CN109675569A - A kind of load-type nickel based alloy catalyst and its preparation method and application - Google Patents

A kind of load-type nickel based alloy catalyst and its preparation method and application Download PDF

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CN109675569A
CN109675569A CN201910078184.6A CN201910078184A CN109675569A CN 109675569 A CN109675569 A CN 109675569A CN 201910078184 A CN201910078184 A CN 201910078184A CN 109675569 A CN109675569 A CN 109675569A
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nickel
catalyst
load
alloy
catalyst precursor
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路勇
朱坚
赵国锋
刘晔
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East China Normal University
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East China Normal University
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    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J23/835—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 germanium, tin or lead
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/20—Carbon compounds
    • B01J27/22—Carbides
    • B01J27/224—Silicon carbide
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention discloses a kind of load-type nickel based alloy catalysts and its preparation method and application.The load-type nickel based alloy catalyst is made of the nickel-base alloy of carrier and load thereon, and the nickel-base alloy is NixMyCzAlloy, wherein 1≤x≤10,1≤y≤10,0≤z≤5, the M are selected from least one of iron, copper, cobalt, zinc, molybdenum, palladium, silver, gallium, indium, tin, germanium, bismuth, lead, and when z is greater than 0, M is not indium, and the gross mass accounting of the nickel-base alloy is 1~50%, remaining is carrier.Catalyst provided by the invention, have stable structure, thermal conductivity are good, permeability is high, conversion ratio and selectivity are high, active height, high mechanical strength, it is easy to form, be easy to load and many advantages, such as high-throughput low pressure drop, be the reaction of prepared by dimethyl oxalate plus hydrogen methyl glycollate, preparing ethylene glycol by using dimethyl oxalate plus hydrogen react, the excellent catalyst of prepared by dimethyl oxalate plus hydrogen ethanol synthesis.

Description

A kind of load-type nickel based alloy catalyst and its preparation method and application
Technical field
The present invention is to be related to a kind of catalyst and its preparation method and application, specifically, be related to it is a kind of loading type nickel-based Alloy catalyst and preparation method thereof is with it in the reaction of prepared by dimethyl oxalate plus hydrogen methyl glycollate, prepared by dimethyl oxalate plus hydrogen second Application in glycol reaction, prepared by dimethyl oxalate plus hydrogen ethanol synthesis, belongs to catalysis technical field.
Background technique
Gradually reinforcement with the increasingly in short supply and people of petroleum resources to environmental protection consciousness, research and searching environment Friendly petroleum-based energy substitute has become one of the direction of world energy sources field technological development.In consideration of it, exploring coal resources High-efficiency cleaning using being to realize Sinopec product diversification, Optimization of Energy Structure improves the important channel of environmental quality.Closely Over 10 years, China's Development of Coal Chemical Industry is swift and violent, during coal chemical industry, after coal oil, natural gas from coal, coal-to-olefin, and coal Low-carbon alcohols (methyl glycollate, ethylene glycol, ethyl alcohol etc.) technology processed is just becoming the hot spot of domestic and international academia Yu industry research.? In the process route of coal low-carbon alcohols, by methanol carbonyl metaplasia at dimethyl oxalate (DMO), and DMO selective hydrogenation is generated The technique of methyl glycollate (MG), ethylene glycol (EG), ethyl alcohol (EtOH) has reaction condition temperature compared to more traditional petrochemical industry route With not by petroleum resources limitation in short supply, Atom economy it is high and the advantages that meet Green Chemistry, it is considered to be optimal future is replaced For one of the process route of petroleum.Currently, the first step methanol carbonyl metaplasia of the technique has compared at DMO technology It is ripe, industrialization was realized in 2010.Therefore developing efficient DMO hydrogenation catalyst is the key that realize coal low-carbon alcohols.
DMO hydrogenation catalyst can be divided mainly into homogeneous catalyst and heterogeneous catalyst.Homogeneous catalyst is in DMO hydrogenation process Very high selectivity of product can be obtained.Such as Matteoli etc. (J.Mol.Catal., 1991,64:257-267) has studied ruthenium base Catalyst, discovery ruthenium-based catalyst are up to 95% for the yield of MG under 100 DEG C, 7MPa Hydrogen Vapor Pressure.Although homogeneous catalysis Agent is very high for the yield of target product, but catalyst is at high cost, and catalyst can not recycle leads to ruthenium agent Catalyst It is limited to change application.For heterogeneous catalyst, copper-based catalysts due to its efficient carbon-oxygen bond hydrogenation capability, weaker carbon-carbon bond Hydrogenation capability and be widely used in DMO and add hydrogen.Simultaneously because ether can occur on acidic site for ethylene glycol and methanol or ethyl alcohol Change reaction, Guerbet reaction can occur in basic sites and generate butanediol or propylene glycol, it is therefore desirable to select suitable catalyst Carrier.Silica is because weak acid-base property is considered as excellent catalyst carrier.Such as Fudan University Dai Weilin (J.Mater.Chem.2011,21:8997-8999) preparation AuCu/HMS catalyst adds hydrogen MG for DMO, in reaction temperature Degree is 180 DEG C, reaction pressure 3MPa, hydrogen ester molar ratio are 120, charging liquid hourly space velocity (LHSV) is 0.8h-1Under conditions of, it obtains 90% DMO conversion ratio, 100% MG selectivity.Fudan University's Chen Liang cutting edge of a knife or a sword (J.Catal., 2008,257:172-180) utilizes Ammonia still process method is prepared for Cu/SiO2Catalyst, reaction temperature is 205 DEG C, reaction pressure 2MPa, hydrogen ester molar ratio are 80, into Material liquid hourly space velocity (LHSV) is 1.0h-1, 100% DMO conversion ratio is obtained, 98% EG selectivity shows excellent DMO and adds hydrogen system The catalytic performance of EG.University Of Tianjin Gong Jinlong prepares Cu/SiO also with ammonia still process method2Catalyst, reaction temperature be 280 DEG C, Hydrogen ester molar ratio is 200, charging liquid hourly space velocity (LHSV) is 2.0h-1, obtain the EtOH selectivity of 100% DMO conversion ratio 83%.Though Right copper-based catalysts show excellent catalytic activity in DMO selective hydrogenation low-carbon alcohols, but are permitted Di Xiwen due to copper Degree is 134 DEG C, and well below the reaction temperature of DMO plus hydrogen, therefore copper particle is easy sintering deactivation during the reaction.In addition right In copper-based catalysts, DMO adds the highly selective temperature operating window to specific product of hydrogen very narrow.Such as the part DMO at low temperature Add hydrogen to MG, to obtain highly selective MG, DMO conversion ratio is often below 70%.This pole is unfavorable for the purification of subsequent MG, especially Be be subsequently used for synthesis high added value polyglycolic acid requirement of the process to DMO content in MG raw material it is extremely harsh.For in DMO Add hydrogen to EG, slightly higher temperature will lead to DMO and add hydrogen to EtOH.DMO plus hydrogen to EtOH needs could be obtained at high temperature High EtOH selectivity, but high temperature will lead to a large amount of generations of butanediol propylene glycol, while aggravate the sintering deactivation of copper particle.
To sum up, this field needs to develop one kind to be easy to large-scale industry preparation, heating conduction good, at the same meet plus The catalyst that hydrogen activity is excellent, low-carbon alcohols selectivity is high, temperature operating window is wide and has good stability.Nickel-base catalyst is because of it It is cheap, with excellent plus hydrogen performance, thus have a wide range of applications.During DMO plus hydrogen MG, catalyst is needed Ester group and hydrogen are activated simultaneously, and nickel-base catalyst can be good at activating hydrogen but be difficult to activate ester group, therefore show Poor DMO conversion ratio out.
