CN106925279A - A kind of Fe systems selective hydrogenation catalyst, preparation method and applications - Google Patents
A kind of Fe systems selective hydrogenation catalyst, preparation method and applications Download PDFInfo
- Publication number
- CN106925279A CN106925279A CN201511032668.5A CN201511032668A CN106925279A CN 106925279 A CN106925279 A CN 106925279A CN 201511032668 A CN201511032668 A CN 201511032668A CN 106925279 A CN106925279 A CN 106925279A
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- Prior art keywords
- catalyst
- carrier
- temperature
- selective hydrogenation
- preparation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 158
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims description 15
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- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 20
- 150000001361 allenes Chemical class 0.000 claims abstract description 9
- 239000010970 precious metal Substances 0.000 claims abstract description 7
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 42
- 239000007789 gas Substances 0.000 claims description 28
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002803 maceration Methods 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
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- 239000003795 chemical substances by application Substances 0.000 claims description 7
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- 229910003145 α-Fe2O3 Inorganic materials 0.000 claims description 6
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- 238000001354 calcination Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
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- VCRLKNZXFXIDSC-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[Al+3].[Zr+4] VCRLKNZXFXIDSC-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 43
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 17
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000002386 leaching Methods 0.000 description 4
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910021329 Fe4Al13 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
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- 229910002796 Si–Al Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
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- 239000008236 heating water Substances 0.000 description 2
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- 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 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 229910052703 rhodium Inorganic materials 0.000 description 2
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
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- 229910002515 CoAl Inorganic materials 0.000 description 1
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- 206010013786 Dry skin Diseases 0.000 description 1
- 229910021328 Fe2Al5 Inorganic materials 0.000 description 1
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- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910015370 FeAl2 Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910017771 LaFeO Inorganic materials 0.000 description 1
- 229910002321 LaFeO3 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
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- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 description 1
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 1
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- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
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- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
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- 229910052747 lanthanoid Inorganic materials 0.000 description 1
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- 150000002736 metal compounds Chemical class 0.000 description 1
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- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B01J35/613—
-
- B01J35/615—
-
- B01J35/633—
-
- B01J35/635—
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- 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
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- 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
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
- C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The present invention relates to a kind of Fe systems selective hydrogenation catalyst, catalyst activity component Fe contents account for 2~15 (wt) %, X contents and account for 0~2 (wt) %, and X is selected from one or several in K, La, Ce.Remaining is oxygen element and carrier.Catalyst specific surface is 10~300m2/ g, pore volume is 0.2~0.65ml/g.Catalyst of the present invention can be used for C2~3The selective hydrogenation of acetylene, propine and allene (MAPD) in cracking cut.The catalyst has gentle hydrogenation activity and excellent olefine selective, and alkene increment is high, and operating flexibility is good, and " green oil " growing amount is low, and long-term operation performance is good.And catalyst cost is far below precious metals pd catalyst.
Description
Technical field
The present invention relates to a kind of Fe systems selective hydrogenation catalyst and its preparation method and application, in the cracking cut of carbon two
Contained acetylene and propine (MA), allene (PD) selective hydrogenation prepare ethene, propylene.
Background technology
Ethene, propylene are one of most important basic materials of petro chemical industry, as the monomer for synthesizing various polymer,
The overwhelming majority is obtained by petroleum hydrocarbon (such as ethane, propane, butane, naphtha and light diesel fuel) steam cracking.Obtained through this method
To the C2 cuts based on ethene in also containing 0.5%~2.5% (molar fraction) acetylene.The presence of acetylene can make ethene
Polymerization process complicate, deteriorate polymer performance.When polyethylene is produced with high-pressure process, due to the accumulation of acetylene, have quick-fried
Fried danger；In addition, when polyethylene is produced, the presence of acetylene can also reduce polymerization catalyst, increase disappearing for catalyst
Consumption.So the acetylene in ethene must be dropped to below certain value, could be used as the monomer of synthetic high polymer.
