CN111085221A - Silver-zinc doped Raney copper catalyst and preparation method and application thereof - Google Patents
Silver-zinc doped Raney copper catalyst and preparation method and application thereof Download PDFInfo
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- CN111085221A CN111085221A CN201811242533.5A CN201811242533A CN111085221A CN 111085221 A CN111085221 A CN 111085221A CN 201811242533 A CN201811242533 A CN 201811242533A CN 111085221 A CN111085221 A CN 111085221A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 title claims abstract description 41
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052709 silver Inorganic materials 0.000 claims abstract description 66
- 239000004332 silver Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 43
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 32
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 26
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 22
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 17
- 239000000725 suspension Substances 0.000 claims abstract description 15
- 150000001412 amines Chemical class 0.000 claims abstract description 14
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 8
- 239000011701 zinc Substances 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000005275 alloying Methods 0.000 claims abstract description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 25
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 238000005259 measurement Methods 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 44
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 3
- -1 acetylene hydrocarbon Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 92
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 23
- 229910001961 silver nitrate Inorganic materials 0.000 description 20
- 238000005406 washing Methods 0.000 description 20
- WFYPICNXBKQZGB-UHFFFAOYSA-N butenyne Chemical group C=CC#C WFYPICNXBKQZGB-UHFFFAOYSA-N 0.000 description 18
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 238000001914 filtration Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 150000000475 acetylene derivatives Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
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
- B01J25/00—Catalysts of the Raney type
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
- C07C7/167—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation for removal of compounds containing a triple carbon-to-carbon bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of catalysts for hydrogenation and alkyne removal in petrochemical industry, in particular to a preparation method of a silver-zinc doped Raney copper catalyst, which comprises the following steps: 1) alloying zinc, copper and aluminum to obtain an active metal alloy; 2) activating the active metal alloy to obtain a catalyst precursor, and adding a solvent to prepare a catalyst suspension; 3) mixing soluble organic amine and silver salt to prepare silver source solution; 4) and reacting the silver source solution with the catalyst suspension to obtain the silver-zinc doped Raney copper catalyst. The silver-zinc doped Raney copper catalyst is used for C4In the process of selective hydrogenation acetylene removal of fractions, the method has the characteristics of high space velocity, high acetylene hydrocarbon selection and low butadiene lossAnd (4) point.
Description
Technical Field
The invention relates to the field of catalysts for hydrogenation and alkyne removal in petrochemical industry, in particular to a preparation method of a silver-zinc doped Raney copper catalyst, the silver-zinc doped Raney copper catalyst prepared by the method and the silver-zinc doped Raney copper catalyst in C4Use of selective hydrogenation of fractions for alkyne removal.
Background
C4Fraction means a mixture of alkanes, alkenes, dienes and alkynes of four carbon atoms, C4The acetylene hydrocarbon in the fraction mainly includes vinyl acetylene, ethyl acetylene and propyne. These alkynes are very dangerous, with vinylacetylene being the most dangerous and above a certain concentration, easily causing decomposition explosions. Therefore, the concentration of vinyl acetylene must be strictly controlled in production, and in addition, in a butadiene plant, since the higher alkyne by-product affects the product quality of butadiene, the removal of vinyl acetylene from butadiene is an indispensable procedure.
Currently from cleavage C4Butadiene is usually extracted from the fraction by a solvent extraction method such as acetonitrile method, N-methylpyrrolidone method and dimethylformamide method. At present, the methods can basically meet the requirement of butadiene purity, but the cracking C is influenced by factors such as cracking depth, cracking technology and the like4The alkyne content in the fraction shows a trend of increasing year by year, which leads to the increase of the loss of the butadiene and the increase of the energy consumption in the extraction process, and simultaneously, the alkyne content in the butadieneThe restrictions are more severe, and these all deteriorate the economics of the butadiene extraction unit.