The present inventor discloses a kind of carbonization nickel indium alloy catalyst in patent CN201710956080.1, by carbon Element and phosphide element make it generate carbonization nickel indium alloy with nickel, improve the ability that nickel-base catalyst adds hydrogen activation ester group, this is specially Carbonization nickel indium alloy catalyst InNi in benefit3C0.5/ Ni-foam is for obtaining in preparing ethylene glycol by using dimethyl oxalate plus hydrogen reaction Obtained under high DMO conversion ratio, ethylene glycol have it is highly selective, still, the expensive (In (NO of indium in the catalyst3)3.4H2O, nearly 2,000,000 yuan one ton), therefore catalyst cost is very high, meanwhile, it needs when which uses in higher temperature Under degree, cryogenic selective is poor, and therefore, which is unfavorable for industrial applications.The present inventor is in patent A kind of self-supporting catalyst of phosphatizing nickel is disclosed in CN201710956090.5, the catalyst of phosphatizing nickel in the patent is used for oxalic acid Dimethyl ester preparation of ethanol by hydrogenating acid methyl esters reaction in, in the case where obtaining high DMO conversion ratio, methyl glycollate have it is highly selective, but It is that preparation process needs are complicated using the phosphine gas and preparation process of severe toxicity in the catalyst, in addition reacts hydrogen ester ratio Height, these are unfavorable for industrial applications.Therefore, it is badly in need of developing a kind of high activity, highly selective, high stability, thermal conductivity Catalyst that is good, being easy to large-scale production.
Summary of the invention
In view of the above-mentioned problems existing in the prior art and demand, it is good, active that the object of the present invention is to provide a kind of stability It is high, selectivity is high, thermal conductivity is good, it is easy to form, be easy to load and the load-type nickel based alloy catalyst of high-throughput low pressure drop and Preparation method is with it in the reaction of prepared by dimethyl oxalate plus hydrogen methyl glycollate, preparing ethylene glycol by using dimethyl oxalate plus hydrogen reaction, grass Application in the reaction of dimethyl phthalate preparation of ethanol by hydrogenating.
For achieving the above object, The technical solution adopted by the invention is as follows:
A kind of load-type nickel based alloy catalyst is made of, the Ni-based conjunction the nickel-base alloy of carrier and load thereon Gold is NixMyCzAlloy, wherein 1≤x≤10,1≤y≤10,0≤z≤5, the M be selected from iron, copper, cobalt, zinc, molybdenum, palladium, silver, At least one of gallium, indium, tin, germanium, bismuth, lead, and when z is greater than 0, M is not indium, and the gross mass accounting of the nickel-base alloy is 1~50%, remaining is carrier.
Preferably, the nickel-base alloy is NixMyCzAlloy, wherein 1≤x≤10,1≤y≤10, z=0 or 0.1≤z≤5, M are selected from least one of iron, copper, cobalt, zinc, molybdenum, palladium, silver, gallium, indium, tin, germanium, bismuth, lead, and when z is greater than 0 When, M is not indium.That is, the nickel-base alloy is NixMyAlloy or NixMyCzAlloy, specifically, when z=0, the Ni-based conjunction Gold is NixMyAlloy (such as: FeNi3、SnNi、MoNi4), at this point, 1≤x≤10,1≤y≤10, M be selected from iron, copper, cobalt, At least one of zinc, molybdenum, palladium, silver, gallium, indium, tin, germanium, bismuth, lead；When 0.1≤z≤5, the nickel-base alloy is NixMyCzAlloy (such as: ZnNi3C0.7), wherein 1≤x≤10,1≤y≤10, M be selected from iron, copper, cobalt, zinc, molybdenum, palladium, silver, At least one of gallium, tin, germanium, bismuth, lead.
Preferably, the material of the carrier be metal, alloy, carbide, carbon, nitride, in oxide extremely Few one kind.
As further preferred scheme, the metal is at least one of nickel, aluminium, copper, titanium, and the alloy is stainless At least one of steel, ferrum-chromium-aluminum, aluminium alloy, copper-nickel alloy, brass.
As further preferred scheme, the carbide is silicon carbide, tungsten carbide, molybdenum carbide, at least one in zirconium carbide Kind.
As further preferred scheme, the carbon is at least one of active carbon, graphitic carbon, graphene.
As further preferred scheme, the nitride is boron nitride, silicon nitride, titanium nitride, silicon nitride, tungsten nitride, nitrogen Change at least one of molybdenum.
As further preferred scheme, the oxide be alkaline-earth metal, boron, aluminium, gallium, indium, silicon, lanthanide rare metal, At least one of titanium, zirconium, zinc, manganese, tungsten, vanadium, tin, oxide of niobium.
Preferably, the morphosis of the carrier be foam, fiber, fibrofelt, silk, silk screen, pipe, piece, foil, The combination of any one or more in grain；The aperture degree of the foam is 10~120PPI；The diameter of the fiber be 4~ 150 microns；The fibrofelt is the three-dimensional porous structure as made of the fiber sintering of 4~150 micron diameters；The diameter of the silk It is 0.15~5.00 millimeter；The silk screen is net made of the silk thread for being 0.15~5.00 millimeter as diameter weaves；The pipe Outer diameter is 2~50 millimeters, wall thickness is 0.5~5 millimeter；Described with a thickness of 0.1~2 millimeter；The foil with a thickness of 0.5~ 100 microns；The partial size of the particle is 25~150 microns.
A method of heretofore described load-type nickel based alloy catalyst is prepared, is first to load Ni on carrier ZT With the composite oxides of M, catalyst precursor is made, reduction then is carried out to catalyst precursor or reduction and carbonization is handled, i.e., Obtain the load-type nickel based alloy catalyst.
The first scheme, the preparation of the catalyst precursor, includes the following steps:
A) on carrier growth in situ nickel oxide precursor crystal layer, be made loading type nickel-based catalyst precursor；
B) impregnation is carried out to prepared loading type nickel-based catalyst precursor with the solution of the ion containing M, then carried out Cleaning and drying, then 1~15 hour is roasted at 200~800 DEG C to get the catalyst precursor.
Nickel oxide precursor described in step a) is nickel oxalate, nickel hydroxide or terephthalic acid (TPA) nickel.
As a kind of embodiment, the preparation of loading type nickel-based catalyst precursor described in step a) includes the following steps:
Carrier is immersed in the aqueous solution of ammonium salt-containing and oxalic acid, reacts 0.5 in autoclave at 50~350 DEG C ~45 hours, taken out after cooling, then cleaned and dried to get on carrier ZT growth in situ have nickel oxalate layer Loading type nickel-based catalyst precursor, wherein the material of carrier is that (so-called copper-nickel alloy is using nickel as main adding elements for nickel or copper-nickel alloy Copper-based H alloy H, is silvery white in color, and has a H metallic luster H, therefore named copper-nickel alloy, can infinitely be dissolved each other between cupro-nickel, to be formed continuous Solid solution, it may be assumed that though mutual ratio how much, and permanent is α -- single-phase alloy).
Preferably, the molar ratio of ammonium salt and oxalic acid is 0.001:1~10:1, is preferred with 0.01:1~1:1.
Preferably, the ammonium salt is at least one of ammonium chloride, ammonium fluoride, ammonium nitrate, ammonium sulfate.
Preferably, the concentration of ammonium salt is 0.001~10 mol/L, and the solution concentration of oxalic acid is rubbed for 0.001~10 You/liter.
As another embodiment, the preparation of loading type nickel-based catalyst precursor described in step a) includes following step It is rapid:
Carrier is immersed in the aqueous solution containing nickel salt and ammonium salt or containing nickel salt and urea or containing nickel ammine, 50~ It is reacted 0.5~45 hour in autoclave at 350 DEG C, is taken out after cooling, then cleaned and dried to get in carrier Upper growth in situ has the loading type nickel-based catalyst precursor of nickel hydroxide crystal layer.
