CN108927173B - Alkyne selective hydrogenation catalyst and preparation method and application thereof - Google Patents
Alkyne selective hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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- CN108927173B CN108927173B CN201810887717.0A CN201810887717A CN108927173B CN 108927173 B CN108927173 B CN 108927173B CN 201810887717 A CN201810887717 A CN 201810887717A CN 108927173 B CN108927173 B CN 108927173B
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- Prior art keywords
- catalyst
- alkyne
- carrier
- solution
- palladium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 128
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 95
- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 102
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical group [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 26
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 15
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000605 extraction Methods 0.000 claims abstract description 14
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 150000001340 alkali metals Chemical class 0.000 claims description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 24
- 239000012266 salt solution Substances 0.000 claims description 24
- 229910052783 alkali metal Inorganic materials 0.000 claims description 23
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 23
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 230000032683 aging Effects 0.000 claims description 13
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 238000004537 pulping Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 230000004048 modification Effects 0.000 claims description 8
- 238000012986 modification Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 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 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
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 229910052745 lead Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 4
- 229910052792 caesium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052701 rubidium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 241000219793 Trifolium Species 0.000 claims description 3
- 150000000475 acetylene derivatives Chemical class 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 238000007865 diluting Methods 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
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- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
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- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 2
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- 239000001119 stannous chloride Substances 0.000 claims description 2
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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Abstract
The invention belongs to the technical field of petrochemical industry, and particularly relates to an alkyne hydrogenation selective catalyst, and a preparation method and application thereof. The catalyst is composed of an active component, a cocatalyst component and a carrier, wherein the active component is palladium, the cocatalyst component for improving the hydrogenation stability and selectivity of the catalyst is added, and the cocatalyst component is introduced into the catalyst in different ways, so that the surface acidity of the catalyst is reasonably regulated and controlled, and the dispersion of the active component palladium is promoted to form more active sites. The catalyst is suitable for selective hydrogenation of alkyne-containing materials, particularly for selective hydrogenation of high alkyne content carbon-IV materials discharged by a butadiene extraction device, vinylacetylene and ethylacetylene are converted into butadiene and butylene, and hydrogenated products are returned to a raw material storage tank or the butadiene extraction device to recover the butadiene and the butylene. The catalyst has the advantages of mild hydrogenation reaction conditions, high activity and selectivity, particularly good stability and long running period, and is suitable for hydrogenation of materials with high alkyne content.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to an alkyne hydrogenation selective catalyst, and a preparation method and application thereof.
Background
Butadiene is an important petrochemical basic organic raw material and a synthetic rubber monomer, is one of the most important components in the four-carbon fraction, and has the second place in petrochemical olefin raw materials to ethylene and propylene. The butadiene is mainly obtained by separating a byproduct mixed carbon four of an ethylene device as a raw material by a solvent extraction method. The mixed carbon four fraction by-produced in ethylene plants usually contains 40-60 wt% butadiene, 0.5-2.0 wt% alkynes, mainly including Methylacetylene (MA), Ethylacetylene (EA) and Vinylacetylene (VA), and the others are butanes (n-butane and isobutane) and butenes (n-butene, isobutene, trans-butene-2 and cis-butene-2).
At present, Acetonitrile (ACN), N-methylpyrrolidone (NMP) or Dimethylformamide (DMF) are mainly used as a solvent for extracting butadiene in industry, and the extracted butadiene can meet the requirement of purity of the butadiene as a polymerization monomer. Under the influence of factors such as cracking depth, cracking technology and the like, the alkyne content in the mixed carbon four tends to increase gradually, and in order to ensure the purity of butadiene, the extraction depth needs to be increased, so that the energy consumption of the device is increased, the discharge amount of alkyne-containing tail gas (mainly comprising vinyl acetylene, butadiene and butylene) is increased, the yield of butadiene is reduced, and the economy of the device is deteriorated. Because the acetylene-containing tail gas contains a large amount of vinyl acetylene (generally 20-35 wt%), the acetylene-containing tail gas has large flammable and explosive risks and low industrial application value, and is generally diluted by other carbon tetrads or methane and then discharged into a torch for combustion or sold as low-value fuel. If the alkyne-containing tail gas is treated, a large amount of butadiene and butylene can be recovered, the potential safety hazard caused by the emission of the alkyne-containing tail gas can be eliminated, and the aim of changing waste into valuable is fulfilled.
The acetylene-containing tail gas is treated by mainly adopting a catalytic selective hydrogenation method, and a high-selectivity hydrogenation catalyst is utilized to convert vinyl acetylene contained in the tail gas into 1, 3-butadiene, convert ethyl acetylene into butylene and generate a small amount of butane. The acetylene-containing tail gas after hydrogenation is separated from non-condensable gas and then returns to a raw material storage tank to be mixed with the raw material or directly returns to a butadiene extraction device to recover butadiene and butylene, so that the purity of butadiene is improved, the loss of butadiene is reduced, the acetylene-containing tail gas is well utilized, and the emission of the acetylene-containing tail gas is eliminated.