Besides the solvent extraction method, the catalyst hydrogenation alkyne removal method is also an effective alkyne removal method. The method utilizes a selective hydrogenation catalyst to carry out hydrogenation reaction on C4Alkynes such as methylacetylene, ethylacetylene, vinylacetylene and the like in the fraction are converted into butadiene, butene and a small amount of butane, and the alkynes can be effectively removed. At present, a small amount of industrial application exists abroad, but the method also has a remarkable defect that the requirement on the catalyst is high, high activity and high selectivity are required, and in addition, high stability is important for achieving the purpose of long-term and low-cost operation. At present, two types of catalysts for removing acetylene by hydrogenation are selected, one type is a Pd series catalyst which has high activity and can realize hydrogenation reaction at high space velocity, but the defects are that the loss of butadiene is large and the service life is short. Still another type is copper based catalysts, which have low butadiene loss but low space velocity and short life. The catalyst adopted by the industrialized U.S. DOW KLP technology is a copper catalyst, ten sets of devices are built all over the world, and the catalyst adopted by the KLP technology also has the problems of frequent regeneration, low airspeed and the like. The Beijing institute of chemical industry developed a copper catalyst applied to C4In selective hydrogenation alkyne removal reactions, the catalyst is highly active but is intended to remove C simultaneously4All acetylenes in the distillate tend to result in high butadiene losses.
In conclusion, a catalyst pair C with high space velocity and high selectivity was developed4The selective hydrogenation of the fractions for the removal of hydrocarbons is of great importance.
Disclosure of Invention
The object of the present invention is to overcome the existing C of the prior art4The preparation method of the silver-zinc doped Raney copper catalyst and the silver-zinc doped Raney copper catalyst prepared by the method have the defects of low catalyst airspeed, low alkyne selectivity and high butadiene loss in the selective hydrogenation alkyne removal process of fractions. The silver-zinc doped Raney copper catalyst is used for the catalyst C4Fraction selectivityIn the acetylene hydrogenation and removal process, the method has the characteristics of high space velocity, high acetylene hydrocarbon selection and low butadiene loss.
The inventor of the invention finds that the silver-zinc doped Raney copper catalyst can be prepared by dropwise adding a silver source solution prepared by mixing soluble organic amine and silver salt into a suspension of a catalyst precursor prepared by activating an active metal alloy. The silver-zinc doped Raney copper catalyst is applied to high airspeed C4When the acetylene is removed by fraction selective hydrogenation, the vinyl acetylene can be removed in a targeted manner, namely, the selectivity to the vinyl acetylene is higher (the residual vinyl acetylene is less than 8ppm), and the loss amount of butadiene is low (less than 0.3 weight percent).
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a silver-zinc doped raney copper catalyst, comprising the steps of:
1) alloying zinc, copper and aluminum to obtain an active metal alloy;
2) activating the active metal alloy to obtain a catalyst precursor, and adding a solvent to prepare a catalyst suspension;
3) mixing soluble organic amine and silver salt to prepare silver source solution;
4) and reacting the silver source solution with the catalyst suspension to obtain the silver-zinc doped Raney copper catalyst.
In a second aspect, the invention provides a silver-zinc doped raney copper catalyst prepared by the method of the first aspect.
In a third aspect of the invention, the silver-zinc doped Raney copper catalyst is prepared at C4Use of selective hydrogenation of fractions for alkyne removal.
By adopting the technical scheme, the silver-zinc doped Raney copper catalyst provided by the invention is used for C4In the process of selective hydrogenation and alkyne removal of the fraction, the method has the characteristics of high space velocity, high alkyne selection and low butadiene loss.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of a silver-zinc doped Raney copper catalyst, which comprises the following steps:
1) alloying zinc, copper and aluminum to obtain an active metal alloy;
2) activating the active metal alloy to obtain a catalyst precursor, and adding a solvent to prepare a catalyst suspension;
3) mixing soluble organic amine and silver salt to prepare silver source solution;
4) and reacting the silver source solution with the catalyst suspension to obtain the silver-zinc doped Raney copper catalyst.