Preferably, the nickel salt be nickel chloride, nickel sulfate, nickel nitrate, nickel acetate, in nickel acetylacetonate at least It is a kind of.
Preferably, the ammonium salt is at least one of ammonium chloride, ammonium fluoride, ammonium nitrate, ammonium sulfate.
Preferably, the concentration of ammonium salt is 0.001~10 mol/L, and the solution concentration of nickel salt is rubbed for 0.001~10 You/liter, nickel ammine solution concentration is 0.001~10 mol/L.
As another embodiment, the preparation of loading type nickel-based catalyst precursor described in step a) includes following step It is rapid:
Carrier is immersed in the dimethyl formamide solution containing nickel salt and terephthalic acid (TPA), in height at 45~350 DEG C It is reacted 0.5~45 hour in pressure reaction kettle, is taken out after cooling, then cleaned and dried to get the growth in situ on carrier There is the loading type nickel-based catalyst precursor of terephthalic acid (TPA) nickel crystal layer.
Preferably, the nickel salt be nickel chloride, nickel sulfate, nickel nitrate, nickel acetate, in nickel acetylacetonate at least It is a kind of.
Preferably, the solution concentration of nickel salt is 0.001~10 mol/L, and terephthalic acid solution's concentration is 0.001~10 mol/L.
M ion described in step b) is provided by M salt, and M salt is hydrochloride, sulfate, nitrate, acetate, the acetyl of M At least one of acetone salt.
Second scheme, the preparation of the catalyst precursor, includes the following steps:
Carrier is immersed in the solution containing nickel salt and M ion, reacts 0.5 in autoclave at 50~350 DEG C It~45 hours, is taken out after cooling, is then cleaned and dried to get the catalyst precursor.
Preferably, the nickel salt be nickel chloride, nickel sulfate, nickel nitrate, nickel acetate, in nickel acetylacetonate at least It is a kind of.
Preferably, M ion is provided by M salt, and M salt is chlorate, sulfate, nitrate, acetate, the acetyl of M At least one of acetone salt.
Preferably, the concentration of the nickel salt is 0.001~10 mol/L, and the concentration of the M solion is 0.001~10 mol/L.
The third scheme, the preparation of the catalyst precursor, includes the following steps:
With the solution step impregnation carrier respectively containing nickel ion and M ion, or with the mixing containing nickel ion and M ion simultaneously Solution co-impregnation carrier；Then it is cleaned and is dried, then roast 1~15 hour at 200~800 DEG C to get the catalysis Agent presoma.
Preferably, nickel ion is provided by nickel salt, the nickel salt be nickel chloride, nickel sulfate, nickel nitrate, nickel acetate, At least one of nickel acetylacetonate.
Preferably, M ion is provided by M salt, and M salt is chlorate, sulfate, nitrate, acetate, the acetyl of M At least one of acetone salt.
4th kind of scheme, the preparation of the catalyst precursor include the following steps:
After nickeliferous solid chemical compound and solid chemical compound and carrier mixed grinding containing M, 1 is roasted at 200~800 DEG C ~24 hours to get the catalyst precursor.
Preferably, the nickeliferous solid chemical compound is nickel nitrate, nickel sulfate, nickel acetate, nickel acetylacetonate, phosphoric acid At least one of nickel, nickelous carbonate, nickel oxide, nickel hydroxide.
Preferably, the solid chemical compound containing M is its nitrate, chlorate, sulfate, acetate, acetyl At least one of acetone salt, phosphate, carbonate, oxide, hydroxide.
When carrying out reduction treatment to catalyst precursor, reducing agent used appointing in hydrogen, hydrazine, boron hydride It anticipates one kind, reduction temperature is 200~600 DEG C.
A kind of scheme carries out reduction treatment to catalyst precursor and includes the following steps:
Catalyst precursor is placed in hydrogen atmosphere, carries out reduction treatment 0.5~8 hour at 200~600 DEG C, i.e., Obtain the load-type nickel based alloy catalyst.
Another scheme carries out reduction treatment to catalyst precursor and includes the following steps:
Catalyst precursor is placed in aqueous hydrazine, is carried out reduction treatment 0.5~48 hour at 20~200 DEG C, Up to the load-type nickel based alloy catalyst.
Another scheme carries out reduction treatment to catalyst precursor and includes the following steps:
Catalyst precursor is placed in the methanol solution of boron hydride, at 20~200 DEG C carry out reduction treatment 0.5~ 48 hours to get the load-type nickel based alloy catalyst.
Preferably, the boron hydride is potassium borohydride or sodium borohydride.
When carrying out reduction and carbonization processing to catalyst precursor, reduction and carbonization temperature is 200~800 DEG C.
As a kind of embodiment, reduction and carbonization processing is carried out to catalyst precursor and is included the following steps:
Catalyst precursor is placed in the mixed atmosphere that hydrogen and carbonaceous gas are formed or is placed in the atmosphere of carbonaceous gas In, reduction and carbonization is carried out at 200~800 DEG C handles 0.5~8 hour to get the load-type nickel based alloy catalyst.
Preferably, the carbonaceous gas be selected from gaseous carbon monoxide, carbon dioxide, hydrocarbon (such as: methane, second Alkane, propane, ethylene, propylene, acetylene, propine etc.), aldehyde (such as: formaldehyde, glutaraldehyde etc.), ketone (such as: acetone, ketene dimer Deng), at least one of ester (such as: methyl formate, ethyl acetate, vinyl acetate etc.), preferably carbon monoxide.
Load-type nickel based alloy catalyst of the present invention can be used as prepared by dimethyl oxalate plus hydrogen methyl glycollate reaction, Preparing ethylene glycol by using dimethyl oxalate plus hydrogen reaction, prepared by dimethyl oxalate plus hydrogen ethanol synthesis catalyst.
Compared with prior art, the present invention have following conspicuousness the utility model has the advantages that
Load-type nickel based alloy catalyst provided by the invention, with stable structure, thermal conductivity is good, permeability is high, conversion Rate and selectivity high (especially cryogenic selective is high), active height, high mechanical strength, temperature range it is wide, it is easy to form, be easy to fill Fast speed heat/matter is transmitted in many advantages, such as filling out with high-throughput low pressure drop, the strong suction/exothermic reaction that can meet simultaneously in chemical process It is the superior catalytic of prepared by dimethyl oxalate plus hydrogen methyl glycollate, ethylene glycol, ethanol synthesis Deng the requirement with good catalytic Agent has conspicuousness industrial application value；In addition, preparation process of the invention is economical and practical, preparation process is simple, and raw material is easy , structure-controllable is not necessarily to special installation and harsh conditions, it is easy to accomplish large-scale production has extremely strong practical value.
Detailed description of the invention
Fig. 1 is the X-ray diffraction spectrogram of loading type nickel-based catalyst precursor prepared by embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of loading type nickel-based catalyst precursor prepared by embodiment 1；
Fig. 3 is the X-ray diffraction spectrogram of load-type nickel based alloy catalyst prepared by embodiment 1；
Fig. 4 is the X-ray diffraction spectrogram of loading type nickel-based catalyst precursor prepared by embodiment 2；
Fig. 5 is the scanning electron microscope (SEM) photograph of loading type nickel-based catalyst precursor prepared by embodiment 2；
Fig. 6 is the X-ray diffraction spectrogram of load-type nickel based alloy catalyst prepared by embodiment 2；
Fig. 7 is the X-ray diffraction spectrogram of loading type nickel-based catalyst precursor prepared by embodiment 3；
Fig. 8 is the scanning electron microscope (SEM) photograph of loading type nickel-based catalyst precursor prepared by embodiment 3；
Fig. 9 is the X-ray diffraction spectrogram of load-type nickel based alloy catalyst prepared by embodiment 3；
Figure 10 is the X-ray diffraction spectrogram of catalyst precursor prepared by embodiment 4；
Figure 11 is the scanning electron microscope (SEM) photograph of catalyst precursor prepared by embodiment 4；
Figure 12 is that load-type nickel based alloy catalyst prepared by embodiment 1 is used for prepared by dimethyl oxalate plus hydrogen ethanol synthesis 200 hours stability experiment results；
Figure 13 is that load-type nickel based alloy catalyst prepared by embodiment 4 is used for prepared by dimethyl oxalate plus hydrogen ethanol synthesis 200 hours stability experiment results.