Precious metals pd series hydrocatalyst, the acetylene and C3 being selectively removed in C2 cuts is generally used to evaporate in industry at present
Propine (MA), allene (PD) in point.Patent US4404124 is prepared for active component palladium shell and is distributed by step impregnation method
Selective hydrogenation catalyst, the selection hydrogenation of carbon two, C3 fraction is can be applied to, with eliminating acetylene and propylene in ethene
Propine allene.With aluminum oxide as carrier, regulation co-catalyst silver is acted on US5587348 with palladium, adds alkali metal, chemical bonding
Fluorine be prepared for the C2 hydrogenation catalyst of function admirable.The catalyst has reduction green oil generation, improves ethylene selectivity, subtracts
The characteristics of few oxygenatedchemicals growing amount.US5519566 discloses a kind of method that wet reducing prepares silver and palladium catalyst, leads to
The addition organic or inorganic reducing agent in maceration extract is crossed, silver and palladium bi-component selective hydrogenation catalyst is prepared.
Due to using precious metals pd as active component, catalyst cost remains high, and noble metal catalyst due to
It is active high, gone into operation stability in device, there are some problems in operating flexibility and catalyst long-term operation aspect of performance.Research and development valency
The hydrogenation catalyst system of New Type of Carbon two that lattice are cheap, performance is remarkable, is always the target of field scientific research personnel effort.
CN2005800220708.2 discloses the selection hydrogenation catalyst of acetylene and alkadienes in a kind of light olefin raw material
Agent, the catalyst by selected from copper, the first component of gold, silver and selection nickel, platinum, palladium, iron, cobalt, ruthenium, rhodium second component group
Into catalyst also includes at least one inorganic salts and oxide selected from zirconium, lanthanide series and alkaline earth metal compound in addition.Urge
Agent calcining, using or regeneration after form fluorite structure.Catalyst oxide total content 0.01~50%, preferably sintering temperature
700~850 DEG C.By adding the third oxide, modified aluminas or silica support, help to increase catalyst choice
With active, the selectivity after regeneration.The technology be still with copper, gold, silver, palladium etc. as active component, nickel, platinum, palladium, iron, cobalt,
Ruthenium, rhodium etc., by the oxide modifying to carrier, improve the regenerability of catalyst as component is helped.
CN102218323A discloses a kind of hydrogenation catalyst of unsaturated hydrocarbons, and active component is 5~15% nickel oxide
With the mixture of 1~10% other metal oxides, other metal oxides can be in molybdenum oxide, cobalt oxide and iron oxide
One or several, additionally include 1~10% auxiliary agent.The inventive technique is mainly used in second in coal-to-oil industry tail gas
The hydro-conversions such as alkene, propylene, butylene are saturated hydrocarbons, with good deep hydrogenation ability.The technology be mainly used in rich in CO and
The full hydrogenation of ethene, propylene, butylene etc. in the various industrial tail gas of hydrogen, is not suitable for the selection hydrogenation of alkynes, alkadienes.
ZL201080011940.0 discloses between a kind of ordered cobalt-aluminium and iron-aluminium compound as acetylene hydrogenation catalyst,
Described intermetallic compound is selected from by CoAl, CoAl3、Co2Al5、Co2Al9、o-Co4Al13、h-Co4Al13、m-Co4Al13、
FeAl、FeAl2、Fe3Al、Fe2Al5、Fe4Al13The group of composition.Wherein preferred Fe4Al13And o-Co4Al13.Change between described metal
Compound is prepared using the heat melting method in solid state chemistry.Catalyst hydrogenation performance test is carried out in quartz tube furnace, instead
Temperature 473K is answered, after stabilization reaction 20h, o-Co4Al13Catalyst conversion of alkyne reaches 62%, and ethylene selectivity reaches 71%,
Fe4Al13Conversion of alkyne reaches 40% on catalyst, and ethylene selectivity reaches 75%.The technology is to prepare under the high temperature conditions
Intermetallic compound, for the selective hydrogenation of acetylene, conversion of alkyne is low, and reaction temperature is high, is unfavorable for industrial applications.And
And catalyst is prepared using heat melting method, condition is harsh.
