CN107175110B - Hydrocarbon hydrogenation catalyst containing carbon-carbon triple bond - Google Patents
Hydrocarbon hydrogenation catalyst containing carbon-carbon triple bond Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 156
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 56
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 56
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 56
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 53
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 25
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 42
- 238000001035 drying Methods 0.000 description 41
- 238000002360 preparation method Methods 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 29
- 238000002156 mixing Methods 0.000 description 22
- 239000000203 mixture Substances 0.000 description 22
- 239000011148 porous material Substances 0.000 description 20
- 238000011156 evaluation Methods 0.000 description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 description 18
- 241000219782 Sesbania Species 0.000 description 18
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 18
- 229910017604 nitric acid Inorganic materials 0.000 description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 description 18
- 239000000843 powder Substances 0.000 description 18
- 150000001345 alkine derivatives Chemical class 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- NBFQLHGCEMEQFN-UHFFFAOYSA-N N.[Ni] Chemical compound N.[Ni] NBFQLHGCEMEQFN-UHFFFAOYSA-N 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 9
- 229910006251 ZrOCl2.8H2O Inorganic materials 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 7
- XLKNMWIXNFVJRR-UHFFFAOYSA-N boron potassium Chemical compound [B].[K] XLKNMWIXNFVJRR-UHFFFAOYSA-N 0.000 description 7
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 150000005673 monoalkenes Chemical class 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- B01J23/83—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
-
- B01J35/615—
-
- B01J35/635—
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with rare earths or actinides
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a hydrogenation catalyst for hydrocarbon containing carbon-carbon triple bond and a method for hydrotreating material containing hydrocarbon containing carbon-carbon triple bond, which mainly solve the problems of high content of single olefin in a reaction product of hydrogenation of hydrocarbon containing carbon-carbon triple bond to alkane and poor stability of the catalyst.
Description
Technical Field
The invention relates to a hydrogenation catalyst for hydrocarbon containing carbon-carbon triple bonds and a method for hydrotreating a material containing hydrocarbon containing carbon-carbon triple bonds, in particular to a hydrogenation method for treating acetylene by-products containing higher alkynes such as diacetylene, vinyl acetylene and the like.
Background
The by-product of the acetylene preparation process by partial oxidation of natural gas is part of high-grade acetylene gas. It mainly contains unsaturated hydrocarbon such as diacetylene (37.17V%), methylacetylene, propyne (6.74V%), vinylacetylene (10.51V%) and acetylene (19.85V%) and part of C6H6+(25.72V%) heavy ends. The unsaturated hydrocarbons are extremely unstable, for example, the decomposition pressure of diacetylene is only 0.02MPa, vinyl acetylene is easy to polymerize to form an explosive polymer, and the like, so that great potential safety hazards are brought to enterprise production, and the unsaturated hydrocarbons need to be diluted by a large amount of synthesis gas and then sent to a torch to be burnt. The dilution gas contains more than 50% of CO and H2The components are equal, and the economic value is higher. The high-grade alkyne contains a plurality of chemical raw materials with wide application, but because the components are complex and difficult to separate, the high-grade alkyne is difficult to be fully utilized, and the waste of resources is caused. Therefore, it is important to recycle the higher alkynes of the acetylene plant from the viewpoint of production safety and resource utilization.
DE-A-1468206 discloses a process for purifying acetylene by absorption of vinylacetylene and diacetylene in N-methylpyrrolidone (NMP) solvent with Pd/Al2O3Is used as a catalyst for reaction to carry out catalytic hydrogenation reaction, and the hydrogenation product has weaker polarity and is very easy to be dissolved in a solventAnd (5) separating. US4128595 discloses a hydrogenation reaction in which an alkyne-containing material and an inert hydrocarbon solvent are fed together into a reactor and contacted with a palladium-based catalyst, which process has the disadvantage that the alkyne-containing material is poorly soluble in the hydrocarbon solvent under the reaction conditions; the patent publication shows that the catalyst deactivation rate is relatively fast when the hydrogenation reaction is carried out in a polar solvent such as N, N Dimethylformamide (DMF). US2010/0016646A1 discloses a process for hydrogenating diacetylene which is absorbed in a polar solvent such as NMP or DMF using supported Pd/Al2O3And (3) carrying out hydrogenation reaction on the catalyst at the reaction temperature of 0-100 ℃ and the pressure of 1-40 bar to obtain butane and butylene, wherein the catalyst is gradually inactivated due to the surface carbon deposition in the operation process. Because the alkyne has an active triple bond, a polymerization process is easy to occur in the continuous hydrogenation reaction process, green oil and colloid are generated, and the catalyst is inactivated. Therefore, the development of a new alkyne hydrogenation method for improving the operation stability of a hydrogenation device has important significance.
However, in the prior art, the reaction product for hydrogenating hydrocarbon containing carbon-carbon triple bonds into alkane has high content of single olefin and poor stability of the catalyst.
Disclosure of Invention
One of the technical problems to be solved by the invention is the technical problems of high content of the mono-olefin in the reaction product of the hydrogenation of hydrocarbon containing carbon-carbon triple bonds into alkane and poor catalyst stability in the prior art, and the invention provides the hydrogenation catalyst of hydrocarbon containing carbon-carbon triple bonds.
The second technical problem to be solved by the present invention is a method for hydrotreating a carbon-carbon triple-bond hydrocarbon-containing material using the catalyst of the above technical problems.
In order to solve one of the above technical problems, the technical solution of the present invention is as follows: a hydrocarbonhydrogenation catalyst containing carbon-carbon triple bonds is composed of the first-stage catalyst consisting of carrier 1 and Ni or its oxide and B or its compound and the second-stage catalyst consisting of carrier 2 and Ni or its oxide.
In the technical scheme, the weight ratio of the first-stage catalyst to the second-stage catalyst is preferably 0.5-1.