Specific embodiment
Technical solution of the present invention is described in further detail and completely below with reference to embodiment, comparative example and application examples.
Embodiment 1
1) 1 gram of nickel foam (110PPI) is weighed, is placed in the aqueous sodium carbonate that mass fraction is 1% and is ultrasonically treated 30 points Clock removes surface grease stain, and distilled water is cleaned, and is then placed in nickel foam in the dilute hydrochloric acid solution of 1 mol/L and is ultrasonically treated 30 points Clock removes oxide on surface, distills water washing, until solution is in neutrality；Then nickel foam is transferred in autoclave, is added Enter 20 mMs of nickel nitrates, 80 mMs of ammonium chlorides, 80 milliliters of water, at 100 DEG C, hydro-thermal reaction 6 hours, reaction was completed, from So be cooled to room temperature, take out distilled water ultrasound and clean, 100 DEG C of drying to get on carrier growth in situ have nickel hydroxide crystal The loading type nickel-based catalyst precursor of layer；
2) 1.73 grams of Fe(NO3)39H2O are weighed and is dissolved in 0.7 gram of water, the aqueous solution containing iron ion is made；Weigh load-type nickel 1 gram of based catalyst precursors, incipient impregnation is carried out to it with the aqueous solution containing iron ion prepared at room temperature, is then cleaned With drying (100 DEG C of drying), then it is placed in air atmosphere, roasts 2 hours at 350 DEG C to get catalyst precursor；
3) catalyst precursor obtained is placed in the aqueous hydrazine that mass fraction is 20%, is gone back at room temperature 24 hours are managed to get the load-type nickel based alloy catalyst in original place.
Fig. 1 is the X-ray diffraction spectrogram (XRD) of loading type nickel-based catalyst precursor made from the present embodiment, can by Fig. 1 See, grown Ni (OH) in nickel foam surface in situ2。
Fig. 2 is the SEM figure of loading type nickel-based catalyst precursor made from the present embodiment, from Figure 2 it can be seen that the support type of preparation Nickel-base catalyst precursor is in porous flake pattern.
Fig. 3 is the XRD spectra of load-type nickel based alloy catalyst made from the present embodiment, as seen from Figure 3, the catalyst By foam nickel carrier and Fe3Ni composition.
Through known to macroscopic measurement: catalyst described in the present embodiment, percent by volume shared by carrier therein are 15%, porosity 85%.It is learnt through plasma inductance linking atom emission spectrum (ICP) measurement: prepared by the present embodiment In catalyst, Fe3The mass content of Ni alloy is 15%.
In addition, the present embodiment can also carry out following develop:
In step 1), nickel nitrate/ammonium chloride molar ratio can be 0.001~10, nickel in nickel nitrate and aqueous ammonium chloride solution The concentration of ion and ammonium chloride may each be 0.001~10 mol/L, remaining condition is constant.
In step 1), the hydro-thermal time be can be 0.5~45 hour, and hydrothermal temperature can be 50~350 DEG C, remaining condition is not Become.
In step 1), nickel salt can be one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate or more Kind, remaining condition is constant.
In step 1), the ammonium chloride can be replaced ammonium fluoride, ammonium nitrate, ammonium sulfate, urea.
In step 1), the aperture degree of the foam nickel carrier ZT can be 10~120PPI, remaining condition is constant.
In step 1), the foam nickel carrier ZT can also be the fiber of metallic nickel, fibrofelt, silk, silk screen, pipe, piece, The combination of any one or more in foil, particle, remaining condition are constant；The diameter of the fiber is 4~150 microns；It is described Fibrofelt is the three-dimensional porous structure as made of the fiber sintering of 4~150 micron diameters；The diameter of the silk is 0.15~5.00 Millimeter；The silk screen is net made of the silk thread for being 0.15~5.00 millimeter as diameter weaves；The outer diameter of the pipe is 2~50 millis Rice, wall thickness are 0.5~5 millimeter；Described with a thickness of 0.1~2 millimeter；The foil with a thickness of 0.5~100 micron；It is described The partial size of particle is 25~150 microns.In step 1), the material of foam carrier can be aluminium, copper, titanium, iron, copper-nickel alloy, brass, titanium Remaining condition is constant.
In step 2), molysite can be ferric nitrate, frerrous chloride, iron chloride, ferric sulfate, ferrous sulfate, ferric acetate, acetic acid One of Asia, ferric acetyl acetonade, acetylacetone,2,4-pentanedione ferrous iron are a variety of, remaining condition is constant.
In step 2), thus it is possible to vary the type and maturing temperature of molysite, controlling resulting iron oxide can be oxygen Change iron, ferrous oxide, one of ferroso-ferric oxide or a variety of, remaining condition are constant.
In step 2), the iron in ferric nitrate could alternatively be copper, cobalt, molybdenum, palladium, silver, gallium, indium, tin, germanium, bismuth, appointing in lead It anticipates one kind, remaining condition is constant.
In step 2), the maturing temperature can select in 200~650 DEG C, and the calcining time can be small 1~24 When interior selection, remaining condition is constant.
In step 3), reduction mode can be hydrogen, potassium borohydride or sodium borohydride reduction, remaining condition is constant.
In step 3), the concentration of aqueous hydrazine can be 0.001~100 mol/L.
In step 3), the reduction temperature can select in 20~200 DEG C, and the recovery time can be 0.5~48 Selection, remaining condition are constant in hour.
Embodiment 2
1) 1 gram of nickel foam (110PPI) is weighed, is placed in the aqueous sodium carbonate that mass fraction is 1% and is ultrasonically treated 30 points Clock removes surface grease stain, and distilled water is cleaned, and is then placed in nickel foam in the dilute hydrochloric acid solution of 1 mol/L and is ultrasonically treated 30 points Clock removes oxide on surface, distills water washing, until solution is in neutrality；Then nickel foam is transferred in autoclave, is added Enter 180 mMs of oxalic acid, 15 mMs of ammonium chlorides, 80 milliliters of water, at 180 DEG C, hydro-thermal reaction 24 hours, reaction was completed, from So be cooled to room temperature, take out distilled water ultrasound and clean, 100 DEG C of drying to get on carrier growth in situ have nickel oxalate layer Loading type nickel-based catalyst precursor；
2) it weighs 0.55 gram of zinc nitrate and is dissolved in 0.7 gram of water, the aqueous solution containing zinc ion is made；Weigh loading type nickel-based catalysis 1 gram of agent precursor, incipient impregnation is carried out to it with the aqueous solution containing zinc ion prepared at room temperature, is then cleaned and is dried (100 DEG C of drying), is then placed in air atmosphere, roasts 2 hours at 450 DEG C to get catalyst precursor；
3) catalyst precursor obtained is placed in the mixed atmosphere that hydrogen and carbon monoxide are formed, at 350 DEG C also Original carbonization 1 hour to get the load-type nickel based alloy catalyst.
Fig. 4 is the XRD spectra of loading type nickel-based catalyst precursor made from the present embodiment, from fig. 4, it can be seen that in nickel foam table Face growth in situ NiC2O4。
Fig. 5 is the SEM figure of loading type nickel-based catalyst precursor made from the present embodiment, as seen from Figure 5, the support type of preparation Nickel-base catalyst precursor is in porous Rod-like shape.