One of the keys of the selective hydrogenation technology for acetylene-containing tail gas is a catalyst, which is required to have high hydrogenation activity and selectivity, and particularly to have good running stability, i.e. acetylene hydrocarbon in the tail gas is removed to a low level (can be directly returned to a butadiene device as an extraction raw material), vinyl acetylene is ensured to be converted into 1, 3-butadiene as much as possible to recover butadiene to the maximum extent, and the catalyst is required to have high stability, good water resistance, solvent resistance, heavy component and other impurities, and long running stability so as to meet the requirement of long-period running of an industrial device.
At present, the selective hydrogenation catalyst for acetylene-containing tail gas is mainly a noble metal catalyst and a non-noble metal catalyst, and comprises a single metal catalyst which only takes palladium or copper as an active component, or a multi-metal catalyst which takes palladium, copper and the like as active components. When the copper catalyst is used for selective hydrogenation for removing alkyne, the selectivity is higher, but because the reaction temperature is high, diene and alkyne are easy to generate polymers to deposit on the surface of the catalyst, the catalyst is quick to deactivate, and the service life is short. The palladium catalyst has higher activity than the copper catalyst and mild use conditions, so the catalyst has long service life, but the selectivity is slightly poorer than the copper catalyst, and palladium is easy to be complexed with alkyne to cause palladium loss.
U.S. Pat. No. 3,898,298 discloses a Pd/Al alloy2O3The catalyst comprises an active component palladium content of 0.05-0.2 wt% and a carrier of alumina, and is usually used for selective hydrogenation of alkyne-containing C-C materials with low alkyne content (less than 1.0 wt%), wherein the vinylacetylene hydrogenation rate usually exceeds 90%, but the 1, 3-butadiene hydrogenation loss rate is high.
The U.S. Pat. No. 4,547,600 discloses a Pd-Ag bimetallic catalyst, which has high hydrogenation activity when used for hydrogenation of low alkyne content (about 1.95% of vinylacetylene), and the vinylacetylene content can be reduced to about 300ppm, while when used for hydrogenation of medium alkyne content (about 4.10% of vinylacetylene), the conversion rate of vinylacetylene is only about 70%. Meanwhile, after the catalyst operates for more than 700 hours, the palladium loss is serious, and the loss rate is up to 10 percent, so the catalyst is not suitable for hydrogenation of materials with higher alkyne content.
Patent CN201110205694.9 discloses a bimetallic catalyst for selective hydrogenation of nickel and copper in hydrocarbon tetraalkyne, wherein the nickel and copper are impregnated on a carrier by adopting a soluble salt water solution, because of the high content of active components, the catalyst has strong tolerance capability to impurities such as water, a solvent, a recombinant component and the like, but the adiabatic temperature rise of the reaction is high, and the outlet temperature of the reactor exceeds 80 ℃, which can aggravate the polymerization of alkyne and dialkene and influence the long-period operation of the catalyst. The catalyst is also only suitable for hydrogenation of materials with low alkyne content.
Patent 03159237.6 discloses a method for utilizing butadiene plant residues by using a one-stage, two-stage or multi-stage hydrogenation process to treat alkyne-containing materials and then recover butadiene, 1-butene or use them as fuel, wherein acetylene hydrocarbon is selectively hydrogenated to butadiene catalyst using palladium-copper-silver or palladium-copper catalyst. According to the process, a large amount of products circulate in each section of reactor, the circulation ratio of circulating materials to fresh materials is 10-30, and the large circulation ratio increases the energy consumption of the device. The process catalyst has poor butadiene selectivity, and acetylene hydrocarbon is mainly converted into butene.
Patent CN103787811B discloses a hydrogenation method of butadiene tail gas, which adopts liquid-phase hydrocarbon to absorb the butadiene tail gas and then uses the butadiene tail gas as ethylene cracking raw material through two-stage hydrogenation. The first hydrogenation adopts nickel catalyst with large circulation ratio of 8-30, and the second hydrogenation adopts nickel-molybdenum catalyst for high-temperature hydrogenation. The method has high energy consumption, and the hydrogenation product can only be used as an ethylene cracking material.
Patent CN201410771106.1 discloses a selective hydrogenation method for alkyne, which uses palladium-lead catalyst using niobium oxide-alumina as carrier, and requires that the alkyne content in alkyne-containing material no more than 25% and alkyne content in the material to be hydrogenated no more than 10%, and when the alkyne content is high, the raffinate carbon four is used for dilution.
Patent CN1,321,544A discloses a multi-metal catalyst for selective hydrogenation for acetylene removal, the active components are copper and palladium, the carrier is treated with alkali metal, alkaline earth metal or their mixture, and auxiliary metals such as Ag, Pb, Bi, Zr, Pt, etc. can also be added. The catalyst can only treat carbon four cuts with alkyne contents below 1.3 wt.%. The catalyst has high Cu content, and when a material with high alkyne content is treated, the operation temperature is high, and the selectivity and the stability of the catalyst are poor.