In sum, the selective hydrogenation of low-carbon (LC) alkynes and alkadienes, mainly uses noble metal catalyst at present, for non-
Extensive work is carried out in the research and development of noble metal catalyst, but still has far distance apart from industrial applications.In order to solve this
Problem, the present invention provides a kind of new Fe series hydrocatalysts and preparation method thereof.
The content of the invention
It is an object of the invention to provide a kind of Fe series catalysts, add for alkynes in C-2-fraction and diene hydrocarbon-selective
Hydrogen.Using catalyst of the invention, contained a small amount of acetylene and propine (MA), allene (PD) in cracking atmosphere can be selected
Selecting property is hydrogenated with, and is converted into ethene, propylene.Ethene, propylene refining reaction are can be used for, will be contained in ethene, propylene feedstocks gas
Trace acetylene and propine (MA), allene (PD) are removed completely, for producing polymer grade raw material.
In order to achieve the above object, the present invention uses following technical scheme：It is non-with high-temperature inorganic oxide as carrier
Noble metal catalyst, in terms of catalyst quality 100%, catalyst contains Fe 2~15%, and preferred content is accounted for for 4~10%, X contents
0~2%, wherein X be selected from K, La, Ce in one or several, X preferred contents be 0.2~1.5%；Catalyst specific surface is
10~300m2/ g preferably 30~170m2/ g, pore volume is 0.2~0.65ml/g, and preferably 0.30~0.63ml/g, wherein Fe are to pass through
Impregnation method is loaded with carrier, through 300 DEG C~700 DEG C roastings, is reduced at a temperature of 250~500 DEG C with the atmosphere of hydrogen
It is obtained, the Fe elements in catalyst are main with α-Fe2O3Form is present.
Fe elements can be with Fe, Fe in catalyst of the invention2O3、Fe3O4, the variform such as FeO exist, but wherein α-
Fe2O3The Fe of form is higher than the content of other forms, preferably accounts for more than the 50% of Fe gross masses.
Carrier of the invention is high-temperature inorganic oxide, key problem in technology of the invention be containing Fe in catalyst, and
Roasting and reduction process are have passed through, to carrier and is had no special requirements, such as can be aluminum oxide, silica, zirconium oxide, magnesia
In one or more.But but most common is also most preferably aluminum oxide or alumina series carrier, alumina series carrier refers to
The complex carrier of aluminum oxide and other oxides, wherein aluminum oxide accounts for more than the 50% of carrier quality, such as can be aluminum oxide with
The compound of the oxides such as silica, zirconium oxide, magnesia, preferably alumina-zirconia composite carrier, wherein aluminum oxide contain
Amount is more than 60%.Aluminum oxide can be θ, α, γ type or the mixture of its various crystal formation, preferably α-Al2O3Or-the Al containing α2O3
Mixing crystal formation aluminum oxide.
Present invention also offers the preparation method of the catalyst：
Catalyst distinguishes impregnated carrier, is aged respectively, does by preparing the Fe predecessors aqueous solution, the X predecessor aqueous solution
It is dry, roasting or with after its mixed solution impregnated carrier be aged, dry, roasting, finally reduction obtain.
Preferred condition is in preparation method of the present invention：
30~60 DEG C of dipping temperature, 10~60min of dip time, maceration extract pH value 1.5~5.0, Aging Temperature 30~60
DEG C, 30~120min of digestion time, 400 DEG C~500 DEG C of sintering temperature, 180~300min of roasting time.
Dried in the present invention and be preferably temperature programming drying, drying temperature program setting is：
Roasting is activation process in the present invention, preferably temperature-programmed calcination, and sintering temperature program setting is：
Heretofore described catalyst can be sprayed using incipient impregnation, excessive dipping, surface, vacuum impregnation and repeatedly
It is prepared by any one impregnation method in infusion process.
The method for preparing catalyst that the present invention recommends is comprised the following steps that：
(1) carrier is weighed after measurement carrier water absorption rate.
