furnace under air. The sample is tableted, crushed, sieved by 20-40 meshes, and then subjected to reduction treatment for 2 hours at 450 ℃ in a hydrogen atmosphere, and the sample is used for activity test and is marked as a #4 catalyst (the mass content of Pt is 0.35%, and the mass content of Ir is 0.35%).
Example 5
0.02109 g of In (NO) 3 ) 3 1mL0.0513mol/L hexachloroplatinic acidMixing sodium and 0.61g of ethylenediamine at normal temperature, adding the mixture and the ZSM-5 molecular sieve mother solution in the 1.1 into a 100mL high-pressure reaction kettle, performing hydrothermal crystallization at 170 ℃ for 48h, taking the kettle, centrifuging the sample for 3 times, drying the sample at 100 ℃ for 12h, then roasting the sample at 550 ℃ for 10h in a muffle furnace under the air atmosphere to obtain a roasted product, and placing the roasted product into 0.01mol/L sodium hydroxide solution for alkali treatment for 2h (the solid-liquid ratio is 1g:100 mL), wherein the alkali treatment temperature is 80 ℃. The distilled water is centrifuged for 1 time, dried for 12h at 100 ℃, and calcined for 5h at 450 ℃ under the air of a muffle furnace. The sample is tableted, crushed, sieved by 20-40 meshes, and then subjected to reduction treatment at 450 ℃ for 2 hours In a hydrogen atmosphere, and the sample is used for activity test and is marked as a #5 catalyst (the mass content of Pt is 0.35%, and the mass content of In is 0.35%).
Example 6
0.03684 g Zn (NO) 3 ) 2 1mL of 0.0513mol/L sodium hexachloroplatinate and 0.61g of ethylenediamine are uniformly mixed at normal temperature, the mixture and the ZSM-5 molecular sieve mother solution in the 1.1 are added into a 100mL high-pressure reaction kettle together, the kettle is taken after hydrothermal crystallization is carried out for 48 hours at the temperature of 170 ℃, a sample is centrifuged for 3 times, dried at the temperature of 100 ℃ for 12 hours, then roasted at the temperature of 550 ℃ in a muffle furnace for 10 hours to obtain a roasted product, the roasted product is placed into 0.01mol/L sodium hydroxide solution for alkali treatment for 2 hours (the solid-to-liquid ratio is 1g:100 mL), and the alkali treatment temperature is 80 ℃. The distilled water is centrifuged for 1 time, dried for 12h at 100 ℃ and calcined for 5h at 450 ℃ in a muffle furnace under air. The sample is tableted, crushed, sieved by 20-40 meshes, and then subjected to reduction treatment for 2 hours at 450 ℃ in a hydrogen atmosphere, and the sample is used for activity test and is marked as a #6 catalyst (the mass content of Pt is 0.35%, and the mass content of Zn is 0.35%).
Example 7
0.02504 g Ga (NO) 3 ) 3 1mL of 0.0513mol/L chloroplatinic acid and 0.61g of ethylenediamine are uniformly mixed at normal temperature, the mixture and the ZSM-5 molecular sieve mother solution in the 1.1 are added into a 100mL high-pressure reaction kettle together, the kettle is taken after hydrothermal crystallization is carried out for 48 hours at the temperature of 170 ℃, a sample is centrifuged for 3 times, dried at the temperature of 100 ℃ for 12 hours, then roasted at the temperature of 550 ℃ in a muffle furnace for 10 hours to obtain a roasted product, the roasted product is placed into a 0.01mol/L sodium hydroxide solution for alkali treatment for 2 hours (the solid-to-liquid ratio is 1g:100 mL), and the alkali treatment temperature is 80 ℃. Steaming foodThe distilled water is centrifuged for 1 time, dried for 12h at 100 ℃ and calcined for 5h at 450 ℃ in a muffle furnace. The sample is tableted, crushed, sieved by 20-40 meshes, and then subjected to reduction treatment at 450 ℃ for 2 hours in a hydrogen atmosphere, and the sample is used for an activity test and is marked as a #7 catalyst (the mass content of Pt is 0.35%, and the mass content of Ga is 0.35%).