Preferably, the zinc content is 0.01-20 wt%, the copper content is 10-50 wt%, and the aluminum content is 40-80 wt%, based on the total weight of the active metal alloy;
the silver source solution is used in an amount such that the weight ratio of the silver to the catalyst precursor is (0.05-1.0): 100.
in order to further improve the selectivity of the silver-zinc doped raney copper catalyst prepared by the method of the invention to alkyne, namely the selectivity of vinyl acetylene, preferably, the dosage of the silver source solution is such that the weight ratio of the silver to the zinc doped raney copper catalyst is (0.1-0.6): 100.
in the present invention, the method for alloying zinc, copper and aluminum is not particularly limited, and may be an alloying method known to those skilled in the art. As a specific embodiment of the invention, the active metal alloy can be obtained by calcining for 2-4h at the temperature of 630-680 ℃ under the protection of nitrogen atmosphere and naturally cooling to room temperature.
In the present invention, preferably, the activation is carried out in a lye, the concentration of which is 2 to 40% by weight; more preferably 5 to 20 wt%.
In the present invention, the alkali solution is preferably an aqueous sodium hydroxide solution and/or an aqueous potassium hydroxide solution, and more preferably an aqueous sodium hydroxide solution.
In the present invention, preferably, the activation conditions include: the activation temperature is 20-100 ℃, and the activation time is 0.5-3 h.
In the present invention, it is preferable that the average particle diameter of the catalyst precursor is 2 to 3 mm.
In the present invention, the solvent used in the preparation of the catalyst suspension by adding the solvent to the catalyst precursor is not particularly limited, and may be any of various solvents known in the art for preserving a raney catalyst.
In the invention, the preparation process of the silver source solution comprises the following steps: the soluble organic amine is mixed with a silver salt, preferably silver nitrate. As a specific embodiment of the present invention, the following method may be adopted: adding a certain amount of silver nitrate into a certain amount of water, and stirring until the silver nitrate is dissolved; then, a certain amount of organic amine is dripped into a certain amount of water; and (3) dropwise adding the organic amine solution into a silver nitrate solution to form a transparent and uniform solution, and then carrying out constant volume to obtain a silver source solution.
Preferably, the concentration of silver in the silver source solution is 0.05-20mgAg/mL, more preferably 1-6 mgAg/mL.
In the present invention, preferably, the molar ratio of the organic amine to silver is (1-10): 1, preferably (2-5): 1.
in the present invention, the organic amine is not particularly limited and may be any of various organic amines capable of forming a complex with metallic silver, and preferably, the organic amine is at least one selected from the group consisting of ethylenediamine tetraacetic acid, triethanolamine, diethanolamine, ethanolamine, butylamine, isopropylamine, aniline, diethylamine, N-dimethylaniline, ethylenediamine, dodecylamine, triethylenediamine, cyclohexylamine, and hexamethylenetetramine; more preferably at least one of triethanolamine, isopropylamine, ethanolamine, ethylenediamine and hexamethylenediamine.
In the invention, preferably, the silver source solution is dropwise added into the catalyst suspension to react for 1-2h, and the silver-zinc doped raney copper catalyst is prepared after filtration and washing.
In a second aspect, the invention provides a silver-zinc doped raney copper catalyst prepared by the method of the first aspect.
In a third aspect of the invention, the silver-zinc doped Raney copper catalyst is prepared at C4Use of selective hydrogenation of fractions for alkyne removal.
Preferably, said C4The reaction conditions for the selective hydrogenation of the distillate to remove acetylene include: the temperature of a reaction inlet is 30-60 ℃, the reaction pressure is 0.5-2.0MPa, and C is used4The reaction space velocity of liquid volume measurement in the fraction is 2-20h-1Hydrogen and C4The molar ratio of alkynes in the fraction is (0.2-10): 1. with C4The alkyne content is 0.6-1.5 wt% based on the total weight of the fraction. More preferably, with C4The reaction space velocity of liquid volume measurement in the fraction is 10-20h-1。
Preferably, said C4The distillate selective hydrogenation alkyne removal reaction is carried out in a fixed bed reactor.
The substantial difference between the present invention and the prior art is:
(1) the silver-zinc doped Raney copper catalyst can improve C4The selectivity of total alkynes in the fraction, particularly the selectivity to vinyl acetylene is higher.
(2) The silver-zinc doped Raney copper catalyst of the invention is prepared at C4In the selective hydrogenation alkyne removal reaction, the loss of butadiene is lower.