In the above technical solution, the first stage catalyst preferably comprises the following components in percentage by weight:
(a) 5-20% of metal Ni or its oxide;
(b) 0.5-3% of B or its compound.
In the above technical solutions, when the Ni element is in the form of an oxide, those skilled in the art know that the Ni element should be reduced to metallic Ni for use.
In the above technical solution, the second stage catalyst preferably comprises the following components in percentage by weight:
(a) 10-25% of metallic nickel or its oxide;
(b) 0.2-1% of at least one metal selected from rare earth or its oxide;
(c) 0.2-2.0% of at least one metal or oxide thereof selected from IIA in the periodic table of elements;
(d) 2-5% of Zr or its oxide.
In the above technical scheme, when the nickel element is in the form of oxide, the nickel element should be reduced to metallic nickel for use by a person skilled in the art.
In the technical scheme, when the rare earth elements simultaneously comprise Ce element and La element, the two elements have mutual promotion effect on the aspects of improving the conversion rate of the alkyne and the yield of the butane.
In the above technical solution, the carrier 1 and/or the carrier 2 is not particularly limited, but alumina is preferable, and the BET specific surface area of the carrier 1 is more preferably 100 to 160m2A pore volume of 0.45 to 0.80ml/g, and a BET specific surface area of 120 to 200m is more preferably selected for the carrier 22The pore volume is 0.42 to 0.70 ml/g.
To solve the second technical problem, the technical solution of the present invention is as follows: a process for the hydroprocessing of a feed containing hydrocarbons having carbon-carbon triple bonds using a catalyst as set forth in one of the above technical problems, comprising the steps of:
(1) contacting hydrogen and the material with the first-stage catalyst according to any one of the embodiments of the technical problems to react to generate an intermediate material containing monoene;
(2) the intermediate product is hydrogenated in the presence of a second stage catalyst to obtain a feed containing alkane.
In the above technical scheme, the specific amount of the alkyne remaining in the intermediate material is not limited, but the lower the residue, the better the residue is, preferably the residue of the alkyne is within 1%, and the intermediate material preferably contains monoolefin and may also contain alkane. For example, but not limited to, the weight ratio of alkane to monoolefin is 0.5 to 10.
In the above technical scheme, as long as the step of passing through the step (1) and then the step (2) can be satisfied, the person skilled in the art can reasonably determine the upper feeding, the lower feeding or the transverse feeding. For example, when top-in-bottom out-of-feed is selected, the first stage catalyst and the second stage catalyst can be placed in the same reactor, with the first stage catalyst placed on top of the second stage catalyst; when a lower feed is used, the first stage catalyst and the second stage catalyst may be placed in the same reactor, with the first stage catalyst being placed below the second stage catalyst. It is also possible to place the two stages of catalyst separately in two reactors connected in series.
In the technical scheme, the reaction temperature in the step (1) and/or the step (2) is preferably 40-90 ℃; more preferably 60 to 80 DEG C
In the technical scheme, the reaction pressure in the step (1) and/or the step (2) is preferably 0.6-3 MPa; more preferably 1.2 to 2.0MPa
In the technical scheme, the weight space velocity of the carbon-carbon triple bond hydrocarbon in the step (1) is preferably 0.05-0.4 h-1. More preferably, the weight space velocity is 0.05-0.2 h-1。
In the technical scheme, the mole ratio of the hydrogen/carbon-carbon triple bond hydrocarbon in the step (1) is preferably 6-30.
In the above technical scheme, the material containing the hydrocarbon with carbon-carbon triple bond preferably contains a diluent.
In the technical scheme, the content of the carbon-carbon triple bond hydrocarbon in the material is preferably more than zero and less than 5.0 percent by weight; the content of the diluent is preferably 93-99%.
In the above technical solution, the diluent may be at least one selected from N-methylpyrrolidone, N dimethylformamide, and acetone.
In the above-mentioned embodiments, the carbon-carbon triple bond-containing hydrocarbon is not particularly limited, and examples thereof include, but are not limited to, propyne, vinylacetylene, and diacetylene.
By way of more specific, non-limiting example, the feed comprises, by weight, 0.1 to 2% of vinylacetylene, 0.1 to 3% of benzene, 0.1 to 4% of diacetylene, and 95 to 99% of N-methylpyrrolidone.
The preparation method of the two-stage catalyst carrier of the present invention is not particularly limited, and includes, as a non-limiting example, the steps of:
mixing alumina, a modifier, a peptizing agent and water according to required amounts, extruding into strips, drying at 60-110 ℃ for 5-24 hours, and roasting at 500-1000 ℃ for 4-10 hours to obtain the carrier.
A more preferred method of preparing carrier 1 comprises:
mixing alumina, a modifier, a peptizing agent and water according to required amounts, extruding into strips, drying at 60-110 ℃ for 5-24 hours, and roasting at 500-750 ℃ for 4-10 hours to obtain the carrier 1.
A more preferred method of preparing carrier 2 comprises:
mixing alumina, a modifier, a peptizing agent and water according to required amounts, extruding into strips, drying at 60-110 ℃ for 5-24 hours, and roasting at 500-700 ℃ for 4-10 hours to obtain the carrier 2.
The method for preparing the two-stage catalyst of the present invention is not particularly limited, and the method for preparing the first-stage catalyst includes, as non-limiting examples, the steps of: and (3) impregnating the carrier with a solution prepared from required amount of nickel, drying, and reducing by potassium borohydride to obtain the reduction type Ni-B catalyst.
The method for preparing the two-stage catalyst of the present invention is not particularly limited, and the method for preparing the second-stage catalyst includes, as non-limiting examples, the steps of: impregnating the carrier with a solution prepared from a promoter component and then with a solution prepared from a desired amount of a nickel compound, or impregnating the carrier with a solution prepared from a desired amount of a nickel compound and a promoter component used in the catalyst; and drying the impregnated carrier, and roasting in air at 350-500 ℃ to obtain the oxidized nickel-based catalyst.