Example 8
1mL of chloroplatinic acid of 0.0513mol/L and 0.61g of ethylenediamine are uniformly mixed at normal temperature, the mixture and the ZSM-5 molecular sieve mother solution in the 1.1 are added into a 100mL high-pressure reaction kettle together, the kettle is taken after hydrothermal crystallization is carried out for 48 hours at the temperature of 170 ℃, a sample is centrifuged for 3 times, dried for 12 hours at the temperature of 100 ℃, then roasted for 10 hours at the temperature of 550 ℃ in a muffle furnace under the air atmosphere to obtain a roasted product, and the roasted product is placed in a 0.01mol/L sodium hydroxide solution for alkali treatment for 2 hours (the solid-to-liquid ratio is 1g:100 mL), and the alkali treatment temperature is 80 ℃. The distilled water is centrifuged for 1 time, dried for 12h at 100 ℃ and calcined for 5h at 450 ℃ in a muffle furnace under air. The sample is tableted, crushed, sieved by 20-40 meshes, and then subjected to reduction treatment at 450 ℃ in a hydrogen atmosphere for 2h for activity test, and is marked as a #8 catalyst (the loading amount of Pt is 0.35%).
Comparative example 1 in-situ pore-creating encapsulation type (pore-creating agent is added directly during in-situ encapsulation)
0.5g NaOH, 1.6815g TPABr (tetrapropylammonium bromide) aqueous solution (25% by mass), 0.7g TPHAC (hexadecyltrimethoxysilane, as a pore-forming agent) were added in this order to 81.85g H g 2 And (3) uniformly stirring the mixture in O at 500rpm until the mixture is clear, slowly dropwise adding TEOS (tetraethyl orthosilicate) 5.0g, stirring the mixture at room temperature and aging the mixture for 6 hours to obtain a ZSM-5 molecular sieve parent solution.
0.023g of SnCl 4 ·5H 2 O dissolved in 1mL H 2 And mixing the solution with 1mL of 0.0513mol/L chloroplatinic acid solution and 0.61g of ethylenediamine at normal temperature, adding the mixture and the ZSM-5 molecular sieve mother solution into a 100mL high-pressure reaction kettle, performing hydrothermal crystallization at 170 ℃ for 48 hours, taking the kettle, centrifuging a sample for 3 times, drying at 100 ℃ for 12 hours, and then roasting at 550 ℃ for 10 hours in a muffle furnace under the air atmosphere to obtain the catalyst precursor. The sample is tableted, crushed, sieved by 20-40 meshes, and then reduced for 2 hours at 450 ℃ in a hydrogen atmosphere for activity test, and is marked as a #9 catalyst (Pt supported catalyst)The amount was 0.35%, and the supported amount of Sn was 0.35%).
Comparative example 2 (ZSM-5 pore-forming impregnation metal Pt, Sn)
0.202g of NaOH and 17.179g of 25% TPAOH aqueous solution are added in sequence to 25.362g H 2 Stirring the mixture evenly in O at 500rpm until the mixture is clear, slowly dropwise adding 12.30g TEOS, stirring and aging at room temperature for 6 h. Pouring the mixture into a 100mL high-pressure reaction kettle, carrying out hydrothermal crystallization at 170 ℃ for 48h, taking the kettle, centrifuging the sample for 3 times, drying the sample at 100 ℃ for 12h, and roasting the dried sample at 550 ℃ for 10h in a muffle furnace under the air atmosphere to obtain the ZSM-5 molecular sieve.
The ZSM-5 molecular sieve is put into 0.01mol/L sodium hydroxide solution for alkali treatment for 2h (the solid-to-liquid ratio is 1g:100 mL), and the alkali treatment temperature is 80 ℃. And (3) centrifuging the distilled water for 1 time, drying the distilled water at 100 ℃ for 12 hours, and calcining the dried distilled water at 450 ℃ for 5 hours in a muffle furnace to obtain the porous ZSM-5 molecular sieve.