(2) a certain amount of Fe predecessors (recommending soluble nitrate, chloride or sulfate) are accurately weighed by load capacity,
According to carrier water absorption rate and dipping method, dipping solution, and regulation maceration extract pH value 1.5~5.0 on request are prepared, and by solution
Be heated to 30~60 DEG C it is standby.
(3) using incipient impregnation or when spraying method, the carrier that will can be weighed is put into rotary drum, adjusts rotary drum rotating speed
25~30 turns/min, it is totally turned over carrier, the maceration extract of 30~60 for preparing DEG C is poured into or sprayed with given pace
It is spread across on carrier, loads 5~10min.
During using excessive infusion process, the carrier that will be weighed is placed in container, is subsequently adding 30~60 DEG C of preparation of dipping
Solution, the visibly moved device of Quick shaking, liberated heat discharges rapidly in making adsorption process, and makes active component uniform load to carrier
On, standing 5~10min makes surface active composition be balanced with active component competitive Adsorption in solution.
During using vacuum impregnation technology, the carrier that will be weighed is placed in cyclonic evaporator, is vacuumized, and adds 30~60 DEG C
Maceration extract impregnates 5~10min, and heating water bath to carrier surface moisture is completely dried.
(4) catalyst for having impregnated is moved into container, and catalyst aging 30~120min is carried out at 25~60 DEG C.
(5) solution unnecessary after dipping is leached, is then dried using the method for temperature programming in an oven, dried
Temperature program(me)：
(6) dried catalyst is calcined in Muffle furnace or tube furnace and is activated, be calcined heating schedule：
Catalyst component X is loaded using above-mentioned same steps, 300~700 DEG C of sintering temperature, preferably 400~500
DEG C, two kinds of components can also be configured to mixed solution, disposably be impregnated to carrier surface according to above-mentioned steps.
Present invention reduction refers to that catalyst uses preceding, it is necessary to be reduced with hydrogen-containing gas, H2Content is preferably 10~50%, also
Former temperature is preferably 250~500 DEG C, 240~360min of recovery time, 100~500h of volume space velocity-1, reduction pressure 0.1~
0.8MPa；The condition of recommendation is to use N2+H2Gaseous mixture is reduced for 300~400 DEG C under the conditions of pressure-fired, and the recovery time is most
It is well 240~360min, the best 200~400h of volume space velocity~1, reduce pressure and be preferably 0.1~0.5MPa.
The active component of catalyst is mainly Fe in the present invention, is non-precious metal catalyst, it might even be possible to without cobalt, nickel,
Molybdenum, tungsten, greatly reduce cost, and catalyst cost is far below precious metals pd catalyst.
Fe elements can be with Fe, Fe in catalyst of the present invention2O3、Fe3O4, several forms are present in FeO, pushed away in the present invention
One or several in adding K, La, Ce in the activity composition of iron content are recommended, is conducive to the formation of activation of catalyst phase, divided
Dissipate, and be conducive to activating the stabilization of phase, improve catalyst choice and anticoking capability.
The activity composition of the activation temperature of catalyst and catalyst, content and carrier related, activated mistake in the present invention
α-Fe are formd after journey2O3The Fe of form, and it is relatively stable, and activation temperature can not be too high；On the other hand, its activation degree is again
Determine the reducing condition of catalyst, provided in the present invention in the catalyst for using still with α-Fe2O3The Fe of form for it is main into
Point, undue reduction can influence the effect of catalyst, influence selectivity, easy coking on the contrary.
Catalyst of the present invention has the advantages that：
(1) catalyst cost of the present invention is far below precious metals pd catalyst, the harmless easy acquirement of raw materials, and prepares
Method is simple, technically easily realizes.
(2) catalyst hydrogenation activity of the present invention is gentle, and operating flexibility is good, is suitable to industrialized unit application.
(3) catalyst choice of the present invention is good, and alkene increment is higher than noble metal catalyst.
(4) catalyst " green oil " growing amount of the present invention is far below noble metal catalyst, is suitable to catalyst long period fortune
OK.
Fe systems of the invention selective hydrogenation catalyst is best suited for contained acetylene and propine, the choosing of allene in ethene atmosphere
Selecting property hydrogenation and removing.