The above oxidation catalyst can also be reduced, and the specific reduction mode can be reasonably mastered by a person skilled in the art, and the nickel in the compound state is reduced to be in a metal state. For example, the reduction process conditions for the second stage catalyst of the present invention are: space velocity of hydrogen gas of 100h-1And raising the temperature to 230-280 ℃ at a temperature raising rate of 30-60 ℃/h under the pressure of 0.2-0.5 MPa, maintaining for 3-6 h, raising the temperature to 330-380 ℃ at a rate of 15 ℃/h, maintaining for 6-12 h, raising the temperature to 420-500 ℃ at 15 ℃/h, and maintaining for 6-12 h.
By adopting the method, the reaction temperature is 60 ℃, the reaction pressure is 1.8MPa, and the weight space velocity of the carbon-carbon triple bond hydrocarbon is 0.1h-1The molar ratio of the hydrocarbon with triple bonds of hydrogen and carbon is 10, the conversion rate of the alkyne is 99.9 percent, the yield of the butane is 97.5 percent, and better technical effects are achieved.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Detailed Description
The raw materials used in the experiment are high-grade alkyne which is a byproduct of a device for preparing acetylene from natural gas in a Sichuan vinylon factory, and the specific properties are shown in table 1.
[ example 1 ]
1. Preparation of Carrier 1
Weighing and mixing pseudo-boehmite equivalent to 25 g of alumina, 160 g of alumina and 9 g of sesbania powder, adding 20 g of polyvinyl alcohol solution (mass concentration is 5%), 4.0 g of nitric acid with mass concentration of 68% and 280 ml of water, extruding, drying wet strips at 120 ℃ for 4 hours, and roasting at 750 ℃ for 4 hours to obtain a carrier Z1 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 142m2The pore volume is 0.60 ml/g.
2. First stage catalyst preparation
89.5 g of the carrier Z1 and 110 g of aqueous solution containing 10 g of nickel are mixed, dried at 110 ℃ for 4 hours, mixed and reduced with 100 g of aqueous solution containing 1.0 g of boron potassium borohydride at room temperature for 4 hours, and when no gas is generated, products are washed by distilled water and absolute ethyl alcohol respectively for 4 times to obtain a first-stage catalyst, and the composition of the first-stage catalyst is shown in Table 2. Finally, the sample is stored in an anhydrous and oxygen-free atmosphere or medium.
3. Preparation of support 2
Pseudo-boehmite corresponding to 12 g of alumina, 69.5 g of alumina and 9 g of sesbania powder are weighed and mixed, and then 20 g of polyvinyl alcohol solution (mass concentration is 5 percent) and 4.0 g of nitric acid with mass concentration of 68 percent, which are corresponding to 0.5 g of La, are added2O3La (NO) of3)3.6H2O, Ca (NO) corresponding to 1 g CaO3)2.4H2O, equivalent to 3.0 g ZrO2ZrOCl2.8H2O, 130 ml of water, extruding, drying the wet strip at 120 ℃ for 4 hours, and then roasting the dried wet strip at 700 ℃ for 4 hours to obtain a carrier Z2 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 147m2The pore volume is 0.56 ml/g.
4. Second stage catalyst preparation
Mixing the carrier Z2 with nickel ammonia solution 90 g containing 14 g of nickel, drying at 60 ℃ for 8 hours, drying at 110 ℃ for 2 hours, roasting at 450 ℃ for 4 hours, reducing with hydrogen for 4 hours at the reduction temperature of 450 ℃ and the volume space velocity of hydrogen of 50 hours-1To obtain the second stage catalyst, the specific composition is shown in Table 3.
5. Catalyst evaluation
The hydrogenation operation is carried out in a fixed bed reactor. The upper bed layer of the reactor was packed with the first stage catalyst prepared in example 1, and the lower bed layer was packed with the second stage catalyst prepared in example 1, and the mass ratio of the first stage catalyst to the second stage catalyst was 0.8. The hydrogenation operation is carried out on the material containing the hydrocarbon with the carbon-carbon triple bond in a continuous mode, the top of the reactor is fed, and the bottom of the reactor is discharged. During the experiment, the operating conditions were as follows: the reaction temperature is 60 ℃, the reaction pressure is 1.60MPa, and the weight space velocity of the carbon-carbon triple bond hydrocarbon feeding is 0.1h-1The hydrogen/carbon triple bond hydrocarbon molar ratio was 10, and the hydrogenation evaluation was continuously conducted for 300 hours, and the average hydrogenation results are shown in Table 4.
[ COMPARATIVE EXAMPLE 1 ]
The first stage catalyst and the second stage catalyst are placed upside down, and other process conditions are completely the same as those of the example 1, and specifically, the method comprises the following steps:
1. preparation of Carrier 1
Weighing and mixing pseudo-boehmite equivalent to 25 g of alumina, 160 g of alumina and 9 g of sesbania powder, adding 20 g of polyvinyl alcohol solution (mass concentration is 5%), 4.0 g of nitric acid with mass concentration of 68% and 280 ml of water, extruding, drying wet strips at 120 ℃ for 4 hours, and roasting at 750 ℃ for 4 hours to obtain a carrier Z1 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 142m2The pore volume is 0.60 ml/g.
2. First stage catalyst preparation
89.5 g of the carrier Z1 and 110 g of aqueous solution containing 10 g of nickel are mixed, dried at 110 ℃ for 4 hours, mixed and reduced with 100 g of aqueous solution containing 1.0 g of boron potassium borohydride at room temperature for 4 hours, and when no gas is generated, products are washed by distilled water and absolute ethyl alcohol for 4 times in sequence to obtain a first-stage catalyst, wherein the composition of the first-stage catalyst is shown in Table 2. Finally, the sample is stored in an anhydrous and oxygen-free atmosphere or medium.