CN101,428,228A discloses a selective hydrogenation catalyst and its preparation method, which uses alumina as carrier, and comprises active component palladium, assistant copper, and assistant X1And auxiliary agent X2Based on 100 percent of the total weight of the catalyst: contains Pd 0.1-0.5%, Cu 0.1-6%, and X1 0.5～15％，X20.5-5% of one or more auxiliary metal selected from cobalt, nickel, molybdenum, tungsten, lanthanum, silver, cerium, samarium and neodymium, and 0-2% of auxiliary metal; wherein X1Selected from the group consisting of IVA elements, X2Selected from alkali metals, alkaline earth metals or mixtures thereof. The introduction of the auxiliary element in the catalyst is realized by impregnating a carrier or a catalyst precursor, and the catalyst is suitable for selective hydrogenation alkyne removal of alkyne-rich residual materials after butadiene extraction, but can only process carbon-four materials with high alkyne content and low butadiene content.
Coking is one of the other important causes of catalyst deactivation, and the main causes of coking are poor catalyst selectivity, too many side reactions such as polymerization of alkynes and dienes, and too high reaction temperature or too high adiabatic temperature rise, which leads to the aggravation of unsaturated hydrocarbon polymerization at high temperature. Once the gum is formed, it can cover the active center or block the catalyst channels, thereby reducing the activity, selectivity and stability of the catalyst, and finally leading to the catalyst deactivation and failure of the normal operation.
In the prior art, a catalyst taking palladium as an active component is easily interfered by impurities such as water, a solvent and heavy components in a hydrogenation material, so that the hydrogenation activity, particularly the running stability is poor. In the prior art, when a carrier is impregnated by soluble salt of an auxiliary agent, due to the problems of non-uniformity of the pore structure of the carrier, difficulty in realizing the consistency of control of impregnation conditions and the like, the auxiliary agent is non-uniformly distributed in the catalyst, and the synergistic effect of the auxiliary agent and palladium cannot be fully exerted, so that the hydrogenation activity, selectivity and stability of the catalyst are difficult to balance. In particular, the introduction of IB and/or IVA elements, especially Cu, Ag, Si, Sn, Pb, etc., is far higher than the palladium content, and thus the impregnation method is not preferred.
The invention content is as follows:
aiming at the defects in the prior art, the invention provides an alkyne hydrogenation selective catalyst and a preparation method and application thereof. When elements such as Cu, Ag, Si, Sn and Pb of IB and/or IVA are introduced into the catalyst, different introduction modes are selected according to the interaction mechanism of the elements and the palladium and the purpose to be achieved, namely, one part is introduced by adopting a solid-liquid phase impregnation mode, the other part is introduced by adopting a liquid-liquid phase in the preparation of the carrier, the introduction ratio of the two parts is reasonably distributed, and the balance among the activity, the selectivity and the stability of the catalyst is found, so that the distribution of the auxiliary components in the carrier is more uniform, and particularly, when the content of the auxiliary components is high, the effect is more obvious, so that the hydrogenation activity, the selectivity (more than 60 percent) and the stability of the catalyst are improved (the activity is basically not reduced in 1000h operation, the coking rate is less than 1.5 percent, and the palladium is basically not lost). More importantly, the catalyst has high activity and good selectivity, so the hydrogenation condition is mild, the inlet temperature, the adiabatic temperature rise, the operation pressure and the circulation ratio are low, the catalyst is particularly suitable for hydrogenation of alkyne-containing carbon-tetra-materials with high alkyne content, and is particularly suitable for hydrogenation of alkyne-containing carbon-tetra-materials with high butadiene content.
The alkyne selective hydrogenation catalyst for realizing the purpose of the invention takes 0.1-0.8% of metal palladium as an active component, 90-99% of alumina as a carrier, 0-5% of alkali metal and/or alkaline earth metal oxide as a modification auxiliary agent and 0.05-10% of IB and/or IVA element oxide as a cocatalyst component according to weight percentage; in each component of the catalyst, palladium, alkali metal and/or alkaline earth metal are introduced in an impregnation mode, one part of IB and/or IVA elements are introduced in an impregnation mode, and the other part of IB and/or IVA elements are introduced in the preparation of a carrier; the specific surface area of the catalyst is 20-100 m2The pore volume is 0.15-0.75 ml/g.
Wherein the carrier is spherical, dentate spherical, strip, clover or other carrier obtained by extruding, tabletting or rolling ball, preferably
Of clover shape or
Spherical, toothed spherical.
The alkali metal is one or more of Li, K, Rb and Cs, preferably Li and K, and the addition amount is 0.05-2.5%, preferably 0.5-1.5%.
The alkaline earth metal is one or more of Mg, Ca, Sr and Ba, preferably Mg and Sr, and the addition amount is 0.05-2.5%, preferably 0.5-1.5%.
The IB element is one or more of Cu, Ag and Au, one part of the IB element is Ag and/or Au which is introduced in a dipping mode, and the adding amount is 0.1-3.0%, preferably 0.5-2.0%; the other part is Cu which is introduced when the alumina carrier is prepared, and the addition amount is 0.5-10%, preferably 1.5-6.0%.
The IVA element is one or more of Si, Ge, Sn and Pb, part of the IVA element is introduced in a manner of dipping Pb and/or Ge, and the addition amount is 0.2-3.5%, preferably 0.4-2.5%; the other part is Si and/or Sn which is introduced when the alumina carrier is prepared, and the addition amount is 2.0-10%, preferably 3.0-5.0%.