Loading 2g of the porous ZSM-5 molecular sieve with 0.35% of metal platinum by an equal-volume impregnation method, wherein the impregnation solution is 0.7mL of chloroplatinic acid aqueous solution with the concentration of 0.0513mol/L and 0.023g of SnCl 4 ·5H 2 Soaking the O mixed solution for 24h, drying, roasting for 4h at 450 ℃ in a muffle furnace under air atmosphere to obtain a Pt-M/Na type powdery molecular sieve, tabletting the sample, crushing, sieving by 20-40 meshes, and then carrying out reduction treatment for 2h at 450 ℃ in hydrogen atmosphere for activity test, wherein the sample is marked as a #10 catalyst (the mass content of Pt is 0.35%, and the mass content of Sn is 0.35%).
Comparative example 3 (non-pore forming)
Adding 0.023g SnCl 4 ·5H 2 Dissolving O in 1mL of water, uniformly mixing with 1mL of 0.0513mol/L chloroplatinic acid solution and 0.61g of ethylenediamine at normal temperature, adding the mixture and the ZSM-5 molecular sieve mother solution in the 1.1 into a 100mL high-pressure reaction kettle, carrying out hydrothermal crystallization at 170 ℃ for 48 hours, taking the kettle, centrifuging the sample for 3 times, drying the sample at 100 ℃ for 12 hours, drying the dried sample, and roasting the dried sample at 550 ℃ for 10 hours in the air atmosphere in a muffle furnace to obtain the catalyst precursor. The sample is tabletted, crushed, sieved by 20-40 meshes, and then subjected to reduction treatment for 2 hours at 450 ℃ in a hydrogen atmosphere, and the sample is used for activity test and is marked as a #11 catalyst (the loading amount of Pt is 0.35%, and the loading amount of Sn is 0.35%).
Application examples 1 to 8 and comparative application examples 1 to 3 fixed bed reaction evaluation
The n-octane dehydrogenation reaction is carried out on a continuous flow fixed bed microreactor, and eleven catalysts of #1, #2, #3, #4, #5, #6, #7, #8, #9, #10 and #11 are used.
Application example 1 the reaction conditions were: normal pressure, 420 ℃ and the mass space velocity of n-octane of 6h -1 The molar ratio of hydrogen to n-octane was 1.33.
The reaction condition of the application example 2 is normal pressure, the temperature is 420 ℃, and the mass space velocity of the n-octane is 6h -1 The molar ratio of carbon monoxide to n-octane was 1.33.
Application example 3 the reaction conditions were normal pressure, temperature was 420 ℃ and mass space velocity of n-octane was 6h -1 The molar ratio of carbon dioxide to n-octane was 1.33.
Application example 4 the reaction conditions were: normal pressure, 420 ℃ and the mass space velocity of n-octane of 6h -1 The molar ratio of nitrogen to n-octane was 1.33.
Application example 5 the reaction conditions were: normal pressure, 420 ℃ and the mass space velocity of n-octane of 6h -1 The molar ratio of nitrogen to n-octane was 1.33.
Application example 6 the reaction conditions were: normal pressure, 420 ℃ and the mass space velocity of n-octane of 6h -1 The molar ratio of nitrogen to n-octane was 1.33.
Application example 7 the reaction conditions were: normal pressure, 420 ℃ and the mass space velocity of n-octane of 6h -1 The molar ratio of nitrogen to n-octane was 1.33.
Application example 8 the reaction conditions were: normal pressure, 420 ℃ and the mass space velocity of n-octane of 6h -1 The molar ratio of nitrogen to n-octane was 1.33.
Comparative application example 1 the reaction conditions were: normal pressure, 420 ℃ and the mass space velocity of n-octane of 6h -1 The molar ratio of nitrogen to n-octane was 1.33.
Comparative application example 2 the reaction conditions were: normal pressure, 420 ℃ and the mass space velocity of n-octane of 6h -1 The molar ratio of nitrogen to n-octane was 1.33.
Comparative application example 3 the reaction conditions were: normal pressure, 420 ℃ and the mass space velocity of n-octane of 6h -1 The molar ratio of nitrogen to n-octane was 1.33.
The product is analyzed by Agilent 7890B gas chromatography and Agilent 7890A oil phase chromatography, the reaction evaluation results are shown in the figures 1-11, and the comparison results are shown in the table 1.