3. Preparation of support 2
Pseudo-boehmite corresponding to 12 g of alumina, 69.5 g of alumina and 9 g of sesbania powder are weighed and mixed, and then 20 g of polyvinyl alcohol solution (mass concentration is 5 percent) and 4.0 g of nitric acid with mass concentration of 68 percent, which are corresponding to 0.5 g of La, are added2O3La (NO) of3)3.6H2O, Ca (NO) corresponding to 1 g CaO3)2.4H2O, equivalent to 3.0 g ZrO2ZrOCl2.8H2O, 130 ml of water, extruding, drying the wet strip at 120 ℃ for 4 hours, and then roasting the dried wet strip at 700 ℃ for 4 hours to obtain a carrier Z2 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 147m2The pore volume is 0.56 ml/g.
4. Second stage catalyst preparation
Mixing the carrier Z2 with nickel ammonia solution 90 g containing 14 g of nickel, drying at 60 ℃ for 8 hours, drying at 110 ℃ for 2 hours, roasting at 450 ℃ for 4 hours, reducing with hydrogen for 4 hours at the reduction temperature of 450 ℃ and the volume space velocity of hydrogen of 50 hours-1To obtain the second stage catalyst, the specific composition is shown in Table 3.
5. Catalyst evaluation
The hydrogenation operation is carried out in a fixed bed reactor. The upper bed layer of the reactor was packed with the second stage catalyst prepared in example 1, and the lower bed layer was packed with the first stage catalyst prepared in example 1, and the mass ratio of the first stage catalyst to the second stage catalyst was 0.8. The hydrogenation operation is carried out on the material containing the hydrocarbon with the carbon-carbon triple bond in a continuous mode, the top of the reactor is fed, and the bottom of the reactor is discharged. During the experiment, the operating conditions were as follows: the reaction temperature is 60 ℃, the reaction pressure is 1.60MPa, and the weight space velocity of the carbon-carbon triple bond hydrocarbon feeding is 0.1h-1The hydrogen/carbon triple bond hydrocarbon molar ratio was 10, and the hydrogenation evaluation was continuously conducted for 300 hours, and the average hydrogenation results are shown in Table 4.
[ COMPARATIVE EXAMPLE 2 ]
Except that the second stage catalyst also adopts the first stage, the other process conditions are completely the same as the example 1, and specifically:
1. preparation of Carrier 1
Weighing and mixing pseudo-boehmite equivalent to 25 g of alumina, 160 g of alumina and 9 g of sesbania powder, adding 20 g of polyvinyl alcohol solution (mass concentration is 5%), 4.0 g of nitric acid with mass concentration of 68% and 280 ml of water, extruding, drying wet strips at 120 ℃ for 4 hours, and roasting at 750 ℃ for 4 hours to obtain a carrier Z1 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 142m2The pore volume is 0.60 ml/g.
2. First stage catalyst preparation
89.5 g of the carrier Z1 and 110 g of aqueous solution containing 10 g of nickel are mixed, dried at 110 ℃ for 4 hours, mixed and reduced with 100 g of aqueous solution containing 1.0 g of boron potassium borohydride at room temperature for 4 hours, and when no gas is generated, products are washed by distilled water and absolute ethyl alcohol for 4 times in sequence to obtain a first-stage catalyst, wherein the composition of the first-stage catalyst is shown in Table 2. Finally, the sample is stored in an anhydrous and oxygen-free atmosphere or medium.
3. Catalyst evaluation
The hydrogenation operation is carried out in a fixed bed reactor. The upper bed of the reactor was packed with the first stage catalyst prepared in example 1 and the lower bed was also packed with the first stage catalyst. The hydrogenation operation of the material containing the hydrocarbon with carbon-carbon triple bond is carried out in a continuous mode, the top of the reactor is fed,and discharging from the bottom. During the experiment, the operating conditions were as follows: the reaction temperature is 60 ℃, the reaction pressure is 1.60MPa, and the weight space velocity of the carbon-carbon triple bond hydrocarbon feeding is 0.1h-1The hydrogen/carbon triple bond hydrocarbon molar ratio was 10, and the hydrogenation evaluation was continuously conducted for 300 hours, and the average hydrogenation results are shown in Table 4.
[ COMPARATIVE EXAMPLE 3 ]
Except that the first stage also adopts the second stage catalyst, the other process conditions are completely the same as the example 1, specifically:
1. preparation of support 2
Pseudo-boehmite corresponding to 12 g of alumina, 69.5 g of alumina and 9 g of sesbania powder are weighed and mixed, and then 20 g of polyvinyl alcohol solution (mass concentration is 5 percent) and 4.0 g of nitric acid with mass concentration of 68 percent, which are corresponding to 0.5 g of La, are added2O3La (NO) of3)3.6H2O, Ca (NO) corresponding to 1 g CaO3)2.4H2O, equivalent to 3.0 g ZrO2ZrOCl2.8H2O, 130 ml of water, extruding, drying the wet strip at 120 ℃ for 4 hours, and then roasting the dried wet strip at 700 ℃ for 4 hours to obtain a carrier Z2 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 147m2The pore volume is 0.56 ml/g.
2. Second stage catalyst preparation
Mixing the carrier Z2 with nickel ammonia solution 90 g containing 14 g of nickel, drying at 60 ℃ for 8 hours, drying at 110 ℃ for 2 hours, roasting at 450 ℃ for 4 hours, reducing with hydrogen for 4 hours at the reduction temperature of 450 ℃ and the volume space velocity of hydrogen of 50 hours-1To obtain the second stage catalyst, the specific composition is shown in Table 3.