Brief description of the drawings
Fig. 1 is using the catalyst XRD spectra of the embodiment of the present invention 3 (deduction vector background)；
Fig. 2 is the catalyst XRD spectra of comparative example 2 (deduction vector background)；
Fig. 3 is the catalyst XRD spectra of comparative example 5 (deduction vector background)；
XRD determining condition：
German Brooker company D8ADVANCE X diffractometers
Tube voltage：40kV electric currents 40mA
Scanning：0.02 ° of step-length, 4 °~120 ° of frequency 0.5s sweep limits, 25 DEG C of temperature
The wavelength of Cu K α 1, abscissa is the θ of the angle of diffraction 2 in figure, and ordinate is diffracted intensity
Symbol description in Fig. 1：
● it is α-Fe2O3, ▲ be Fe3O4, ◆ it is CeO；
Symbol description in Fig. 2：
● it is α-Fe2O3, ▲ be Fe3O4, ■ is LaFeO3；
Symbol description in Fig. 3：
▲ it is Fe3O4, ▼ is Ce, and ★ is α-Fe；
As can be seen that Fe is main with α-Fe in catalyst in Fig. 12O3Form occurs, relative amount 7.6%；
Second component La in catalyst is can be seen that in Fig. 2, mainly LaFeO is combined to form with ferriferous oxide3, help group
Divide and sintered with active component, destroy Active components distribution and structure, catalyst activity reduction；
α-Fe are free of in Fig. 32O3Phase, Fe mainly with simple substance α-Fe forms occur, relative amount 8.92%, third component with
Simple substance Ce forms occur.
Specific embodiment
Analysis test method：
Specific surface：GB/T-5816
Pore volume：GB/T-5816
Different crystal forms Fe oxide contents：XRD
Active component content in catalyst：Atomic absorption method
Conversion ratio and selectivity are calculated by formula below in embodiment：
Conversion of alkyne (%)=100 × △ acetylene/entrance acetylene content
Ethylene selectivity (%)=100 × △ ethene/△ acetylene
Embodiment 1
The trifolium-shaped alpha-alumina supports 100ml of 4.5 × 4.5mm of Φ is weighed, is placed in 1000ml beakers.Take nitric acid
Iron, heating for dissolving in 60ml deionized waters, adjust pH value 2.5, maceration extract temperature 50 C, incipient impregnation in carrier surface,
Rapid shake carrier impregnation 6min, stands 30min to adsorption equilibrium, beaker mouthful is fully sealed with preservative film, in 60 DEG C of water-baths
Ageing 30min, then in an oven according to program：Drying catalyst,
Catalyst is moved into evaporating dish, activation of catalyst, activation procedure are carried out using programmed temperature method in Muffle furnace： Weigh lanthanum nitrate,
Impregnated according to above-mentioned preparation process.Catalyst physical property is as shown in table 1.
Evaluation method：
Catalyst performance evaluation is carried out on 10ml micro-reactors, catalyst is crushed in mortar, takes 10~20 mesh sieves point
3ml, is diluted to 5ml and is loaded with 20 mesh beades.
Catalyst is first reduced with the nitrogen of 40% hydrogen+60%, 320 DEG C of reduction temperature, pressure 0.5MPa, recovery time
4h。
Reaction condition：Volume space velocity 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas, constitute as follows：
Prepare catalyst physical property as shown in table 1, reaction result is as shown in table 2.
Embodiment 2
At 50 DEG C, by NaAlO2Solution and ZrCl4Solution stirring mixing, is then neutralized with salpeter solution, stirs 10h, coprecipitated
Form sediment the uniform Al-Zr particles of generation.Product is filtered, Na therein is washed with deionized+And Cl-Ion, is subsequently adding suitable
Amount mass concentration be 15% polyvinyl alcohol as pore creating material, it is kneaded and formed.130 DEG C dry 2h, and 650 DEG C of roasting 4h obtain Zr-
Al complex carriers, aluminum oxide and zirconium oxide mass ratio are 4 in carrier:1.