Table 1 application and comparative application examples reaction for 30h reactant conversion and product selectivity results (%)
| Numbering | Catalyst and process for preparing same | Normal octane conversion Chemical conversion rate | Total mono-olefins Selectivity is | 1-octene and 2-octene Total selectivity | Ortho-meta-para-xylene Selectivity is | C8 Cycloolefins and C8 diolefins Selectivity for hydrocarbon | Ethylbenzene separation Selectivity is | Total by-product Selectivity is |
| Application example 1 | Pt-Sn/ZSM-5 （#1） | 21.2 | 92.7 | 60.3 | 3.3 | 2.9 | 1.1 | 7.3 |
| Application example 2 | Pt-La/ZSM-5 （#2） | 19.3 | 78.6 | 46.7 | 8.5 | 9.4 | 4.3 | 21.4 |
| Application example 3 | Pt-Ce/ZSM-5 （#3） | 20.8 | 81.2 | 49.1 | 6.7 | 8.4 | 2.9 | 18.8 |
| Application example 4 | Pt-Ir/ZSM-5 （#4） | 22.7 | 76.9 | 45.8 | 6.6 | 9.8 | 4.7 | 23.1 |
| Application example 5 | Pt-In/ZSM-5 （#5） | 17.5 | 83.2 | 52.6 | 6.3 | 7.9 | 2.2 | 16.8 |
| Application example 6 | Pt-Zn/ZSM-5 （#6） | 16.8 | 82.8 | 48.7 | 5.7 | 7.1 | 2.9 | 17.2 |
| Application example 7 | Pt-Ga/ZSM-5 （#7） | 21.6 | 75.6 | 43.6 | 8.1 | 10.6 | 4.4 | 24.4 |
| Application example 8 | Pt/ZSM-5（# 8） | 15.2 | 69.8 | 33.1 | 13.2 | 8.9 | 8.1 | 30.2 |
| Contrast should be Example 1 | Pt-Sn/ZSM-5 （#9） | 12.9 | 86.2 | 63.2 | 4.2 | 5.8 | 2.6 | 13.8 |
| Contrast should be Example 2 | Pt-Sn/ZSM-5 （#10） | 15.3 | 77.3 | 42.4 | 7.0 | 9.3 | 5.1 | 22.7 |
| Contrast should be Example 3 | Pt-Sn/ZSM-5 （#11） | 14.9 | 63.2 | 33.6 | 10.1 | 18.2 | 9.4 | 36.8 |
As is clear from the results of application examples 1 to 7 and application example 8 in Table 1, the metal promoter can increase the dispersion degree of Pt, improve the dehydrogenation activity, and particularly improve C 5 ~C 10 The dehydrogenation capacity of alkanes. Compared with the comparative application example 1 in which a pore-forming agent is directly added in the in-situ packaging process, and the comparative application example 2 in which the pore is formed first and then the metals Pt and Sn are impregnated, the catalyst is prepared by in-situ packaging first and then the pores are formed, so that the product diffusion is facilitated, the Pt particles are coated by the ZSM-5 molecular sieve, the dispersion degree of Pt is remarkably improved, the agglomeration of Pt in the reaction is inhibited, and the alkane dehydrogenation activity and stability are improved.
Application examples 9 to 13
The difference from application example 1 was that the reaction raw materials were changed, and n-pentane, n-hexane, n-heptane, n-nonane and n-decane were used as the raw materials for the dehydrogenation catalyst. Using the catalyst #1, the reaction conditions of application examples 9 to 13 were the same as those of application example 1. The product is analyzed by Agilent 7890B gas chromatography and Agilent 7890A oil phase chromatography, the reaction evaluation result is shown in the figure of 12-16, and the comparison result of the reactant conversion rate and the product selectivity after reacting for 30 hours is shown in the table 2.