3. Catalyst evaluation
The hydrogenation operation is carried out in a fixed bed reactor. The upper bed of the reactor was packed with the second stage catalyst prepared in example 1 and the lower bed was packed with the second stage catalyst prepared in example 1. The hydrogenation operation is carried out on the material containing the hydrocarbon with the carbon-carbon triple bond in a continuous mode, the top of the reactor is fed, and the bottom of the reactor is discharged. During the experiment, the operating conditions were as follows: reaction temperature: the reaction temperature is 60 ℃, the reaction pressure is 1.60MPa, and the weight space velocity of the carbon-carbon triple bond hydrocarbon feeding is 0.1h-1Hydrogen/carbon triple bond hydrocarbon molThe hydrogenation was evaluated continuously for 300 hours at a molar ratio of 10, and the average hydrogenation results are shown in Table 4.
[ COMPARATIVE EXAMPLE 4 ]
The process conditions were exactly the same as in example 1, except that the first stage catalyst and the second stage catalyst were used in combination, specifically:
1. preparation of Carrier 1
Weighing and mixing pseudo-boehmite equivalent to 25 g of alumina, 160 g of alumina and 9 g of sesbania powder, adding 20 g of polyvinyl alcohol solution (mass concentration is 5%), 4.0 g of nitric acid with mass concentration of 68% and 280 ml of water, extruding, drying wet strips at 120 ℃ for 4 hours, and roasting at 750 ℃ for 4 hours to obtain a carrier Z1 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 142m2The pore volume is 0.60 ml/g.
2. First stage catalyst preparation
89.5 g of the carrier Z1 and 110 g of aqueous solution containing 10 g of nickel are mixed, dried at 110 ℃ for 4 hours, mixed and reduced with 100 g of aqueous solution containing 1.0 g of boron potassium borohydride at room temperature for 4 hours, and when no gas is generated, products are washed by distilled water and absolute ethyl alcohol for 4 times in sequence to obtain a first-stage catalyst, wherein the composition of the first-stage catalyst is shown in Table 2. Finally, the sample is stored in an anhydrous and oxygen-free atmosphere or medium.
3. Preparation of support 2
Pseudo-boehmite corresponding to 12 g of alumina, 69.5 g of alumina and 9 g of sesbania powder are weighed and mixed, and then 20 g of polyvinyl alcohol solution (mass concentration is 5 percent) and 4.0 g of nitric acid with mass concentration of 68 percent, which are corresponding to 0.5 g of La, are added2O3La (NO) of3)3.6H2O, Ca (NO) corresponding to 1 g CaO3)2.4H2O, equivalent to 3.0 g ZrO2ZrOCl2.8H2O, 130 ml of water, extruding, drying the wet strip at 120 ℃ for 4 hours, and then roasting the dried wet strip at 700 ℃ for 4 hours to obtain a carrier Z2 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 147m2The pore volume is 0.56 ml/g.
4. Second stage catalyst preparation
The above-mentioned support Z2 was mixed with 90 g of a nickel ammonia solution containing 14 g of nickelDrying at 60 deg.C for 8 hr, drying at 110 deg.C for 2 hr, calcining at 450 deg.C for 4 hr, and reducing with hydrogen at 450 deg.C for 4 hr at a volume space velocity of 50 hr-1To obtain the second stage catalyst, the specific composition is shown in Table 3.
5. Catalyst evaluation
The hydrogenation operation is carried out in a fixed bed reactor. The upper and lower beds in the reactor were filled with the mixed catalyst of the first stage catalyst and the second stage catalyst prepared in example 1. The hydrogenation operation is carried out on the material containing the hydrocarbon with the carbon-carbon triple bond in a continuous mode, the top of the reactor is fed, and the bottom of the reactor is discharged. During the experiment, the operating conditions were as follows: the reaction temperature is 60 ℃, the reaction pressure is 1.60MPa, and the weight space velocity of the carbon-carbon triple bond hydrocarbon feeding is 0.1h-1The hydrogen/carbon triple bond hydrocarbon molar ratio was 10, and the hydrogenation evaluation was continuously conducted for 300 hours, and the average hydrogenation results are shown in Table 4.
[ example 2 ]
1. Preparation of Carrier 1
Weighing and mixing pseudo-boehmite equivalent to 25 g of alumina, 160 g of alumina and 9 g of sesbania powder, adding 20 g of polyvinyl alcohol solution (mass concentration is 5%), 4.0 g of nitric acid with mass concentration of 68% and 280 ml of water, extruding, drying wet strips at 120 ℃ for 4 hours, and roasting at 750 ℃ for 4 hours to obtain a carrier Z1 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 142m2The pore volume is 0.60 ml/g.
2. First stage catalyst preparation
89.5 g of the carrier Z1 and 110 g of aqueous solution containing 10 g of nickel are mixed, dried at 110 ℃ for 4 hours, mixed and reduced with 100 g of aqueous solution containing 1.0 g of boron potassium borohydride at room temperature for 4 hours, and when no gas is generated, products are washed by distilled water and absolute ethyl alcohol respectively for 4 times to obtain a first-stage catalyst, and the composition of the first-stage catalyst is shown in Table 2. Finally, the sample is stored in an anhydrous and oxygen-free atmosphere or medium.
3. Preparation of support 2
Weighing pseudo-boehmite corresponding to 12 g of alumina, 69.5 g of alumina and 9 g of sesbania powder, mixing, and adding 20 g of polyvinyl alcohol solution (mass concentration is 5%) and nitric acid with mass concentration of 68%4.0 g, corresponding to 0.5 g Ce2O3Ce (NO) of3)3.6H2O, Ca (NO) corresponding to 1 g CaO3)2.4H2O, equivalent to 3.0 g ZrO2ZrOCl2.8H2O, 130 ml of water, extruding, drying the wet strip at 120 ℃ for 4 hours, and then roasting the dried wet strip at 700 ℃ for 4 hours to obtain a carrier Z2 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 147m2The pore volume is 0.56 ml/g.