The preparation method of the alkyne selective hydrogenation catalyst comprises the following steps:
A. preparing a carrier:
diluting an aluminum source with water to obtain 150-250 gAl2O3Adding a precipitator while stirring, gelatinizing at 50-100 ℃, washing, filtering, pulping, aging at 50-100 ℃, filtering, drying and roasting to prepare pseudo-boehmite, and adding IB element Cu and/or IVA element Si and/or Sn in the gelatinizing and/or pulping process to obtain a soluble salt solution;
mixing and kneading the pseudo-boehmite with nitric acid, citric acid, sesbania powder and water, then forming, drying at 80-150 ℃ for 10-12 hours, and roasting at 750-1100 ℃ for 8-12 hours to obtain a finished product of the alumina carrier;
B. modification of a carrier:
taking a finished product of alumina carrier, measuring the water absorption rate of the finished product of alumina carrier, preparing an alkali metal and/or alkaline earth metal aqueous solution according to the water absorption rate and the content of a modifier, adjusting the pH value of the solution, pouring the finished product of alumina carrier into the solution for dipping, aging, drying at 80-150 ℃ for 6-8 h, and roasting at 750-1100 ℃ for 4-8 h to obtain the modified alumina carrier;
C. preparing a catalyst:
preparing a palladium solution and/or a soluble salt solution of IB element Ag and/or Au and/or a soluble salt solution of IVA element Pb and/or Ge according to the content of each component in the catalyst and the water absorption rate of the modified carrier, uniformly mixing, adjusting the pH value to 2.5-6.0, soaking the weighed modified carrier in the solution, aging, drying at 80-150 ℃ for 6-8 hours, and roasting at 350-600 ℃ for 6-8 hours to obtain the finished catalyst.
Wherein the aluminum source is one or more of aluminum hydroxide, aluminum sulfate, aluminum chloride, aluminum nitrate and sodium metaaluminate; the precipitator is one or more of sodium metaaluminate, carbon dioxide, sodium carbonate, urea, ammonium carbonate and ammonium bicarbonate; the soluble salt of copper is selected from one or more of copper nitrate, copper sulfate and copper chloride; the soluble salt of Si is selected from one or more of sodium silicate, sodium metasilicate and silica sol; the soluble salt of Sn is selected from one or more of stannic chloride, stannous chloride and stannic nitrate.
The palladium solution is palladium chloride, palladium nitrate or palladium acetate solution.
The alkali metal is one or more of Li, K, Rb and Cs, preferably Li and/or K, and is introduced in the form of soluble salt; the alkaline earth metal is one or more of Mg, Ca, Sr and Ba, preferably Mg and/or Sr, and the alkaline earth metal is introduced in the form of soluble salt.
The pH value of the impregnation liquid is adjusted by ammonia water, sodium bicarbonate, sodium carbonate, potassium carbonate and potassium bicarbonate solution.
The alkyne selective hydrogenation catalyst is used for selective hydrogenation of alkyne in alkyne-containing carbon four-fraction, and is carried out according to the following steps:
hydrogenation of vinyl acetylene and ethyl acetyleneThe reaction unit is converted into butadiene and butylene, the hydrogenated product returns to the butadiene extraction device from the product separation unit, the butadiene and butylene are recovered or enter an alkyne-containing tail gas collection unit to be mixed with the raw material, liquefaction and purification are carried out again, the reactor is a bubbling type heat-insulating fixed bed reactor, the hydrogenation reaction adopts a two-stage hydrogenation process, the inlet temperature of each stage of reactor is 20-80 ℃, the preferred temperature is 30-60 ℃, the operating pressure is 0.45-1.5 MPa, the preferred pressure is 0.60-1.0 MPa, the molar ratio of hydrogen to alkyne is 0.5-2.5, the preferred pressure is 0.8-1.5, and the airspeed of the fresh material is 0.4-2.5 h-1Preferably 0.8 to 1.5 hours-1The ratio of the product to the fresh material is 2-8, preferably 3-6.
The alkyne selective hydrogenation catalyst is used for an isothermal fixed bed reactor.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
the invention mainly solves the coking problem of the catalyst from the following aspects: firstly, through adding alkali metal and/or alkaline earth metal modifier modification regulation and control carrier surface acidity, reduce the strong acid center of easy polymerization by a wide margin, secondly, add auxiliary agent and active metal palladium and form stronger interact, in order to weaken the initial activity of catalyst, because the coking of reaction initial stage is showing more to catalyst activity influence, through adopting certain means, promote palladium better dispersion simultaneously with the cocatalyst component and form stronger effect between the carrier, produce synergistic effect, reduce side reactions such as coking when improving selectivity, from implementing the effect, the catalyst of this patent preparation has reached this effect.
According to the catalyst, IB and/or IVA element oxides serving as the cocatalyst components are introduced in different modes, part of the IB and/or IVA element oxides can promote the dispersion of palladium, improve the hydrogenation activity, and part of the IB and/or IVA element oxides and palladium form an alloy or solid solution, so that the interaction between the palladium and the cocatalyst components as well as between the palladium and the carrier is enhanced, the hydrogenation selectivity and the operation stability are improved, and the loss of the palladium is inhibited.