Complex carrier 100ml is weighed, is placed in 1000ml large beakers.Iron chloride and potassium chloride are taken, heating for dissolving is in 100ml deionizations
In water, pH value 2.0 is adjusted, 80 DEG C of maceration extract temperature is excessively impregnated on carrier, shake beaker dipping 10min filters unnecessary maceration extract,
Catalyst is aged 50min in 60 DEG C of water-baths, then in an oven according to program：
Drying catalyst, evaporating dish is moved into by catalyst, and activation of catalyst is carried out using programmed temperature method in Muffle furnace, activates journey
Sequence：Catalyst thing
Property is as shown in table 1.
Evaluating catalyst is carried out using the same procedure of embodiment 1, is reduced with 30% hydrogen, 340 DEG C of reduction temperature, pressure
Power 0.5MPa, recovery time 4h.
Reaction condition：Volume space velocity 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas, constitute as follows：
Reaction result is as shown in table 2.
Embodiment 3
Weigh the ball-type alpha-alumina supports 100ml of Φ 1.5mm.Take ferric nitrate to be dissolved in 40ml deionized waters, adjust pH value
3.0,40 DEG C of maceration extract temperature, watering can is sprayed on carrier, and 10min is loaded in rotary drum makes active component upload uniformly, loading process
Control is completed in 6min, then in an oven according to program：Drying catalysis
Agent, evaporating dish is moved into by catalyst, and activation of catalyst, activation procedure are carried out using programmed temperature method in Muffle furnace： A leaching is obtained to urge
Agent.
Using first step same procedure, cerous nitrate is taken, is sprayed after dissolving to a leaching catalyst surface, then dried, be calcined,
Obtain final catalyst.Drying program：Calcination procedure：It is catalyzed after reduction
Agent XRD analysis are as shown in Figure 1.
Catalyst physical property is as shown in table 1.
Evaluated using the same procedure of embodiment 1, catalyst is reduced with 20% hydrogen, 360 DEG C of reduction temperature, pressed
Power 0.5MPa, recovery time 4h.
Reaction condition：Volume space velocity 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas, constitute as follows：
Reaction result is as shown in table 2.
Embodiment 4
Ball-aluminium oxide-the titanium dioxide carrier of the Φ 2.0mm of 50ml is weighed, is placed in rotary evaporator.Ferric nitrate is taken to be dissolved in
In 15ml deionized waters, regulation pH value 3.5 is standby.Rotary evaporator vacuum pumping pump is opened, to vacuum 0.1mmHg, then from charge door
The maceration extract for preparing is slowly added to, 5min is added, rotation is evaporated to catalyst surface mobile moisture and disappears completely under 60 DEG C of heating water baths
Lose, complete load, the catalyst that will have been loaded removes rotary evaporator, in an oven according to program： Drying, in Muffle furnace according to： Roasting.Obtain a leaching catalyst.
Lanthanum nitrate is taken, is impregnated according to above-mentioned same procedure, then dried, be calcined, obtain final catalyst.Dry journey
Sequence：Calcination procedure：
Catalyst physical property is as shown in table 1.
Evaluated using the same procedure of embodiment 1, catalyst is reduced with 15% hydrogen, 380 DEG C of reduction temperature, pressed
Power 0.5MPa, recovery time 4h.
Reaction condition：Volume space velocity 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas, constitute as follows：
Prepare catalyst physical property as shown in table 1, reaction result is as shown in table 2.
Embodiment 5
The alumina support of 100ml Φ 4.0mm is weighed, catalyst is prepared using the same procedure of embodiment 3.Activation temperature
650℃。
Catalyst physical property is as shown in table 1.
Catalyst is reduced with 25% hydrogen, 700 DEG C of temperature, pressure 0.5MPa, soak time 4h.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Volume space velocity 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane Balance Air), constitute as follows：
Prepare catalyst physical property as shown in table 1, reaction result is as shown in table 2.