4. Second stage catalyst preparation
Mixing the carrier Z2 with nickel ammonia solution 90 g containing 14 g of nickel, drying at 60 ℃ for 8 hours, drying at 110 ℃ for 2 hours, roasting at 450 ℃ for 4 hours, reducing with hydrogen for 4 hours at the reduction temperature of 450 ℃ and the volume space velocity of hydrogen of 50 hours-1To obtain the second stage catalyst, the specific composition is shown in Table 3.
5. Catalyst evaluation
The hydrogenation operation is carried out in a fixed bed reactor. The upper bed layer of the reactor was packed with the first stage catalyst prepared in example 1, and the lower bed layer was packed with the second stage catalyst prepared in example 1, and the mass ratio of the first stage catalyst to the second stage catalyst was 0.8. The hydrogenation operation is carried out on the material containing the hydrocarbon with the carbon-carbon triple bond in a continuous mode, the top of the reactor is fed, and the bottom of the reactor is discharged. During the experiment, the operating conditions were as follows: the reaction temperature is 60 ℃, the reaction pressure is 1.60MPa, and the weight space velocity of the carbon-carbon triple bond hydrocarbon feeding is 0.1h-1The hydrogen/carbon triple bond hydrocarbon molar ratio was 10, and the hydrogenation evaluation was continuously conducted for 300 hours, and the average hydrogenation results are shown in Table 4.
[ example 3 ]
1. Preparation of Carrier 1
Weighing and mixing pseudo-boehmite equivalent to 25 g of alumina, 160 g of alumina and 9 g of sesbania powder, adding 20 g of polyvinyl alcohol solution (mass concentration is 5%), 4.0 g of nitric acid with mass concentration of 68% and 280 ml of water, extruding, drying wet strips at 120 ℃ for 4 hours, and roasting at 750 ℃ for 4 hours to obtain a carrier Z1 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 142m2The pore volume is 0.60 ml/g.
2. First stage catalyst preparation
89.5 g of the carrier Z1 and 110 g of aqueous solution containing 10 g of nickel are mixed, dried at 110 ℃ for 4 hours, mixed and reduced with 100 g of aqueous solution containing 1.0 g of boron potassium borohydride at room temperature for 4 hours, and when no gas is generated, products are washed by distilled water and absolute ethyl alcohol respectively for 4 times to obtain a first-stage catalyst, and the composition of the first-stage catalyst is shown in Table 2. Finally, the sample is stored in an anhydrous and oxygen-free atmosphere or medium.
3. Preparation of support 2
Pseudo-boehmite corresponding to 12 g of alumina, 69.5 g of alumina and 9 g of sesbania powder are weighed and mixed, and then 20 g of polyvinyl alcohol solution (mass concentration is 5 percent) and 4.0 g of nitric acid with mass concentration of 68 percent, which are corresponding to 0.25 g of La, are added2O3La (NO) of3)3.6H2O, corresponding to 0.25 g Ce2O3Ce (NO) of3)3.6H2O, Ca (NO) corresponding to 1 g CaO3)2.4H2O, equivalent to 3.0 g ZrO2ZrOCl2.8H2O, 130 ml of water, extruding, drying the wet strip at 120 ℃ for 4 hours, and then roasting the dried wet strip at 700 ℃ for 4 hours to obtain a carrier Z2 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 147m2The pore volume is 0.56 ml/g.
4. Second stage catalyst preparation
Mixing the carrier Z2 with nickel ammonia solution 90 g containing 14 g of nickel, drying at 60 ℃ for 8 hours, drying at 110 ℃ for 2 hours, roasting at 450 ℃ for 4 hours, reducing with hydrogen for 4 hours at the reduction temperature of 450 ℃ and the volume space velocity of hydrogen of 50 hours-1To obtain the second stage catalyst, the specific composition is shown in Table 3.
5. Catalyst evaluation
The hydrogenation operation is carried out in a fixed bed reactor. The upper bed layer of the reactor was packed with the first stage catalyst prepared in example 1, and the lower bed layer was packed with the second stage catalyst prepared in example 1, and the mass ratio of the first stage catalyst to the second stage catalyst was 0.8. The hydrogenation operation is carried out on the material containing the hydrocarbon with the carbon-carbon triple bond in a continuous mode, the top of the reactor is fed, and the bottom of the reactor is discharged. During the experiment, the operating conditions were as follows: the reaction temperature is 60 ℃, the reaction pressure is 1.60MPa, and carbon-carbon triple bonds are formedThe weight space velocity of hydrocarbon feeding is 0.1h-1The hydrogen/carbon triple bond hydrocarbon molar ratio was 10, and the hydrogenation evaluation was continuously conducted for 300 hours, and the average hydrogenation results are shown in Table 4.
[ example 4 ]
1. Preparation of Carrier 1
Weighing 30 g of pseudo-boehmite equivalent to alumina, 170 g of alumina and 9 g of sesbania powder, mixing, adding 20 g of polyvinyl alcohol solution (mass concentration is 5%), 4.0 g of nitric acid with mass concentration of 68% and 280 ml of water, extruding, drying wet strips at 120 ℃ for 4 hours, and roasting at 700 ℃ for 4 hours to obtain a carrier Z1 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 140m2The pore volume is 0.57 ml/g.
2. First stage catalyst preparation
83 g of the carrier Z1 is mixed with 104 g of aqueous solution containing 15 g of nickel, after drying for 4 hours at 110 ℃, the mixture is reduced for 4 hours at room temperature by 100 g of aqueous solution containing 2 g of boron-containing potassium borohydride, and when no gas is generated, the product is washed for 4 times by distilled water and absolute ethyl alcohol in sequence to obtain the first-stage catalyst, and the composition of the first-stage catalyst is shown in Table 2. Finally, the sample is stored in an anhydrous and oxygen-free atmosphere or medium.