The invention is characterized in that: the catalyst of the invention has high hydrogenation activity, good selectivity, strong water resistance, solvent resistance and other impurity performances, excellent running stability, and simple and easy operation of the preparation method of the catalyst. After 1000h evaluation, the performance of the catalyst is not reduced basically, the coking rate is less than 1.5 percent, and palladium is not lost basically. The acetylene-containing four-selective hydrogenation device is suitable for acetylene-containing four-selective hydrogenation with high acetylene hydrocarbon content or acetylene-containing four-selective hydrogenation with high butadiene content in a butadiene extraction device, vinyl acetylene is converted into butadiene, ethyl acetylene is converted into butene, and a hydrogenation product can return to the extraction device to directly recover butadiene and butene or return to a raw material storage tank of the extraction device to be mixed with the raw material to be used as the feeding of the extraction device.
The catalyst of the invention has the following advantages: firstly, the hydrogenation activity and the selectivity realize better balance, and the problem of mismatching of poor activity and selectivity or poor selectivity and activity of the catalyst is solved. And secondly, the catalyst has higher hydrogenation stability, less colloid generation amount and strong water resistance, solvent resistance and recombinant fluctuation capability. Thirdly, the catalyst has mild use conditions, the hydrogenation reaction has better hydrogenation performance at room temperature and lower pressure, particularly the circulation ratio is low, the product circulation amount is less, the impact on the catalyst is reduced, and the energy consumption of the device is reduced. Fourthly, the active component palladium has high dispersity, low loss rate and long running period. Fifthly, the catalyst is not only suitable for hydrogenation of raw materials with high alkyne content, but also particularly suitable for hydrogenation of alkyne-containing carbon-containing four materials with high butadiene content, can effectively improve the latent butadiene content in the feed of a butadiene device, and reduces the influence on a butadiene extraction device.
The alkali metal and/or alkaline earth metal mainly plays a role in modifying the surface acidity of the carrier and improving the thermal stability, and the IB and/or IVA element oxide mainly plays a role in promoting the activity, improving the selectivity, reducing the coking, improving the impurity resistance and prolonging the operation stability.
Drawings
FIG. 1 is a flow diagram of the alkyne selective hydrogenation catalyst of the present invention for the selective hydrogenation of alkynes in a carbon-four alkyne-containing fraction.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to the following examples, but the present invention is not limited to these examples.
Examples 1 to 10
Practice ofExamples 1 to 10 in which Al was used as the carrier for the selective hydrogenation catalyst for acetylene hydrocarbon2O3The components are shown in table 1, and the preparation process comprises the following steps:
A. preparing a carrier:
the preparation concentration is 200gAl2O3Heating 1L/L sodium metaaluminate solution to 70 deg.C to prepare 80gAl2O32L of aluminum sulfate solution is heated to 70 ℃;
adding 1.0L of distilled water into a gelling tank, heating to 70 ℃, adding the two serosity in a concurrent flow manner, keeping the pH value at 8.0, gelling at 70 ℃, and adding a Cu salt solution and/or a Sn salt solution and/or a Si salt solution with the concentration of 0.05mol/L in the gelling process;
aging at 70 deg.C and pH of 8.0 for 60min after the formation of cement paste. After the aging is finished, injecting 65 ℃ deionized water, pulping, washing and filtering the aged slurry at the stirring speed of 200rpm, and drying a filter cake at 100 ℃ for 3 hours to obtain pseudo-boehmite containing Cu and/or Sn and/or Si;
B. modification of a carrier:
mixing the prepared pseudo-boehmite, nitric acid, citric acid, water and the like, kneading, extruding into strips, forming, drying at 120 ℃ for 4h, roasting at 600 ℃ for 6h to obtain a carrier, then impregnating a certain amount of alkali metal and/or alkaline earth metal salt solution, drying at 120 ℃ for 4h, and roasting at 1100 ℃ for 4h to obtain an alkali metal and/or alkaline earth metal-containing carrier;
C. preparing a catalyst:
preparing solution of palladium nitrate, silver nitrate and/or lead nitrate, regulating pH value, impregnating carrier, drying at 120 deg.C for 4 hr, and calcining at 500 deg.C for 8 hr to obtain the catalyst.