Embodiment 6
By commercially available boehmite, silica gel, zirconium oxychloride powder and extrusion aid according to aluminum oxide：Silica：Zirconium oxide=
8:1:3 ratios are well mixed, then the extruded moulding on banded extruder, 120 DEG C of dryings, and 550 DEG C of roasting 3h, obtain in Muffle furnace
Zr-Si-Al composite oxide carriers.
The Zr-Si-Al carriers of 50ml preparations are weighed, catalyst is prepared using the same procedure of embodiment 4.
Catalyst physical property is as shown in table 1.
Catalyst carries out high-temperature activation in tube furnace, and activation phenomenon is the nitrogen of 45% hydrogen+55%, 450 DEG C of temperature, pressure
Power 0.5MPa, soak time 4h.Prepare catalyst physical property as shown in table 1.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Volume space velocity 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane is Balance Air), constitute as follows：
Reaction result is as shown in table 2.
Embodiment 7
The aluminum oxide for taking Φ 4.0mm makees carrier, and catalyst is prepared using the same procedure of embodiment 1, is lived at 450 DEG C
Change.
Catalyst is reduced, 450 DEG C of temperature, pressure 0.5MPa, soak time 4h using preceding with 20% hydrogen.Using
The same procedure of embodiment 1 is evaluated.
Reaction condition：Volume space velocity 8000h-1, pressure 2.5MPa, 50 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane Balance Air), constitute as follows：
Prepare catalyst physical property as shown in table 1, reaction result is as shown in table 2.
Comparative example 1
Φ 4.0mm alumina supports are taken, specific surface is 4.5m2/ g, pore volume is 0.32ml/g.Using equi-volume impregnating,
By on silver nitrate solution incipient impregnation to carrier, ageing-dry-roasting obtains a leaching catalyst, then that palladium bichloride is molten
Solution, incipient impregnation, ageing-dry-roasting obtains final catalyst (petrochemical industry research institute PAH-01 hydrogenation catalysts).Catalysis
Agent Pd contents are that 0.050%, Ag contents are 0.20%.
Catalyst uses hydrogen reducing 160min, pressure 0.5MPa, hydrogen volume air speed 100h at 100 DEG C-1。
Evaluate unstripped gas composition：
Prepare catalyst physical property as shown in table 1, reaction result is as shown in table 2.
Comparative example 2
Carrier is made with Φ 4.0mm aluminum oxide, catalyst, catalyst activation temperature are prepared using the identical method of embodiment 1
850℃。
Catalyst is reduced with 25% hydrogen, 450 DEG C of temperature, pressure 0.5MPa, time 4h.Reduction rear catalyst
XRD diffraction spectrograms are as shown in Figure 2.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Volume space velocity 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane Balance Air), constitute as follows：
Prepare catalyst physical property as shown in table 1, reaction result is as shown in table 2.
Comparative example 3
The aluminum oxide for weighing Φ 4.0mm makees carrier, and catalyst is prepared using the same procedure of embodiment 1, is lived at 450 DEG C
Change.
Catalyst is reduced with 35% hydrogen, 450 DEG C of temperature, pressure 0.5MPa, soak time 4h.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Volume space velocity 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane Balance Air), constitute as follows：
Prepare catalyst physical property as shown in table 1, reaction result is as shown in table 2.
Comparative example 4
The same catalyst of Example 1, directly drives after being activated at 450 DEG C, is reduced without hydrogen.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Volume space velocity 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane Balance Air), constitute as follows：
Prepare catalyst physical property as shown in table 1, reaction result is as shown in table 2.
Comparative example 5
The same catalyst of Example 1, in 450 DEG C of activation.
Catalyst is reduced in tube furnace, and atmosphere is the nitrogen of 30% hydrogen+55%, 850 DEG C of temperature, pressure
0.5MPa, soak time 4h.The XRD diffraction spectrograms for reducing rear catalyst are as shown in Figure 3.
Prepare catalyst physical property as shown in table 1.
Evaluated using the same procedure of embodiment 1.
Reaction condition：Volume space velocity 8000h-1, pressure 1.5MPa, 80 DEG C of reaction temperature.
Reactor feed gas use calibrating gas (ethane is Balance Air), constitute as follows：
Reaction result is as shown in table 2.