(3) Compared with the traditional copper catalyst, the silver-zinc doped Raney copper catalyst can carry out hydrogenation reaction at high space velocity, and the space velocity can reach 20h-1。
The invention has the beneficial effects that:
the silver-zinc doped Raney copper catalyst provided by the invention is used for C4Fraction hydrogenation acetylene removal reaction has high selectivity, the content of vinyl acetylene after the reaction is less than 8ppm, and the loss of butadiene is less than 0.3 weight percent.
The present invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, various raw materials used are commercially available.
Preparation example 1
(1)545g of copper powder, 518g of aluminum powder and 100g of zinc powder are fully mixed, calcined for 3 hours at 650 ℃ under the protection of nitrogen atmosphere, naturally cooled to room temperature and taken out to obtain the active metal alloy.
(2) Preparing 400g of 20 wt% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1h, washing until the pH value of a washing liquid is 8 to obtain a catalyst precursor, adding water to prepare a catalyst suspension, and storing for later use.
(3) Preparing a silver solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until the silver nitrate is dissolved, 2.4mL of isopropylamine solution (isopropylamine density: 0.7g/mL) is dripped into 10mL of deionized water to prepare a uniform solution. The molar ratio of isopropylamine to silver was 4: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
(4) And (3) weighing 30mL (about 28g) of the sample obtained in the step (2), adding the sample into 50mL of aqueous solution, dropwise adding 10mL (the content of silver is 30mg, and the silver accounts for 0.11 wt% of the weight of the added catalyst precursor) of the silver source solution in the step (3), reacting for 2h, filtering, and washing the solution to obtain the silver-zinc doped Raney copper catalyst.
Preparation example 2
(1)545g of copper powder, 518g of aluminum powder and 50g of zinc powder are fully mixed and calcined at 680 ℃ for 2.2h under the protection of nitrogen atmosphere, and then the mixture is naturally cooled to room temperature and taken out to obtain the active metal alloy.
(2) Preparing 400g of 15 wt% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 100 ℃, filtering the solution after 0.5h, washing until the pH value of a washing liquid is 8, and storing the washing liquid in the deionized water for later use.
(3) Preparing a silver solution: weighing 1.2g of silver nitrate (molar weight: 7.1mmol), adding 10mL of deionized water, stirring until the silver nitrate is dissolved, and dropwise adding 1.9mL of triethanolamine solution (density: 1.1g/mL of triethanolamine) into 10mL of deionized water to prepare a uniform solution. The molar ratio of triethanolamine to silver was 4: 1, dropwise adding a solution of triethanolamine into a silver nitrate solution to form a transparent and uniform solution, and quantitatively accommodating the solution in a 200mL volumetric flask to form a silver source solution of 3.0 mgAg/mL.
(4) And (3) weighing 30mL (about 28g) of the sample obtained in the step (2), adding the sample into 50mL of aqueous solution, dropwise adding 10mL (the content of silver is 30mg, and the silver accounts for 0.11 wt% of the weight of the added catalyst precursor) of the silver source solution in the step (3), reacting for 2h, filtering, and washing the solution to obtain the silver-zinc doped Raney copper catalyst.
Preparation example 3
(1)545g of copper powder, 518g of aluminum powder and 200g of zinc powder are fully mixed, calcined for 4 hours at the temperature of 630 ℃ under the protection of nitrogen atmosphere, naturally cooled to room temperature and taken out to obtain the active metal alloy.
(2) Preparing 400g of 5 wt% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 60 ℃, filtering the solution after 1.5h, washing until the pH value of a washing liquid is 8 to obtain a catalyst precursor, adding water to prepare a catalyst suspension, and storing for later use.
(3) Preparing a silver solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until the silver nitrate is dissolved, 2.4mL of isopropylamine solution (isopropylamine density: 0.7g/mL) is dripped into 10mL of deionized water to prepare a uniform solution. The molar ratio of isopropylamine to silver was 4: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
(4) And (3) weighing 30mL (about 28g) of the sample obtained in the step (2), adding the sample into 50mL of aqueous solution, dropwise adding 10mL (the content of silver is 30mg, and accounts for 0.11 wt% of the weight of the added catalyst precursor) of the silver source solution in the step (3), reacting for 2h, filtering, and washing the solution to obtain the silver-zinc doped Raney copper catalyst.