Examples 11 to 20
The selective hydrogenation catalyst carrier for acetylenes of examples 11-20 was Al2O3The components are shown in table 1, and the preparation process comprises the following steps:
A. preparing a carrier:
the concentration of the prepared solution is 200gAl in a gel forming tank2O31L of aluminum nitrate solution with the preparation concentration of 80gAl2O31L of aluminum sulfate solution is mixed uniformly and heated to 75 ℃;
introducing CO into the gel forming tank2Gas, keeping the pH value at 8.0-8.5, gelatinizing at the temperature of 75 ℃, and aging for 60min at the pH value of 8.0 and the temperature of 70 ℃ after gelatinizing;
after the aging is finished, injecting 75 ℃ deionized water, washing, pulping at the stirring speed of 200rpm, simultaneously adding 0.05mol/L Cu salt solution and/or Sn salt solution and/or Si salt solution, pulping for 60min, filtering, and drying the filter cake at 120 ℃ for 8h to obtain pseudo-boehmite containing Cu and/or Sn and/or Si;
B. modification of a carrier:
mixing the prepared pseudo-boehmite, nitric acid, citric acid, water and the like, kneading, extruding into strips, drying at 120 ℃ for 4h, and roasting at 650 ℃ for 8h to obtain a carrier; then dipping a certain amount of alkali metal and/or alkaline earth metal salt solution, drying at 120 ℃ for 4h, and roasting at 1060 ℃ for 6h to obtain a carrier containing alkali metal and/or alkaline earth metal;
C. preparing a catalyst:
respectively preparing solutions of palladium acetate, silver nitrate and/or lead acetate, regulating the pH value of the solution, impregnating the carrier, drying at 120 ℃ for 4h, and roasting at 450 ℃ for 8h to obtain the catalyst.
Examples 21 to 30
The selective hydrogenation catalyst carrier for acetylenes of examples 21 to 30 was Al2O3The components are shown in table 1, and the preparation process comprises the following steps:
A. preparing a carrier:
the preparation concentration is 200gAl2O31L of aluminum nitrate solution with the preparation concentration of 80gAl2O31L of aluminum sulfate solution, mixing the two solutions, and heating to 50 ℃;
preparing a mixed solution of sodium carbonate and ammonium bicarbonate in a gelling tank, heating to 60 ℃, adding the mixed solution of aluminum nitrate and aluminum sulfate into the gelling tank, keeping the pH value at 8.0-8.5, gelling at the temperature of 60 ℃, and adding a Cu salt solution and/or a Sn salt solution and/or a Si salt solution with the concentration of 0.05mol/L in the gelling process;
aging at 60 deg.C and pH of 8.0 for 60min after the formation of cement paste. After the aging is finished, injecting 75 ℃ deionized water for washing, then pulping at the stirring speed of 200rpm, simultaneously adding 0.05mol/L Cu salt solution and/or Sn salt solution and/or Si salt solution, continuously pulping for 60min, washing, filtering, and drying a filter cake at 130 ℃ for 8h to obtain pseudo-boehmite containing Cu and/or Sn and/or Si;
B. modification of a carrier:
mixing the prepared pseudo-boehmite, nitric acid, citric acid, water and the like, kneading, extruding into strips, forming, drying at 120 ℃ for 4h, roasting at 650 ℃ for 8h to obtain a carrier, then impregnating a certain amount of alkali metal and/or alkaline earth metal salt solution, drying at 120 ℃ for 4h, and roasting at 950 ℃ for 6h to obtain an alkali metal and/or alkaline earth metal-containing carrier;
C. preparing a catalyst:
then respectively preparing solutions of palladium nitrate, silver nitrate and/or lead nitrate, adjusting the pH value of the solution, impregnating the carrier, drying at 120 ℃ for 4h, and roasting at 600 ℃ for 8h to obtain the catalyst.
The alkyne selective hydrogenation catalyst of examples 1 to 30 is used for selective hydrogenation of alkynes in alkyne-containing carbon four-fraction, and is performed according to the following steps as shown in fig. 1:
vinyl acetylene and ethyl acetylene are converted into butadiene and butylene through a hydrogenation reaction unit, a hydrogenation product returns to a butadiene extraction device from a product separation unit, the butadiene and butylene are recovered or enter an acetylene-containing tail gas collection unit to be mixed with a raw material, liquefaction and purification are carried out again, the reactor is a bubbling type adiabatic fixed bed reactor, the hydrogenation reaction adopts a two-stage hydrogenation process, the inlet temperature of each stage of reactor is 20-80 ℃, the preferred temperature is 30-60 ℃, the operating pressure is 0.45-1.5 MPa, the preferred pressure is 0.60-1.0 MPa, the molar ratio of hydrogen to acetylene is 0.5-2.5, the preferred pressure is 0.8-1.5, and the air speed of a fresh material is 0.4-2.5 h-1Preferably 0.8 to 1.5 hours-1The ratio of the product to the fresh material is 2-8, preferably 3-6.
Comparative examples 1 to 5
Comparative examples 1 to 5 Components Al is shown in Table 12O3Roasting the carrier at 550 ℃ for 8h, then soaking a certain amount of alkali metal and/or alkaline earth metal salt solution, drying at 120 ℃ for 4h, and roasting at 1060 ℃ for 6h to obtain the carrier containing alkali metal and/or alkaline earth metal; then impregnating with a certain amount ofDrying the solution containing Cu and/or Sn and/or Si at 120 ℃ for 4h, roasting at 500 ℃, then impregnating palladium nitrate, silver nitrate and/or lead nitrate, drying at 120 ℃ for 4h, and roasting at 500 ℃ for 8h to obtain the catalyst.