Table 2 results of application examples 9-13 reaction for 30h on reactant conversion and product selectivity (%)
| Numbering | Raw materials | Conversion rate | Total selection of mono-olefinsSelectivity is | Total selectivity of 1-olefin and 2-olefin | Cyclic compound | Cleavage products | Total by-product |
| Application example 9 | N-pentane | 15.3 | 40.2 | 3.1 | 5.3 | 37.2 | 59.8 |
| Application example 10 | N-hexane | 14.2 | 46.8 | 5.2 | 7.4 | 23.6 | 53.2 |
| Application example 11 | N-heptane | 13.4 | 67.2 | 32.1 | 13.5 | 17.8 | 32.8 |
| Application example 12 | N-nonane | 14.8 | 81.1 | 31.6 | 5.6 | 11.7 | 18.9 |
| Application example 13 | N-decane | 13.2 | 80.6 | 28.5 | 6.8 | 12.3 | 19.4 |
As is clear from Table 2, the catalyst of the present invention can be applied to C in naphtha 5 ~C 10 Dehydrogenation is universal, can obtain terminal olefin and has wide application.
Application example 14
The service life test of the n-octane dehydrogenation reaction is carried out on a continuous flow fixed bed microreactor, and the reaction conditions are as follows: normal pressure, 420 ℃ and the mass space velocity of n-octane of 6h -1 The molar ratio of hydrogen to n-heptane was 1.33. Using the #1 catalyst, the product was analyzed by Agilent 7890B gas chromatography and Agilent 7890A oil chromatography and the results of the reaction evaluations are shown in FIG. 17. Specific data corresponding to FIG. 17 are shown in Table 3.
As can be seen from fig. 17 and table 3, the dehydrogenation catalyst of the present invention has good stability, long service life, and can stably operate for 120 hours.
TABLE 3 application example 14 reaction 120h reactant conversion and product selectivity results (%)
| Reaction time (h) | N-octane conversion | Overall mono-olefin selectivity | Total selectivity to 1-octene and 2-octene | O-m-p-xylene selectivity | C8 cycloolefin and C8 diolefin selectivity | Ethylbenzene selectivity | Overall selectivity to by- |
| 6 | 19.3 | 89.6 | 59.8 | 3 | 3.1 | 1.2 | 10.4 |
| 18 | 20.8 | 92.9 | 60.1 | 3.1 | 3 | 1 | 7.1 |
| 24 | 22.4 | 93.2 | 60 | 3.2 | 2.9 | 1.1 | 6.8 |
| 30 | 21.2 | 92.7 | 60.3 | 3.3 | 2.9 | 1.1 | 7.3 |
| 36 | 20.6 | 92.8 | 59.8 | 3 | 3.1 | 1.2 | 7.2 |
| 42 | 20.8 | 92.9 | 60.1 | 3.1 | 3 | 1 | 7.1 |
| 48 | 22.4 | 93.2 | 60 | 3.2 | 2.9 | 1.1 | 6.8 |
| 54 | 21.2 | 92.7 | 60.3 | 3.3 | 2.9 | 1.1 | 7.3 |
| 60 | 20.8 | 93.1 | 59.2 | 4 | 3.1 | 1.2 | 6.9 |
| 66 | 20.8 | 92.9 | 60.1 | 3 | 3 | 1 | 7.1 |
| 72 | 22.4 | 90.7 | 58.9 | 3.2 | 2.9 | 1.1 | 9.3 |
| 78 | 21.2 | 91.2 | 60.3 | 3.3 | 2.9 | 1.1 | 8.8 |
| 84 | 19.3 | 90.2 | 59.8 | 3 | 3.1 | 1.2 | 9.8 |
| 90 | 18.8 | 88.9 | 55.7 | 3.5 | 3 | 1 | 11.1 |
| 96 | 19.4 | 88 | 59.2 | 3.3 | 2.9 | 1.1 | 12 |
| 102 | 17.2 | 87.2 | 54.8 | 4 | 2.9 | 1.1 | 12.8 |
| 108 | 16.8 | 86.7 | 56.8 | 3.5 | 3.1 | 1.2 | 13.3 |
| 114 | 16.9 | 85.8 | 55.9 | 3.5 | 3 | 1 | 14.2 |
| 120 | 15.8 | 85.4 | 55.4 | 3.8 | 2.9 | 1.1 | 14.6 |
Fig. 18 is a transmission electron micrograph of the #1 catalyst, and it can be seen from fig. 18 that no Pt particles are aggregated and no large-particle Pt clusters are formed.