Preparation example 4
The process of preparation example 1 was followed except that step (4) was carried out as follows:
and (3) weighing 30mL (about 28g) of the sample obtained in the step (2), adding the sample into 50mL of aqueous solution, dropwise adding 20mL of the silver source solution (the content of silver is 60mg, and the silver accounts for 0.21 wt% of the weight of the added catalyst precursor) obtained in the step (3), reacting for 2h, filtering, and washing the solution to obtain the silver-zinc doped Raney copper catalyst.
Preparation example 5
The process of preparation example 1 was followed except that step (4) was carried out as follows:
measuring 30mL (about 28g) of the sample obtained in the step (2), adding the sample into 50mL of aqueous solution, dropwise adding 40mL of the silver source solution (the content of silver is 120mg, and the silver accounts for 0.43 wt% of the weight of the added catalyst precursor) obtained in the step (3), reacting for 2h, filtering, and washing the solution to obtain the silver-zinc doped Raney copper catalyst.
Preparation example 6
The process of preparation example 1 was followed except that step (4) was carried out as follows:
measuring 30mL (about 28g) of the sample obtained in the step (2), adding the sample into 50mL of aqueous solution, dropwise adding 5mL of the silver source solution (the content of silver is 15mg, and the silver accounts for 0.05 wt% of the weight of the added catalyst precursor) in the step (3), reacting for 2h, filtering, and washing the solution to obtain the silver-zinc doped Raney copper catalyst.
Preparation example 7
The process of preparation example 1 was followed except that step (4) was carried out as follows:
and (3) weighing 30mL (about 28g) of the sample obtained in the step (2), adding the sample into 50mL of aqueous solution, dropwise adding 100mL of the silver source solution (the content of silver is 300mg, and the silver accounts for 1.0 wt% of the weight of the added catalyst precursor) obtained in the step (3), reacting for 2 hours, filtering, and washing the solution to obtain the silver-zinc doped raney copper catalyst.
Preparation example 8
The process of preparation example 1 was followed except that step (3) was carried out as follows:
preparing a silver solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until being dissolved, 1.2mL of isopropylamine solution (density: 0.7g/mL of isopropylamine) is dripped into 10mL of deionized water to prepare uniform solution. The molar ratio of isopropylamine to silver is 2: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
Preparation example 9
The process of preparation example 1 was followed except that step (3) was carried out as follows:
preparing a silver solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until being dissolved, 1.2mL of isopropylamine solution (density: 0.7g/mL of isopropylamine) is dripped into 10mL of deionized water to prepare uniform solution. The molar ratio of isopropylamine to silver was 10: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
Comparative preparation example 1
(1)545g of copper powder, 518g of aluminum powder and 100g of zinc powder are fully mixed, calcined for 3 hours at 650 ℃ under the protection of nitrogen atmosphere, naturally cooled to room temperature and taken out to obtain the active metal alloy.
(2) Preparing 400g of 20 wt% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1h, washing until the pH value of a washing liquid is 8 to obtain a catalyst precursor, adding water to prepare a catalyst suspension, and storing for later use.
Comparative preparation example 2
(1)545g of copper powder and 518g of aluminum powder are fully mixed and calcined for 3 hours at 650 ℃ under the protection of nitrogen atmosphere, and then the mixture is naturally cooled to room temperature and taken out to obtain the active metal alloy.
(2) Preparing 400g of 20 wt% NaOH aqueous solution by using deionized water, adding 80g of the catalyst obtained in the step (1), keeping the temperature at 85 ℃, filtering the solution after 1h, washing until the pH value of a washing liquid is 8 to obtain a catalyst precursor, adding water to prepare a catalyst suspension, and storing for later use.
(3) Preparing a silver solution: 1.2g of silver nitrate (molar weight: 7.1mmol) is weighed, 10mL of deionized water solution is added and stirred until the silver nitrate is dissolved, 2.4mL of isopropylamine solution (isopropylamine density: 0.7g/mL) is dripped into 10mL of deionized water to prepare a uniform solution. The molar ratio of isopropylamine to silver was 4: 1, dropwise adding the solution of isopropylamine into the silver nitrate solution to form a transparent and uniform solution, and placing the solution into a 200mL volumetric flask to form a 3.0mgAg/mL silver source solution.