Comparative examples 6 to 10
The components of comparative examples 6 to 10 are shown in Table 1, and the alumina carrier is prepared by mixing and kneading pseudo-boehmite, nitric acid, citric acid, water, a Cu-containing and/or Sn-containing and/or Si-containing solution, extruding into strips, forming, drying at 120 ℃ and roasting at 550 ℃ for 4 hours; then dipping a certain amount of alkali metal and/or alkaline earth metal salt solution, drying at 120 ℃ for 4h, and roasting at 1000 ℃ for 6h to obtain a carrier containing alkali metal and/or alkaline earth metal; then certain amount of palladium nitrate, silver nitrate and/or lead nitrate is dipped, dried for 4h at 120 ℃ and roasted for 8h at 500 ℃ to prepare the catalyst.
The catalytic ability of the catalysts prepared in examples 1 to 30 and comparative examples 1 to 10 was evaluated under the following conditions: an adiabatic bubbling fixed bed reactor and a single-stage or two-stage hydrogenation process are adopted, the inlet temperature of the reactor is 30-45 ℃, the reaction pressure is 0.8-1.0 MPa, and H is2The mol ratio of/VA is 0.75-2.0, and the hourly space velocity of fresh feed liquid is 1.0-2.0 h-1And the catalyst loading was 50 ml.
The reaction process flow comprises the following steps: the carbon four fraction is measured by a metering pump and then is increased to the reaction pressure, the preheated carbon four fraction and hydrogen gas are mixed and enter a catalyst bed layer from the lower part of the reactor, the reaction product is cooled and then is subjected to gas-liquid separation, the separated non-condensable gas is discharged, and the liquid is discharged into a product tank. When two-stage hydrogenation is adopted, the first-stage hydrogenation product directly enters a second-stage reactor without separation, and hydrogen is added into the second-stage reactor according to the alkyne content in the product.
And (3) catalyst reduction: before evaluation, the temperature is 120 ℃, the pressure is 1.0MPa, hydrogen is introduced for reduction for 8 hours, and the space velocity of the hydrogen is 100 hours-1。
Catalyst regeneration: the catalyst after 1000 hours of evaluation was unloaded and calcined in a muffle furnace at 550 ℃ with air for 4 hours.
Gas chromatography is adopted to analyze the composition of raw materials and products.
In this example, the alkyne hydrogenation rate and butadiene selectivity were calculated according to the following formulas:
the specific evaluation conditions and results of the catalysts of examples and comparative examples are shown in Table 1.
Table 1 evaluation results of catalysts of examples and comparative examples
The catalyst prepared in example 14 was loaded in a first and second stage reactor, respectively, using a two stage hydrogenation process, each reactor being loaded with 50ml of catalyst. At the inlet temperature of 30 deg.C, the operation pressure of 0.95MPa, and the first section of H21.0 part of the formula,/VA (mol) (/ H)20.8 of/VA (mol), and the space velocity of fresh materials is 1.2-1.5 h-1Under the conditions, the evaluation was carried out for 1000 hours in a cumulative manner, and the results of the catalyst performance evaluation are shown in Table 2.
TABLE 2 example 14 catalyst 1000h evaluation results
The results of the analytical tests on the catalyst, regenerated catalyst and fresh catalyst after 1000 hours evaluation are shown in Table 3.
Table 3 example 14 catalyst test results
| Fresh agent | After 1000h evaluation | Regenerant | |
| Palladium content (wt%) | 0.40 | - | 0.395 |
| Specific surface area (m)2/g) | 52.5 | 40.8 | 50.4 |
| Coking Rate (wt%) | - | 1.45 | - |
As can be seen from the comparison of the results in tables 1 to 3, the catalysts prepared in the present invention have the same conversion rate as the comparative examples, and have better selectivity, and the palladium content and specific surface area do not change significantly after long-term use, demonstrating excellent stability.
Claims (11)
1. An alkyne selective hydrogenation catalyst, characterized in that: according to the weight percentage, 0.1-0.8% of metal palladium is used as an active component, 90-99% of alumina is used as a carrier, 0-5% of alkali metal and/or alkaline earth metal oxide is added as a modification auxiliary agent, and 0.05-10% of IB and/or IVA element oxide is used as a cocatalyst component; wherein in each component of the catalyst, palladium, alkali metal and/or alkaline earth metalThe introduction is carried out in an impregnation mode, one part of IB and/or IVA elements is introduced in an impregnation mode, and the other part is introduced in the preparation of the carrier; the IB element is one or more of Cu, Ag and Au, one part of the IB element is Ag and/or Au which is introduced in a dipping mode, and the addition amount is 0.1-3.0%; the other part is Cu which is introduced when the alumina carrier is prepared, and the addition amount is 0.5-10%; the IVA element is one or more of Si, Ge, Sn and Pb, part of the IVA element is introduced in a manner of dipping Pb and/or Ge, and the addition amount is 0.2-3.5%; the other part is Si and/or Sn which are introduced when the alumina carrier is prepared, and the addition amount is 2.0-10%; the specific introduction mode during the preparation of the carrier is that an aluminum source is diluted by water to have the concentration of 150-250 g/Al2O3Adding a precipitator under stirring, gelatinizing at 50-100 ℃, washing, filtering, pulping, aging at 50-100 ℃, filtering, drying and roasting to obtain pseudo-boehmite, adding IB element Cu and/or IVA element Si and/or Sn in the gelatinizing or pulping process to obtain a soluble salt solution, taking the pseudo-boehmite, adding nitric acid, citric acid, sesbania powder and water, mixing and kneading, forming, drying at 80-150 ℃ for 10-12 hours, and roasting at 750-1100 ℃ for 8-12 hours to obtain a finished product alumina carrier; the specific surface area of the catalyst is 20-100 m2The pore volume is 0.15-0.75 ml/g.