The carrier of table 1 and catalyst physical property
The catalyst of table 2 is to C2-3Cracking material selection hydrogenation result
Note：Acetylene and ethene gather and generation n-butene, further gather and generate " green oil ", are generally given birth to n-butene in analysis
Catalyst green oil is levied into scale " growing amount.
Claims (10)
1. a kind of Fe systems selective hydrogenation catalyst, is non-precious metal catalyst, it is characterised in that in terms of catalyst quality 100%,
Catalyst contains Fe 2~15%, and preferred content is 4~10%, X 0~2%, and wherein X is selected from a kind of or several in K, La, Ce
Kind, X preferred contents are 0.2~1.5%；Catalyst specific surface is 10~300m2/ g, preferably 30~170m2/ g, pore volume be 0.2~
0.65ml/g, preferably 0.30~0.63ml/g, wherein Fe are loaded with carrier, through 300 DEG C~700 DEG C roastings by impregnation method
Burn, reduced at a temperature of 250~500 DEG C with the atmosphere of hydrogen and be obtained；In catalyst, Fe is mainly with α-Fe2O3Form is present.
2. Fe systems selective hydrogenation catalyst according to claim 1, it is characterised in that：In catalyst, α-Fe2O3The Fe of form
Account for more than the 50% of Fe gross masses.
3. Fe systems selective hydrogenation catalyst according to claim 1, it is characterised in that：Carrier is that aluminum oxide or alumina series are carried
Body, alumina series carrier refers to the complex carrier of aluminum oxide and other oxides, wherein aluminum oxide account for the 50% of carrier quality with
On, the alumina series carrier is aluminum oxide and silica, zirconium oxide, the preferably compound of magnesia, aluminium oxide-zirconium oxide
Complex carrier, wherein alumina content is more than 60%；Aluminum oxide is the mixture of θ, α, γ type or its various crystal formation, preferably
α-Al2O3Or-the Al containing α2O3Mixing crystal formation aluminum oxide.
4. Fe systems selective hydrogenation catalyst according to claim 1, it is characterised in that the impregnation method be incipient impregnation,
Excessive dipping, surface are sprayed, vacuum impregnation or multiple dipping.
5. the preparation method of any Fe systems selective hydrogenation catalysts of a kind of claim 1-4, it is characterised in that：Catalyst
Preparation process includes：The aqueous solution of predecessor containing Fe, the maceration extract of the X predecessor aqueous solution are prepared, impregnated carrier, difference are old respectively
Change, dry, being calcined or with ageing, dry, roasting, finally reduction acquisition after its mixed solution impregnated carrier.
6. preparation method according to claim 5, it is characterised in that：30~60 DEG C of dipping temperature, dip time 10~
60min, maceration extract pH value 1.5~5.0,30~60 DEG C of Aging Temperature, 30~120min of digestion time, 300 DEG C of sintering temperature~
700 DEG C, preferably 180~300min of roasting time, 400~500 DEG C.
7. preparation method according to claim 5, it is characterised in that：Dry as temperature programming is dried, drying temperature program
It is set as：
8. preparation method according to claim 5, it is characterised in that：It is roasted to temperature-programmed calcination, sintering temperature program
It is set as：
9. preparation method according to claim 5, it is characterised in that：Catalyst reduction refers to that catalyst uses preceding, roasting
Catalyst afterwards is reduced with hydrogen-containing gas, H2Volume content is preferably 10~50%, 250~500 DEG C of reduction temperature, recovery time
240~360min, 100~500h of volume space velocity-1, 0.1~0.8MPa of reduction pressure；Optimum condition is to use N2+H2Gaseous mixture enters
Row reduction, is reduced, 200~400h of volume space velocity at 300~400 DEG C-1, reduce pressure and be preferably 0.1~0.5MPa.
10. the application of Fe systems selective hydrogenation catalyst described in a kind of claim 1, it is characterised in that：Fe systems select hydrogenation catalyst
Agent is used for contained acetylene and propine, the selective hydrogenation and removing of allene in ethene atmosphere.
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