(4) And (3) weighing 30mL (about 28g) of the sample obtained in the step (2), adding the sample into 50mL of aqueous solution, dropwise adding 10mL (the content of silver is 30mg, and the silver accounts for 0.11 wt% of the weight of the added catalyst precursor) of the silver source solution in the step (3), reacting for 2h, filtering, and washing the solution to obtain the silver-zinc doped Raney copper catalyst.
Example 1
45mL of the catalyst obtained in production examples 1 to 9 and comparative production examples 1 to 2 was charged in a fixed bed reactor, and after replacement with nitrogen, hydrogen and C were added4The molar ratio of alkynes in the fraction was 5: 1 is passed into the reactor. C4The compositions (mass percentages) of the fractions are shown in Table 1. The reaction conditions are as follows:
at an inlet temperature of 45 ℃ and a reaction pressure of 1.5MPa, and C4The space velocity of the reaction measured by the volume of the liquid in the fraction is 10h-1With C4The alkyne content was 0.95 wt% based on the total weight of the fractions.
Determination of C by gas chromatography4The contents of the components in the fractions.
For the above catalyst C4The selective hydrogenation catalytic performance of the fractions was evaluated, and the amounts of residual vinylacetylene and butadiene lost after the reaction was continued for 100 hours are shown in Table 2.
TABLE 1
| Components | Content (wt%) |
| Isobutane | 2.35 |
| N-butane | 4.73 |
| Trans-2-butene | 4.49 |
| 1-butene | 13.9 |
| Isobutene | 21.31 |
| Cis-2-butene | 3.36 |
| 1, 2-butadiene | 0.17 |
| 1, 3-butadiene | 48.56 |
| Methylacetylene | 0.08 |
| Ethyl acetylene | 0.73 |
| Vinyl acetylene | 0.14 |
TABLE 2
| Catalyst sample | Residual vinyl acetylene (ppm) | Butadiene loss amount (% by weight) |
| Preparation example 1 | 3.8 | 0.15 |
| Preparation example 2 | 3.2 | 0.20 |
| Preparation example 3 | 3.6 | 0.19 |
| Preparation example 4 | 4.1 | 0.18 |
| Preparation example 5 | 3.9 | 0.21 |
| Preparation example 6 | 7.2 | 0.29 |
| Preparation example 7 | 7.5 | 0.30 |
| Preparation example 8 | 4.2 | 0.22 |
| Preparation example 9 | 7.6 | 0.29 |
| Comparative preparation example 1 | 15 | 0.6 |
| Comparative preparation example 2 | 50 | 1.6 |
Example 2
The process of example 1 was followed except that the reaction conditions were:
at an inlet temperature of 45 ℃ and a reaction pressure of 1.5MPa, and C4The reaction space velocity of liquid volume measurement in the fraction is 15h-1With C4The alkyne content was 0.95 wt% based on the total weight of the fractions. The results are shown in Table 3.
TABLE 3
Example 3
The process of example 1 was followed except that the reaction conditions were:
at an inlet temperature of 45 ℃ and a reaction pressure of1.5MPa and C4The reaction space velocity of the liquid volume metering in the fraction is 20h-1With C4The alkyne content was 0.95 wt% based on the total weight of the fractions. The results are shown in Table 4.
TABLE 4
| Catalyst sample | Residual vinyl acetylene (ppm) | Butadiene loss amount (% by weight) |
| Preparation example 1 | 6.5 | 0.20 |
| Preparation example 2 | 6.3 | 0.17 |
| Preparation example 3 | 5.9 | 0.21 |
| Preparation example 4 | 6.1 | 0.16 |
| Preparation example 5 | 5.7 | 0.21 |
| Preparation example 6 | 7.8 | 0.30 |
| Preparation example 7 | 8.0 | 0.28 |
| Preparation example 8 | 6.3 | 0.23 |
| Preparation example 9 | 7.6 | 0.28 |
| Comparative preparation example 1 | 29 | 0.9 |
| Comparative preparation example 2 | 68 | 2.2 |
As can be seen from the results in tables 2-4, the silver-zinc doped Raney copper catalyst prepared by the method of the invention is applied to C4When the fraction is in the process of removing alkyne by hydrogenation, the time is 10 to 20 hours-1Can remove the vinyl acetylene in a targeted way, has higher selectivity to the vinyl acetylene (the residual vinyl acetylene is less than 8ppm), and simultaneously has low loss of butadiene (less than 0.3 weight percent).