2. The selective hydrogenation catalyst for acetylenes according to claim 1 characterised in that said support is in the shape of sphere, dentate sphere, bar, clover or other shape obtained by extrusion, tabletting or rolling.
3. The selective hydrogenation catalyst for alkyne of claim 1 wherein the alkali metal is one or more of Li, K, Rb and Cs, and the addition amount is 0.05-2.5%.
4. The selective hydrogenation catalyst for alkyne of claim 1 wherein the alkaline earth metal is one or more of Mg, Ca, Sr and Ba, and the addition amount is 0.05-2.5%.
5. A process for the preparation of a catalyst for the selective hydrogenation of alkynes according to claim 1, which comprises the steps of: A. preparing a carrier: diluting an aluminum source with water to obtain 150-250 gAl2O3Adding a precipitator while stirring, gelatinizing at 50-100 ℃, washing, filtering, pulping, aging at 50-100 ℃, filtering, drying and roasting to prepare pseudo-boehmite, and adding IB element Cu and/or IVA element Si and/or Sn in the gelatinizing and/or pulping process to obtain a soluble salt solution; mixing and kneading the pseudo-boehmite with nitric acid, citric acid, sesbania powder and water, then forming, drying at 80-150 ℃ for 10-12 hours, and roasting at 750-1100 ℃ for 8-12 hours to obtain a finished product of the alumina carrier; B. modification of a carrier: taking a finished product of alumina carrier, measuring the water absorption rate of the finished product of alumina carrier, preparing an alkali metal and/or alkaline earth metal aqueous solution according to the water absorption rate and the content of a modifier, adjusting the pH value of the solution, pouring the finished product of alumina carrier into the solution for dipping, aging, drying at 80-150 ℃ for 6-8 h, and roasting at 750-1100 ℃ for 4-8 h to obtain the modified alumina carrier; C. preparing a catalyst: preparing a palladium solution and/or a soluble salt solution of IB element Ag and/or Au and/or a soluble salt solution of IVA element Pb and/or Ge according to the content of each component in the catalyst and the water absorption rate of the modified carrier, uniformly mixing, adjusting the pH value to 2.5-6.0, soaking the weighed modified carrier in the solution, aging, drying at 80-150 ℃ for 6-8 hours, and roasting at 350-600 ℃ for 6-8 hours to obtain the finished catalyst.
6. The method for preparing an alkyne selective hydrogenation catalyst as claimed in claim 5, wherein said aluminum source is one or more of aluminum hydroxide, aluminum sulfate, aluminum chloride, aluminum nitrate, and sodium metaaluminate; the precipitator is one or more of sodium metaaluminate, carbon dioxide, sodium carbonate, urea, ammonium carbonate and ammonium bicarbonate; the soluble salt of copper is selected from one or more of copper nitrate, copper sulfate and copper chloride; the soluble salt of Si is selected from one or more of sodium silicate, sodium metasilicate and silica sol; the soluble salt of Sn is selected from one or more of stannic chloride, stannous chloride and stannic nitrate.
7. The method for preparing an alkyne selective hydrogenation catalyst as recited in claim 5, wherein the palladium solution is a palladium chloride solution, a palladium nitrate solution or a palladium acetate solution.
8. The method for preparing an alkyne selective hydrogenation catalyst as claimed in claim 5, wherein the alkali metal is one or more of Li, K, Rb and Cs, and the alkali metal is introduced in the form of soluble salt; the alkaline earth metal is one or more of Mg, Ca, Sr and Ba, and the alkaline earth metal is introduced in the form of soluble salt.
9. The method according to claim 5, wherein the pH of the impregnation solution is adjusted by using a solution of ammonia, sodium bicarbonate, sodium carbonate, potassium carbonate, or potassium bicarbonate.
10. The use of an alkyne selective hydrogenation catalyst, which is characterized in that the selective hydrogenation of alkynes in alkyne-containing C-fraction is carried out according to the following steps: vinyl acetylene and ethyl acetylene are converted into butadiene and butylene through a hydrogenation reaction unit, a hydrogenation product returns to a butadiene extraction device from a product separation unit, the butadiene and butylene are recycled or enter an alkyne-containing tail gas collection unit to be mixed with a raw material, liquefaction and purification are carried out again, the reactor is a bubbling type adiabatic fixed bed reactor, the hydrogenation reaction adopts a two-section hydrogenation process, the inlet temperature of each section of reactor is 20-80 ℃, the operating pressure is 0.45-1.5 MPa, the molar ratio of hydrogen to alkyne is 0.5-2.5, the airspeed of a fresh material is 0.4-2.5 h < -1 >, and the ratio of the product to the fresh material is 2-8.
11. Use of a catalyst according to claim 10, characterized in that it is used in an isothermal fixed bed reactor.
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