Fig. 6 is the XRD spectra of load-type nickel based alloy catalyst made from the present embodiment, as seen from Figure 6, the catalyst By foam nickel carrier and ZnNi3C0.7Composition.
It analyzes and measures through x-ray photoelectron spectroscopy (XPS), in catalyst prepared by the present embodiment, the Ni-based conjunction of load Gold is ZnNi3C0.7；It is learnt through plasma inductance linking atom emission spectrum (ICP) measurement: catalyst prepared by the present embodiment In, ZnNi3C0.7The mass content of alloy is 14%.
In addition, the present embodiment can also carry out following develop:
In step 1), oxalic acid/ammonium chloride molar ratio can be 0.001~10, oxalic acid and aqueous ammonium chloride solution mesoxalic acid It may each be 0.001~10 mol/L with the concentration of ammonium chloride, remaining condition is constant.
In step 1), the hydro-thermal time be can be 0.5~45 hour, and hydrothermal temperature can be 50~350 DEG C, remaining condition is not Become.
In step 2), zinc salt can be zinc nitrate, cerous nitrate zinc, zinc chloride, zinc sulfate, zinc acetate, in zinc acetylacetonate It is one or more, remaining condition is constant.
In step 2), zinc nitrate could alternatively be the reducibilitys such as iron, copper, cobalt, molybdenum, palladium, silver transition metal or gallium, The water soluble salt of the main group metals such as indium, tin, germanium, bismuth, lead etc., remaining condition are constant.
In step 2), the maturing temperature can select in 200~650 DEG C, and the calcining time can be small 1~24 When interior selection, remaining condition is constant.
In step 3), the mixed atmosphere can be hydrogen and carbon monoxide, carbon dioxide, hydrocarbon, aldehyde, ketone, in ester At least one is formed, remaining condition is constant.
In step 3), the reduction and carbonization temperature can select in 200~600 DEG C, and the reduction and carbonization time can It is selected in 0.5~48 hour, remaining condition is constant.
Embodiment 3
1) 1 gram of nickel foam (110PPI) is weighed, is placed in the aqueous sodium carbonate that mass fraction is 1% and is ultrasonically treated 30 points Clock removes surface grease stain, and distilled water is cleaned, and is then placed in nickel foam in the dilute hydrochloric acid solution of 1 mol/L and is ultrasonically treated 30 points Clock removes oxide on surface, distills water washing, until solution is in neutrality；Then nickel foam is transferred in autoclave, is added Enter 80 mMs of terephthalic acid (TPA)s, 80 mMs of nickel nitrates, 80 milliliters of dimethylformamides, at 140 DEG C, when solvent thermal reaction Between 24 hours, reaction was completed, is naturally cooling to room temperature, takes out distilled water ultrasound and cleans, and 100 DEG C of drying are to get former on carrier Position growth has the loading type nickel-based catalyst precursor of terephthalic acid (TPA) nickel crystal layer；
2) it weighs 0.52 gram of stannous chloride and is dissolved in 0.7 gram of water, the aqueous solution containing tin ion is made；Weigh loading type nickel-based urge 1 gram of agent precursor, incipient impregnation is carried out to it with the aqueous solution containing tin ion prepared at room temperature, is then cleaned and is done Dry (100 DEG C of drying), is then placed in air atmosphere, roasts 2 hours at 350 DEG C to get catalyst precursor；
3) catalyst precursor obtained is placed in hydrogen atmosphere, restores 1 hour in 350 DEG C to get the load Type nickel-base alloy catalyst.
Fig. 7 is the XRD spectra of loading type nickel-based catalyst precursor made from the present embodiment, as seen from Figure 7, in nickel foam table Face growth in situ NiC8H4O4。
Fig. 8 is the SEM figure of loading type nickel-based catalyst precursor made from the present embodiment, as seen from Figure 8, the support type of preparation Nickel-base catalyst precursor is in porous flake pattern.
Fig. 9 is the XRD spectra of load-type nickel based alloy catalyst made from the present embodiment, as seen from Figure 9, the catalyst By foam nickel carrier and NiSn composition of alloy.
It is learnt through plasma inductance linking atom emission spectrum (ICP) measurement: in catalyst prepared by the present embodiment, The mass content of NiSn alloy is 20%.
In addition, the present embodiment can also carry out following develop:
In step 1), terephthalic acid (TPA) and nickel nitrate molar ratio can be 0.001~10, terephthalic acid (TPA) and nickel nitrate The concentration of terephthalic acid (TPA) and nickel ion may each be 0.001~10 mol/L in dimethyl formamide solution, remaining condition is not Become.
In step 1), the solvent heat time be can be 0.5~45 hour, and solvent heat temperature can be 45~350 DEG C, remaining Part is constant.
In step 1), nickel salt can be one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate or more Kind, remaining condition is constant.
In step 2), pink salt can be nitric acid tin, stannic chloride, in stannous chloride, STANNOUS SULPHATE CRYSTALLINE, tin acetate, acetylacetone,2,4-pentanedione tin It is one or more, remaining condition is constant.
In step 2), stannous chloride could alternatively be iron, copper, cobalt, molybdenum, palladium, silver, gallium, indium, germanium, bismuth, lead In the water soluble salt of any one, remaining condition is constant.
In step 2), the maturing temperature can select in 200~650 DEG C, and the calcining time can be small 1~24 When interior selection, remaining condition is constant.
In step 3), reduction mode can be hydrogen, potassium borohydride or sodium borohydride reduction, remaining condition is constant.
In step 3), the reduction temperature can select in 20~600 DEG C, and the recovery time can be 0.5~48 Selection, remaining condition are constant in hour.
Embodiment 4
1) 1 gram of nickel foam (110PPI) is weighed, is placed in the aqueous sodium carbonate that mass fraction is 1% and is ultrasonically treated 30 points Clock removes surface grease stain, and distilled water is cleaned, and is then placed in nickel foam in the dilute hydrochloric acid solution of 1 mol/L and is ultrasonically treated 30 points Clock removes oxide on surface, distills water washing, until solution is in neutrality；Then nickel foam is transferred in autoclave, is added Enter 40 mMs of ammonium molybdates, 80 mMs of nickel nitrates, 80 milliliters of distilled water, at 150 DEG C, the hydro-thermal reaction time 6 hours, terminates Reaction is naturally cooling to room temperature, takes out distilled water ultrasound and cleans, and 100 DEG C of drying are to get catalyst precursor；
2) catalyst precursor obtained is placed in hydrogen atmosphere, restores in 500 DEG C 1 hour and is born to get prepared Load type nickel-base alloy catalyst.
Figure 10 is the XRD spectra of catalyst precursor made from the present embodiment, as seen from Figure 10, in nickel foam surface in situ It grown NiMoO4。
Figure 11 is the SEM figure of catalyst precursor made from the present embodiment, as seen from Figure 11, the catalyst precursor of preparation In porous nano floriform appearance.
It analyzes and measures through x-ray photoelectron spectroscopy (XPS), in catalyst prepared by the present embodiment, the Ni-based conjunction of load Gold is MoNi4；It is learnt through plasma inductance linking atom emission spectrum (ICP) measurement: in catalyst prepared by the present embodiment, MoNi4The mass content of alloy is 25%.
In addition, the present embodiment can also carry out following develop:
In step 1), ammonium molybdate and nickel nitrate molar ratio can be 0.001~10, in the aqueous solution of ammonium molybdate and nickel nitrate The concentration of ammonium molybdate and nickel ion may each be 0.001~10 mol/L, remaining condition is constant.
The hydro-thermal time can be 0.5~45 hour in step 1), and hydrothermal temperature can be 45~350 DEG C, remaining condition is not Become.
In step 1), nickel salt can be one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate or more Kind, remaining condition is constant.