FIG. 19 shows BET adsorption curves of the catalyst #1 in example 1 (formed pores) and the catalyst #11 in comparative example 3 (not formed pores), and it can be seen from FIG. 19 that the hysteresis loop becomes large after pore formation, thus confirming the formation of a mesoporous structure.
It can be seen from the above examples and comparative examples that the present invention provides an alkane dehydrogenation catalyst, a method for preparing the same, and applications thereof, wherein the catalyst provided by the present invention greatly improves the dispersion degree of active metals, and has high dehydrogenation activity and mono-olefin product selectivity, especially alpha-olefin and beta-olefin selectivity, for alkane dehydrogenation reaction.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. C 5 ~C 10 The preparation method of the alkane dehydrogenation catalyst is characterized by comprising the following steps of:
mixing a platinum source solution and a ligand to obtain a precursor solution; the ligand is ethylenediamine, cyclohexylamine or cyclohexanediamine; the precursor solution comprises or does not comprise an auxiliary agent salt; when the precursor solution comprises the auxiliary agent salt, the auxiliary agent metal element In the auxiliary agent salt is one or more of Sn, Ir, La, Ga, Ce, In and Zn;
mixing the precursor solution and a ZSM-5 molecular sieve synthesis matrix solution, carrying out hydrothermal crystallization, and carrying out solid-liquid separation on the obtained crystallization product to obtain a solid product;
carrying out first roasting on the solid product to obtain a roasted product; the temperature of the first roasting is 400-700 ℃, and the heat preservation time is 4-14 h;
mixing the roasted product with an alkali solution, carrying out alkali treatment, and carrying out second roasting on the obtained product to obtain a catalyst precursor; the alkali treatment time is 15-240 min; the temperature of the alkali treatment is 60-90 ℃; or mixing the roasted product with an acid solution, carrying out acid treatment, and carrying out second roasting on the obtained product to obtain a catalyst precursor; the acid treatment time is 15-60 min; the temperature of the acid treatment is 60-90 ℃; the temperature of the second roasting is 350-600 ℃, and the heat preservation time is 3-10 h;
reducing the catalyst precursor to obtain C 5 ~C 10 An alkane dehydrogenation catalyst;
said C is 5 ~C 10 The alkane dehydrogenation catalyst comprises a ZSM-5 molecular sieve and an active component loaded on the ZSM-5 molecular sieve, wherein the active component is platinum, and the ZSM-5 molecular sieve is in a mesoporous structure;
said C is 5 ~C 10 The alkane dehydrogenation catalyst does not include a promoter or includes a promoter.
2. The production method according to claim 1, wherein the platinum source in the platinum source solution is chloroplatinic acid, tetraammineplatinum chloride, ethylenediamine platinum chloride, sodium hexachloroplatinate, or tetrakis (triphenylphosphine) platinum; the molar ratio of the platinum source to the ligand in the precursor solution is 1 (30-200).
3. The method according to claim 1, wherein a molar ratio of the promoter metal element in the promoter salt to the platinum element in the platinum source is 10 or less.
4. The method according to claim 1, wherein the concentration of the acid solution is 0.005 to 1 mol/L; the acid in the acid solution comprises hydrochloric acid, nitric acid or carbonic acid;
the concentration of the alkali solution is 0.005-1 mol/L, and the alkali in the alkali solution comprises sodium hydroxide, potassium carbonate or sodium carbonate.
5. The method of claim 1, wherein the second firing is performed in an air atmosphere.
6. C produced by the production method according to any one of claims 1 to 5 5 ~C 10 An alkane dehydrogenation catalyst.
7. C of claim 6 5 ~C 10 Application of alkane dehydrogenation catalyst in preparation of mono-olefin by catalyzing alkane dehydrogenation, wherein alkane is C 5 ~C 10 Of (a) an alkane.
8. The use of claim 7, wherein the conditions for catalytic alkane dehydrogenation to produce mono-olefins comprise: the reaction temperature is 320-500 ℃, and the mass space velocity is 0.2-12 h -1 (ii) a The reaction atmosphere comprises one or more of nitrogen, hydrogen, carbon monoxide and carbon dioxide, and the ratio of the molar amount of the gas providing the reaction atmosphere to the molar amount of the alkane is below 5.
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