3. Preparation of support 2
Weighing pseudo-boehmite corresponding to 12 g of alumina, 69.0 g of alumina and 9 g of sesbania powder, mixing, adding 20 g of polyvinyl alcohol solution (mass concentration is 5 percent) and 4.0 g of nitric acid with mass concentration of 68 percent, corresponding to 0.3 g of La2O3La (NO) of3)3.6H2O, Ca (NO) corresponding to 0.6 g CaO3)2.4H2O, equivalent to 4.0 g ZrO2ZrOCl2.8H2O, 130 ml of water, extruding, drying the wet strip at 120 ℃ for 4 hours, and then roasting the dried wet strip at 700 ℃ for 4 hours to obtain a carrier Z2 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 152m2The pore volume is 0.58 ml/g.
4. Second stage catalyst preparation
Mixing the above carrier Z2 with nickel ammonia solution 90 g containing 12 g of nickel, drying at 60 deg.C for 8 hr, drying at 110 deg.C for 2 hr, calcining at 450 deg.C for 4 hr, reducing with hydrogen for 4 hr, and optionally addingThe original temperature is 450 ℃, and the volume space velocity of hydrogen is 50 hours-1To obtain the second stage catalyst, the specific composition is shown in Table 3.
5. Catalyst evaluation
The hydrogenation operation is carried out in a fixed bed reactor. The upper bed layer of the reactor was packed with the first stage catalyst prepared in example 4, and the lower bed layer was packed with the second stage catalyst prepared in example 4, and the mass ratio of the first stage catalyst to the second stage catalyst was 0.8. The hydrogenation operation is carried out on the material containing the hydrocarbon with the carbon-carbon triple bond in a continuous mode, the top of the reactor is fed, and the bottom of the reactor is discharged. During the experiment, the operating conditions were as follows: the reaction temperature is 70 ℃, the reaction pressure is 1.60MPa, and the weight space velocity of the carbon-carbon triple bond hydrocarbon feeding is 0.08h-1The hydrogen/carbon triple bond hydrocarbon molar ratio was 8, and the hydrogenation evaluation was continuously conducted for 300 hours, and the average hydrogenation results are shown in Table 4.
[ example 5 ]
1. Preparation of Carrier 1
Weighing pseudo-boehmite equivalent to 25 g of alumina, 170 g of alumina and 9 g of sesbania powder, mixing, adding 20 g of polyvinyl alcohol solution (mass concentration is 5%), 4.0 g of nitric acid with mass concentration of 68% and 280 ml of water, extruding, drying wet strips at 120 ℃ for 4 hours, and roasting at 750 ℃ for 4 hours to obtain a carrier Z1 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 142m2The pore volume is 0.6 ml/g.
2. First stage catalyst preparation
82 g of the carrier Z1 and 100 g of aqueous solution containing 15.0 g of nickel are mixed, dried at 110 ℃ for 4 hours, mixed and reduced by 100 g of potassium borohydride aqueous solution containing 3 g of boron for 4 hours at room temperature, and when no gas is generated, products are washed by distilled water and absolute ethyl alcohol respectively for 4 times to obtain a first-stage catalyst, wherein the composition of the first-stage catalyst is shown in Table 2. Finally, the sample is stored in an anhydrous and oxygen-free atmosphere or medium.
3. Preparation of support 2
Pseudo-boehmite corresponding to 12 g of alumina, 69.7 g of alumina and 9 g of sesbania powder are weighed and mixed, and then 20 g of polyvinyl alcohol solution (mass concentration is 5 percent) and 4.0 g of nitric acid with mass concentration of 68 percent, which are corresponding to 0.3 g of La, are added2O3La (NO) of3)3.6H2O, Ca (NO) corresponding to 2.0 g CaO3)2.4H2O, equivalent to 2.0 g ZrO2ZrOCl2.8H2O, 130 ml of water, extruding, drying the wet strip at 120 ℃ for 4 hours, and then roasting the dried wet strip at 750 ℃ for 4 hours to obtain a carrier Z2 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 135m2The pore volume is 0.63 ml/g.
4. Second stage catalyst preparation
Mixing the carrier Z2 with nickel ammonia solution 90 g containing 14 g of nickel, drying at 60 ℃ for 8 hours, drying at 110 ℃ for 2 hours, roasting at 400 ℃ for 4 hours, reducing with hydrogen for 4 hours at the reduction temperature of 450 ℃ and the volume space velocity of the hydrogen of 50 hours-1To obtain the second stage catalyst, the specific composition is shown in Table 3.
5. Catalyst evaluation
The hydrogenation operation is carried out in a fixed bed reactor. The upper bed layer of the reactor was packed with the first stage catalyst prepared in example 5, and the lower bed layer was packed with the second stage catalyst prepared in example 5, and the mass ratio of the first stage catalyst to the second stage catalyst was 0.8. The hydrogenation operation is carried out on the material containing the hydrocarbon with the carbon-carbon triple bond in a continuous mode, the top of the reactor is fed, and the bottom of the reactor is discharged. During the experiment, the operating conditions were as follows: the reaction temperature is 80 ℃, the reaction pressure is 1.80MPa, and the weight space velocity of the carbon-carbon triple bond hydrocarbon feeding is 0.12h-1The hydrogen/carbon triple bond hydrocarbon molar ratio was 10, and the hydrogenation evaluation was continuously conducted for 300 hours, and the average hydrogenation results are shown in Table 4.
[ example 6 ]
1. Preparation of Carrier 1
Weighing and mixing pseudo-boehmite equivalent to 25 g of alumina, 160 g of alumina and 9 g of sesbania powder, adding 20 g of polyvinyl alcohol solution (mass concentration is 5%), 4.0 g of nitric acid with mass concentration of 68% and 280 ml of water, extruding, drying wet strips at 120 ℃ for 4 hours, and roasting at 750 ℃ for 4 hours to obtain a carrier Z1 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 142m2The pore volume is 0.60 ml/g.