In step 2), molybdenum salt can be nitric acid molybdenum, molybdenum chloride, molybdenum trisulfate, acetic acid molybdenum, acetyl acetone, ammonium molybdate, secondary molybdenum One of sour ammonium, sodium molybdate, sodium paramolybdate are a variety of, remaining condition is constant.
In step 2), ammonium molybdate could alternatively be iron, copper, cobalt, palladium, silver, gallium, indium, tin, germanium, bismuth, in lead The water soluble salt of any one, remaining condition are constant.
In step 2), the reduction temperature can select in 200~800 DEG C, and the recovery time can be 0.5~8 Selection, remaining condition are constant in hour.
Embodiment 5
1) weigh 1.8 grams of nickel nitrate, 0.5 gram of frerrous chloride, 10 gram mass scores 30% silica solution (i.e. carrier is SiO2) be dissolved in 60 milliliters of water, the ammonium hydroxide of mass fraction 25% is gradually added dropwise, until pH value of solution is greater than 11, gained sample is set At room temperature, stirring is placed 4 hours, then sample is placed in 90 DEG C of water-baths, agitating and heating, until pH value of solution is less than 7.5, most After filter, the drying of 100 DEG C of oven overnights is to get catalyst precursor；
2) catalyst precursor obtained is placed in the aqueous hydrazine that mass fraction is 20%, is gone back at room temperature 24 hours are managed to get the load-type nickel based alloy catalyst in original place.
It analyzes and measures through x-ray photoelectron spectroscopy (XPS), in catalyst prepared by the present embodiment, the Ni-based conjunction of load Gold is FeNi3；It is learnt through plasma inductance linking atom emission spectrum (ICP) measurement: in catalyst prepared by the present embodiment, FeNi3The mass content of alloy is 20%.
In addition, the present embodiment can also carry out following develop:
In step 1), nickel nitrate/frerrous chloride molar ratio can be 0.001~10, nickel nitrate and ferrous chloride aqueous solution The concentration of middle nickel ion and ferrous ion may each be 0.001~10 mol/L, remaining condition is constant.
In step 1), thickness of silica gel can be 0.001~10 mol/L, and ammonia concn can be 0.1~10 mol/L, Remaining condition is constant.
In step 1), SiO2Carrier could alternatively be alkaline-earth metal, boron, aluminium, gallium, indium, lanthanide rare metal, titanium, zirconium, Zinc, manganese, tungsten, vanadium, tin, niobium oxide in any one, remaining condition is constant.
In step 1), carrier could alternatively be silicon carbide, tungsten carbide, molybdenum carbide, any one in zirconium carbide, remaining Part is constant.
In step 1), carrier could alternatively be active carbon, graphitic carbon, any one in graphene, remaining condition is constant.
In step 1), carrier could alternatively be boron nitride, silicon nitride, titanium nitride, silicon nitride, tungsten nitride, in molybdenum nitride Any one, remaining condition is constant.
In step 1), nickel salt can be one of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate or more Kind, remaining condition is constant.
In step 1), molysite can be ferric nitrate, frerrous chloride, iron chloride, ferric sulfate, ferrous sulfate, ferric acetate, acetic acid One of Asia, ferric acetyl acetonade, acetylacetone,2,4-pentanedione ferrous iron are a variety of, remaining condition is constant.
In step 1), bath temperature can be 50~90 DEG C, remaining condition is constant.
In step 1), ferric nitrate could alternatively be the reducibilitys such as copper, cobalt, molybdenum, palladium, silver transition metal or gallium, indium, The water soluble salt of the main group metals such as tin, germanium, bismuth, lead, boron, phosphorus, selenium etc., remaining condition are constant.
In step 2), reduction mode can be hydrogen, potassium borohydride or sodium borohydride reduction, remaining condition is constant.
In step 2), the concentration of aqueous hydrazine can be 0.001~100 mol/L.
In step 3), the reduction temperature can select in 20~600 DEG C, and the recovery time can be 0.5~48 Selection, remaining condition are constant in hour.
Embodiment 6
1) weigh 0.5 gram of frerrous chloride, 1.8 grams of nickel nitrate be dissolved in 5.5 grams of water, (i.e. carrier is 1 gram of fumed silica SiO2), excessive dipping is carried out at room temperature, and gained sample is placed in after 100 DEG C of baking ovens are dried 12 hours in air atmosphere at 350 DEG C Roasting 2 hours to get catalyst precursor；
2) be placed in obtained in hydrogen atmosphere up to catalyst precursor, in 350 DEG C progress reduction treatment 1 hour, i.e., Obtain prepared loading type nickel-based catalyst.
It analyzes and measures through x-ray photoelectron spectroscopy (XPS), in catalyst prepared by the present embodiment, the Ni-based conjunction of load Gold is FeNi3；It is learnt through plasma inductance linking atom emission spectrum (ICP) measurement: in catalyst prepared by the present embodiment, FeNi3The mass content of alloy is 20%.
In addition, the present embodiment can also carry out following develop:
In step 1), the maturing temperature can select in 200~800 DEG C, and the calcining time can be small 1~24 When interior selection, remaining condition is constant.
Embodiment 7
1) 0.1 gram of iron oxide, 0.4 gram of nickel oxide are weighed, 1 gram of tungsten carbide (i.e. carrier is tungsten carbide) is placed in mortar sufficiently Grinding roasts 1 hour in air atmosphere after grinding uniformly to get catalyst precursor at 350 DEG C；
2) catalyst precursor obtained is placed in hydrogen atmosphere, in lower 350 DEG C of reduction treatments 1 hour to get made Standby loading type nickel-based catalyst.
It analyzes and measures through x-ray photoelectron spectroscopy (XPS), in catalyst prepared by the present embodiment, the Ni-based conjunction of load Gold is FeNi3；It is learnt through plasma inductance linking atom emission spectrum (ICP) measurement: in catalyst prepared by the present embodiment, FeNi3The mass content of alloy is 20%.
In addition, the present embodiment can also carry out following develop:
In step 1), nickeliferous solid chemical compound can be nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel acetylacetonate, One of nickel phosphate, nickelous carbonate, nickel oxide, nickel hydroxide are a variety of, remaining condition is constant.
Comparative example 1
Referring to the preparation method of embodiment 3 in patent of invention (CN201710956080.1), comparative catalyst is prepared.
1) at room temperature, ammonium chloride (15 mMs) and oxalic acid (100 mMs) are dissolved in 50 milliliters of water, by acquired solution It moves into hydrothermal reaction kettle, weighs 5 grams of nickel foams (aperture degree 100PPI, be expressed as Ni-foam) and be immersed, at 100 DEG C Kept for 24 hours, natural cooling, it is washed after drying to get on carrier growth in situ have the load-type nickel of nickel oxalate layer Based catalyst precursors；
2) with the aqueous solution for containing 1.79 gram of three nitric hydrate indium, it is 1. made that 5 grams of steps of incipient impregnation are carried out at room temperature The NiC obtained2O4/ Ni-foam roasts 2 hours in 450 DEG C in air after drying to get catalyst precursor；
3) catalyst precursor obtained is placed in the mixed atmosphere of hydrogen and carbon monoxide and carbon dioxide, in 400 Reduction and carbonization 10 hours is carbonized nickel indium alloy catalyst at DEG C to get support type.
It analyzes and measures through x-ray photoelectron spectroscopy (XPS), in catalyst prepared by this comparative example, the alloy of load is InNi3C0.5；It is learnt through plasma inductance linking atom emission spectrum (ICP) measurement: catalyst prepared by this comparative example example In, InNi3C0.5The weight content of alloy is 29.5%.
Comparative example 2
Referring to the preparation method of embodiment 1 in patent of invention (CN201710956090.5), comparative catalyst is prepared.