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A preparation method of a silver-zinc doped Raney copper catalyst comprises the following steps:
1) alloying zinc, copper and aluminum to obtain an active metal alloy;
2) activating the active metal alloy to obtain a catalyst precursor, and adding a solvent to prepare a catalyst suspension;
3) mixing soluble organic amine and silver salt to prepare silver source solution;
4) and reacting the silver source solution with the catalyst suspension to obtain the silver-zinc doped Raney copper catalyst.
2. The method of claim 1, wherein the zinc is present in an amount of 0.01 to 20 wt.%, the copper is present in an amount of 10 to 50 wt.%, and the aluminum is present in an amount of 40 to 80 wt.%, based on the total weight of the reactive metal alloy;
the silver source solution is used in an amount such that the weight ratio of the silver to the catalyst precursor is (0.05-1.0): 100, preferably (0.1-0.6): 100.
3. the process according to claim 1 or 2, wherein in step 2), the activation is carried out in a lye, the lye having a concentration of 2-40% by weight;
preferably, the activation conditions include: the activation temperature is 20-100 ℃, and the activation time is 0.5-3 h.
4. The process according to claim 1 or 2, wherein the catalyst precursor has an average particle diameter of 2 to 3 mm.
5. The method according to claim 1 or 2, wherein in the silver source solution, the concentration of silver is 0.05-20mgAg/mL, preferably 1-6 mgAg/mL;
preferably, the molar ratio of the organic amine to silver is (1-10): 1, preferably (2-5): 1.
6. the method of any of claims 1-5, wherein the organic amine is selected from at least one of ethylenediaminetetraacetic acid, triethanolamine, diethanolamine, ethanolamine, butylamine, isopropylamine, aniline, diethylamine, N-dimethylaniline, ethylenediamine, dodecylamine, triethylenediamine, cyclohexylamine, and hexamethylenetetramine;
preferably at least one of triethanolamine, isopropylamine, ethanolamine, ethylenediamine and hexamethylenediamine.
7. The silver-zinc doped raney copper catalyst prepared according to the process of any one of claims 1 to 6.
8. The silver-zinc doped Raney copper catalyst of claim 7 at C4Use of selective hydrogenation of fractions for alkyne removal.
9. Use according to claim 8, wherein C is4The reaction conditions for the selective hydrogenation of the distillate to remove acetylene include: the temperature of a reaction inlet is 30-60 ℃, the reaction pressure is 0.5-2.0MPa, and C is used4The reaction space velocity of liquid volume measurement in the fraction is 2-20h-1Hydrogen and C4The molar ratio of alkynes in the fraction is (0.2-10): 1. with C4The alkyne content is 0.6-1.5 wt% based on the total weight of the fraction.
10. Use according to claim 9, wherein C is4The reaction space velocity of liquid volume measurement in the fraction is 10-20h-1。
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| CN106475115A (en) * | 2015-08-27 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of raney copper catalyst and its preparation method and application |
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| CN107952490A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of preparation method of silver-raney copper catalyst, catalyst prepared therefrom and application |
| CN107952450A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of preparation method, catalyst and the application of silver carbonization raney copper catalyst |
| CN107952451A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of preparation method, catalyst and the application of silver loaded catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106475115A (en) * | 2015-08-27 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of raney copper catalyst and its preparation method and application |
| CN106622255A (en) * | 2015-10-28 | 2017-05-10 | 中国石油化工股份有限公司 | Alkyne selective hydrogenation catalyst as well as preparation method and application thereof |
| CN107952490A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of preparation method of silver-raney copper catalyst, catalyst prepared therefrom and application |
| CN107952450A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | A kind of preparation method, catalyst and the application of silver carbonization raney copper catalyst |
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