2. First stage catalyst preparation
89.5 g of the carrier Z1 and 110 g of aqueous solution containing 10 g of nickel are mixed, dried at 110 ℃ for 4 hours, mixed and reduced with 100 g of aqueous solution containing 0.5 g of boron potassium borohydride at room temperature for 4 hours, and when no gas is generated, products are washed by distilled water and absolute ethyl alcohol respectively for 4 times to obtain a first-stage catalyst, and the composition of the first-stage catalyst is shown in Table 2. Finally, the sample is stored in an anhydrous and oxygen-free atmosphere or medium.
3. Preparation of support 2
Pseudo-boehmite corresponding to 12 g of alumina, 69.5 g of alumina and 9 g of sesbania powder are weighed and mixed, and then 20 g of polyvinyl alcohol solution (mass concentration is 5 percent) and 4.0 g of nitric acid with mass concentration of 68 percent, which are corresponding to 0.5 g of La, are added2O3La (NO) of3)3.6H2O, Ca (NO) corresponding to 1 g CaO3)2.4H2O, equivalent to 3.0 g ZrO2ZrOCl2.8H2O, 130 ml of water, extruding, drying the wet strip at 120 ℃ for 4 hours, and then roasting the dried wet strip at 700 ℃ for 4 hours to obtain a carrier Z2 with the length of 2 mm and the diameter of 1 mm and the specific surface area of 147m2The pore volume is 0.56 ml/g.
4. Second stage catalyst preparation
Mixing the carrier Z2 with nickel ammonia solution 90 g containing 14 g of nickel, drying at 60 ℃ for 8 hours, drying at 110 ℃ for 2 hours, roasting at 450 ℃ for 4 hours, reducing with hydrogen for 4 hours at the reduction temperature of 450 ℃ and the volume space velocity of hydrogen of 50 hours-1To obtain the second stage catalyst, the specific composition is shown in Table 3.
5. Catalyst evaluation
The hydrogenation operation is carried out in a fixed bed reactor. The upper bed layer of the reactor was packed with the first stage catalyst prepared in example 1, and the lower bed layer was packed with the second stage catalyst prepared in example 1, and the mass ratio of the first stage catalyst to the second stage catalyst was 0.8. The hydrogenation operation is carried out on the material containing the hydrocarbon with the carbon-carbon triple bond in a continuous mode, the top of the reactor is fed, and the bottom of the reactor is discharged. During the experiment, the operating conditions were as follows: the reaction temperature is 60 ℃, the reaction pressure is 1.60MPa, and the weight space velocity of the carbon-carbon triple bond hydrocarbon feeding is 0.1h-1The hydrogen/carbon triple bond hydrocarbon molar ratio is 10, the hydrogenation evaluation is continuously carried out for 300 hours, and the average hydrogenation result is shown in the table4。
TABLE 1
| Composition by weight | Raw materials |
| Vinyl acetylene (%) | 0.8 |
| Benzene (%) | 0.7 |
| Diacetylene (%) | 2.2 |
| N-methylpyrrolidone (%) | 96.1 |
| Others (%) | 0.2 |
TABLE 2 first stage catalyst composition
| Ni，w％ | B，w％ | |
| Example 1 | 10 | 1.0 |
| Example 2 | 10 | 1.0 |
| Example 3 | 10 | 1.0 |
| Example 4 | 12 | 2.0 |
| Example 5 | 15 | 3.0 |
| Example 6 | 10 | 0.5 |
| Comparative example 1 | 10 | 1.0 |
| Comparative example 2 | 10 | 1.0 |
| Comparative example 3 | - | - |
| Comparative example 4 | 10 | 1.0 |
TABLE 3 second stage catalyst composition
TABLE 4
Claims (9)
1. The hydrocarbon hydrogenation catalyst containing carbon-carbon triple bonds comprises a first-stage catalyst and a second-stage catalyst, wherein the first-stage catalyst comprises a carrier 1 and nickel or oxides thereof and boron or compounds thereof, and the second-stage catalyst comprises a carrier 2 and nickel or oxides thereof; the second-stage catalyst comprises the following components in percentage by weight:
(a) 10-25% of metallic nickel or its oxide;
(b) 0.2-1% of at least one element selected from rare earths or an oxide thereof;
(c) 0.2-2.0% of a compound selected from the periodic Table of the elements
At least one metal of A or an oxide thereof;
(d) 2-5% of Zr or its oxide.
2. The catalyst according to claim 1, wherein the weight ratio of the first-stage catalyst to the second-stage catalyst is 0.5 to 1.
3. The catalyst of claim 1, wherein the first stage catalyst comprises the following components in weight percent:
(a) 5-20% of metal Ni or its oxide;
(b)0.5 to 3% of boron or a compound thereof.
4. A process for hydroprocessing a feed containing carbon to carbon triple bond hydrocarbons using the catalyst of any one of claims 1 to 3, comprising the steps of:
(1) contacting hydrogen and the material with the first-stage catalyst to react to generate an intermediate material containing monoene;
(2) and hydrogenating the intermediate material in the presence of a second-stage catalyst to obtain a material containing alkane.
5. The method according to claim 4, wherein the reaction temperature in step (1) and/or step (2) is 40-90%oC。
6. The method according to claim 4, wherein the reaction pressure in step (1) and/or step (2) is 0.5 to 3 MPa.
7. The method as set forth in claim 4, characterized in that the weight space velocity of the carbon-carbon triple bond hydrocarbon in the step (1) is 0.05-0.4 h-1。
8. The method according to claim 4, wherein the molar ratio of the hydrocarbon having a triple bond of hydrogen to carbon in the step (1) is 6 to 30.
9. The method as set forth in claim 4, characterized in that said feed containing hydrocarbons having carbon-carbon triple bonds contains a diluent.
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