1) 1g nickel foam is weighed, is ultrasonically treated 30 minutes in 20mL industrial alcohol, dilute nitre of 1M is used after distillation water washing Acid processing 2 minutes, is immersed in the hydrothermal reaction kettle containing nickel nitrate and aqueous ammonium chloride solution, wherein nitric acid after distilling water washing Nickel concentration is 0.01M, and ammonium chloride concentration 0.04M, hydrothermal temperature is 100 DEG C, and the hydro-thermal time is 3 hours, and reaction was completed, distillation After water washing in 100 DEG C drying to get on skeleton matrix growth in situ there is the self-supporting nickel phosphide of nickel hydroxide crystal layer to urge Agent precursor；
2) prepared self-supporting catalyst of phosphatizing nickel precursor is placed in reaction tube, purges 30 points through 50mL/min nitrogen Zhong Hou is passed through in the atmosphere of hydrogen phosphide, starts to warm up phosphorating treatment: being handled 0.5 hour at 300 DEG C, is finally used 50mL/min nitrogen Air-blowing is swept to room temperature to get self-supporting catalyst of phosphatizing nickel.
It is learnt through plasma inductance linking atom emission spectrum (ICP) measurement: in catalyst prepared by this comparative example example, Ni2The weight content of P is 29.5%.
Application examples
The catalyst of embodiment 1-4 and comparative example 1-2 preparation is investigated respectively using fixed bed reactors in dimethyl oxalate Catalytic performance in hydrogenation reaction: using stainless steel tube as reactor, wherein outer diameter 20mm, internal diameter 8mm, long 300mm, are catalyzed 0.5 gram of agent loading amount, reaction end gas is after condensing and separating, and the quantitative analysis of methyl glycollate and ethyl alcohol in collection liquid is in the day island proper It carries out on saliva 2014C gas chromatograph, is detected using chromatographic column HP-INNOWax and fid detector.
Conversion ratio and selectivity are calculated using normalization method.
Conversion ratio (%)=(1-ADMOfDMO/ΣAifi) × 100%
Selectivity (%)=(Aifi/ΣAifi) × 100%
Ai: each component FID chromatographic peak area；fi: each component FID relative friction index.
Reaction condition is 1.: in reaction pressure 2.5MPa, 230 DEG C of temperature are pumped into mass concentration 13% with highly pressurised liquid constant-flux pump The methanol solution of dimethyl oxalate (DMO), the quality liquid hourly space velocity (LHSV) based on DMO are 0.44h-1, hydrogen is to add hydrogen agent, hydrogen ester mole The rule that the catalytic performance of load-type nickel based alloy catalyst changes with the reaction time are prepared than investigating embodiment 1 under the conditions of being 90 Rule, reaction result is as shown in Figure 12.
Figure 12 is that load-type nickel based alloy catalyst prepared by embodiment 1 is used for prepared by dimethyl oxalate plus hydrogen ethanol synthesis 200 hours stability experiment results.It can be recognized from fig. 12 that nickel-base alloy catalyst prepared by embodiment 1 is steady at 200 hours In qualitative test, catalyst is maintained at 100% without inactivation sign, DMO conversion ratio, and ethanol selectivity is maintained at 95% or more, says Bright catalyst prepared by the present invention not only has excellent catalytic properties prepared by dimethyl oxalate plus hydrogen ethanol synthesis, also has excellent Good stability.
Reaction condition is 2.: in reaction pressure 2.5MPa, 180 DEG C and 190 DEG C of temperature are pumped into quality with highly pressurised liquid constant-flux pump The methanol solution of 13% dimethyl oxalate of concentration (DMO), the quality liquid hourly space velocity (LHSV) based on DMO are 0.44h-1, hydrogen is to add hydrogen agent, It is anti-in preparing ethylene glycol by using dimethyl oxalate plus hydrogen to prepare catalyst for investigation embodiment 2 and comparative example 1 under the conditions of hydrogen ester molar ratio is 90 Catalytic performance in answering, reaction result are as shown in table 1.
The catalytic performance that catalyst made from 1 embodiment 2 of table and comparative example 1 reacts preparing ethylene glycol by using dimethyl oxalate plus hydrogen
Sample Reaction temperature (DEG C) DMO conversion ratio (%) Glycol selectivity (%) Ethylene glycol yield (%)
Embodiment 2 180 99.7 92.0 91.7
Embodiment 2 190 100 91.2 91.2
Comparative example 1 180 95.0 67.1 63.7
Comparative example 1 190 99.6 88.6 88.2
Seen from table 1: loading type nickel-based catalyst prepared by the present invention is compared to negative in CN201710956080.1 Load type carbonization nickel indium alloy catalyst, has excellent catalytic properties preparing ethylene glycol by using dimethyl oxalate plus hydrogen reaction, especially In a low temperature of 180 DEG C, up to 99.7%, the selectivity of ethylene glycol is up to 92.0%, DMO and turns the high conversion rate of dimethyl oxalate Rate and glycol selectivity are apparently higher than support type carbonization nickel indium alloy catalyst, while its production cost is well below carbonization Nickel indium alloy catalyst production cost is conducive to industrial applications.
Reaction condition is 3.: in reaction pressure 2.5MPa, 190 DEG C of temperature are pumped into mass concentration 13% with highly pressurised liquid constant-flux pump The methanol solution of dimethyl oxalate (DMO), the quality liquid hourly space velocity (LHSV) based on DMO are 0.44h-1, hydrogen is to add hydrogen agent, hydrogen ester mole Catalyst is prepared in the reaction of prepared by dimethyl oxalate plus hydrogen methyl glycollate than investigating embodiment 3 and comparative example 2 under the conditions of being 90 Catalytic performance, reaction result is as shown in table 2
The catalysis that catalyst made from 2 embodiment 3 of table and comparative example 2 reacts prepared by dimethyl oxalate plus hydrogen methyl glycollate Performance
Sample DMO conversion ratio (%) Methyl glycollate selectivity (%) Methyl glycollate yield (%)
Embodiment 3 70.4 95.7 67.4
Comparative example 2 62.5 95.1 59.4
From table 2: loading type nickel-based catalyst prepared by the present invention is compared to negative in CN201710956090.5 Load type catalyst of phosphatizing nickel has excellent catalytic properties the reaction of prepared by dimethyl oxalate plus hydrogen methyl glycollate, at 190 DEG C Under low temperature, up to 70.4%, the selectivity of methyl glycollate is up to 95.7% for the high conversion rate of dimethyl oxalate, high conversion rate in Support type catalyst of phosphatizing nickel, while preparation method is easy, without using the hydrogen phosphide of severe toxicity, Environmental Safety is conducive to industry Metaplasia produces.
Reaction condition is 4.: in reaction pressure 2.5MPa, 230 DEG C of reaction temperature, it is dense to be pumped into quality with highly pressurised liquid constant-flux pump The methanol solution for spending 13% dimethyl oxalate (DMO), the quality liquid hourly space velocity (LHSV) based on DMO are 0.22h-1, hydrogen is to add hydrogen agent, hydrogen Ester molar ratio investigates the stability of catalyst prepared by embodiment 4 under the conditions of being 180, reaction result is as shown in figure 13.
Figure 13 is that load-type nickel based alloy catalyst prepared by embodiment 4 is used for prepared by dimethyl oxalate plus hydrogen ethanol synthesis 200 hours stability experiments are as a result, as seen from Figure 13, in test in 200 hours, catalyst is protected without inactivation sign, DMO conversion ratio Complete conversion is held, ethanol selectivity is maintained at 85% or more, illustrates that catalyst prepared by the present invention not only adds dimethyl oxalate Hydrogen ethanol synthesis has excellent catalytic properties, and also has excellent stability.
In conclusion load-type nickel based alloy catalyst provided by the invention, with stable structure, thermal conductivity is good, permeates Rate height, conversion ratio and selectivity high (especially cryogenic selective is high), active height, high mechanical strength, temperature range is wide, is easy into Type is easy to many advantages, such as filling and high-throughput low pressure drop, can be used as the reaction of prepared by dimethyl oxalate plus hydrogen methyl glycollate, oxalic acid The catalyst of diformazan ester through hydrogenation reaction for preparing glycol, prepared by dimethyl oxalate plus hydrogen ethanol synthesis has conspicuousness industrial application valence Value；In addition, preparation process of the invention is economical and practical, preparation process is simple, and raw material is easy to get, structure-controllable, is not necessarily to special installation And harsh conditions, it is easy to accomplish large-scale production has extremely strong practical value, therefore compared to the prior art, present invention tool There is conspicuousness progress.
Finally need indicated herein be: the above is only part preferred embodiments of the invention, should not be understood as to this hair The limitation of bright protection scope, those skilled in the art's above content according to the present invention make it is some it is nonessential improvement and Adjustment all belongs to the scope of protection of the present invention.

Claims (10)

1. a kind of load-type nickel based alloy catalyst, it is characterised in that: be made of the nickel-base alloy of carrier and load thereon, institute Stating nickel-base alloy is NixMyCzAlloy, wherein 1≤x≤10,1≤y≤10,0≤z≤5, the M be selected from iron, copper, cobalt, zinc, At least one of molybdenum, palladium, silver, gallium, indium, tin, germanium, bismuth, lead, and when z be greater than 0 when, M is not indium, the nickel-base alloy it is total Quality accounting is 1~50%, remaining is carrier.
2. load-type nickel based alloy catalyst according to claim 1, it is characterised in that: the material of the carrier is gold At least one of category, alloy, carbide, carbon, nitride, oxide；The metal is nickel, aluminium, copper, at least one in titanium Kind, the alloy is at least one of stainless steel, ferrum-chromium-aluminum, aluminium alloy, copper-nickel alloy, brass；The carbide is silicon carbide, carbon Change at least one of tungsten, molybdenum carbide, zirconium carbide；The carbon is at least one of active carbon, graphitic carbon, graphene；It is described Nitride is at least one of boron nitride, silicon nitride, titanium nitride, silicon nitride, tungsten nitride, molybdenum nitride；The oxide is alkali Earth metal, boron, aluminium, gallium, indium, silicon, lanthanide rare metal, titanium, zirconium, zinc, manganese, tungsten, vanadium, tin, niobium oxide at least one Kind.
3. a kind of method for preparing load-type nickel based alloy catalyst described in claim 1, it is characterised in that: be first in carrier The composite oxides that Ni and M is loaded on ZT, are made catalyst precursor, are then restored or restored carbon to catalyst precursor Change processing to get the load-type nickel based alloy catalyst.
4. according to the method described in claim 3, it is characterized in that, the preparation of the catalyst precursor, includes the following steps:
A) on carrier growth in situ nickel oxide precursor crystal layer, be made loading type nickel-based catalyst precursor；
B) impregnation is carried out to prepared loading type nickel-based catalyst precursor with the solution of the ion containing M, is then cleaned And drying, then 1~15 hour is roasted at 200~800 DEG C to get the catalyst precursor.
5. according to the method described in claim 4, it is characterized by: the nickel oxide precursor is nickel oxalate, nickel hydroxide Or terephthalic acid (TPA) nickel.
6. according to the method described in claim 3, it is characterized in that, the preparation of the catalyst precursor, includes the following steps:
Carrier is immersed in the solution containing nickel salt and M ion, reacts 0.5~45 in autoclave at 50~350 DEG C Hour, it is taken out after cooling, is then cleaned and dried to get the catalyst precursor.
7. according to the method described in claim 3, it is characterized in that, the preparation of the catalyst precursor, includes the following steps:
With the solution step impregnation carrier respectively containing nickel ion and M ion, or with the mixed solution containing nickel ion and M ion simultaneously Co-impregnation carrier；Then it is cleaned and is dried, then before roasting 1~15 hour at 200~800 DEG C to get the catalyst Drive body.
8. according to the method described in claim 3, it is characterized in that, the preparation of the catalyst precursor, includes the following steps:
After nickeliferous solid chemical compound and solid chemical compound and carrier mixed grinding containing M, 1~24 is roasted at 200~800 DEG C Hour is to get the catalyst precursor.
9. according to the method described in claim 3, it is characterized by: to catalyst precursor carry out reduction treatment when, it is used Any one of reducing agent in hydrogen, hydrazine, boron hydride, reduction temperature are 200~600 DEG C；To catalyst precursor When carrying out reduction and carbonization processing, reduction and carbonization temperature is 200~800 DEG C.
10. a kind of application of load-type nickel based alloy catalyst described in claim 1, it is characterised in that: with the load Type nickel-base alloy catalyst is anti-as the reaction of prepared by dimethyl oxalate plus hydrogen methyl glycollate, preparing ethylene glycol by using dimethyl oxalate plus hydrogen It answers, the catalyst of prepared by dimethyl oxalate plus hydrogen ethanol synthesis.
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CN110523433A (en) * 2019-08-20 2019-12-03 南昌大学 A kind of nickel-base catalyst and the preparation method and application thereof
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CN110483241A (en) * 2019-08-19 2019-11-22 易高环保能源研究院有限公司 The method and apparatus of preparation of ethanediol by dimethyl oxalate hydrogenation
CN110523433A (en) * 2019-08-20 2019-12-03 南昌大学 A kind of nickel-base catalyst and the preparation method and application thereof
CN113262794B (en) * 2020-02-17 2022-12-27 上海迅凯新材料科技有限公司 Supported nickel catalyst, preparation method and application in hydrogenation reaction of 1, 4-butynediol
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CN111569926A (en) * 2020-04-23 2020-08-25 台州学院 Boron nitride loaded palladium-gold-tin liquid alloy catalyst and preparation method and application thereof
CN111450831A (en) * 2020-05-22 2020-07-28 北京化工大学 High-performance graphene-loaded mesoporous nickel-iron alloy electrocatalyst and preparation method thereof
CN113713840B (en) * 2020-05-25 2023-07-25 台州学院 Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof
CN113713840A (en) * 2020-05-25 2021-11-30 台州学院 Cobalt nitride-nickel gallium liquid alloy composite catalyst and preparation method and application thereof
CN112516988A (en) * 2020-12-16 2021-03-19 中南大学 Catalyst with CeZrK/rGO nano solid solution as main component
CN112516988B (en) * 2020-12-16 2021-09-21 中南大学 Catalyst with CeZrK/rGO nano solid solution as main component
CN114534723A (en) * 2021-04-15 2022-05-27 华烁科技股份有限公司 Catalyst for preparing glycollic acid by selective oxidation of ethylene glycol and preparation method thereof
CN113952959A (en) * 2021-11-24 2022-01-21 中国华能集团清洁能源技术研究院有限公司 Catalyst and preparation method and application thereof
CN113952959B (en) * 2021-11-24 2023-06-30 中国华能集团清洁能源技术研究院有限公司 Catalyst and preparation method and application thereof
CN114534732A (en) * 2022-01-28 2022-05-27 东南大学 Synthesis method of catalyst for preparing hydrogen by reforming propane steam
CN114534732B (en) * 2022-01-28 2023-12-01 东南大学 Synthesis method of catalyst for preparing hydrogen by steam reforming of propane
CN115007172A (en) * 2022-07-25 2022-09-06 合肥飞木生物科技有限公司 Preparation method and application of dimethyl oxalate selective hydrogenation catalyst
CN115007172B (en) * 2022-07-25 2024-03-26 合肥飞木生物科技有限公司 Preparation method and application of dimethyl oxalate selective hydrogenation catalyst
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