CN109647419A - A kind of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, preparation method and application - Google Patents
A kind of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, preparation method and application Download PDFInfo
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- CN109647419A CN109647419A CN201811567437.8A CN201811567437A CN109647419A CN 109647419 A CN109647419 A CN 109647419A CN 201811567437 A CN201811567437 A CN 201811567437A CN 109647419 A CN109647419 A CN 109647419A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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Abstract
The invention discloses a kind of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalysts, preparation method and application, catalyst is using the nickel-base catalyst of alumina load as active component, by parallel flow precipitation at 25-90 DEG C, it is modified using low content rare-earth oxide.Using tank reactor, in lower temperature and without alkaline reagent, realizes that adiponitrile catalyzed conversion is highly selective under reaction time 1-6h, pressure 1-9MPa and prepare hexamethylene diamine.It does not need to add any basic solvent or NH in reaction process of the present invention3The generation for inhibiting cyclisation side reaction, reduces environmental pollution, and catalytic mechanical intensity is big, post-reaction treatment is simple, reaction condition is relatively mild.Method according to the present invention, in section Example, according to set response parameter, for the high conversion rate of adiponitrile up to 100%, product hexamethylene diamine selectively may be up to 90%.With good economic efficiency and prospects for commercial application.
Description
Technical field
The invention belongs to field of chemical technology, are specifically related to a kind of rare earth oxide-modified adiponitrile
Add hydrogen preparing hexanediamine high-selectivity catalyst and preparation method thereof, be using the nickel-base catalyst of alumina load as active component,
By parallel flow precipitation, it is modified using low content rare-earth oxide.Using tank reactor, in lower temperature and nothing
Adiponitrile is reacted by liquid phase catalytic hydrogenation under the conditions of alkaline reagent, it is highly selective to prepare target product hexamethylene diamine.
Background technique
Nitrile catalytic hydrogenation is the essential industry approach for preparing a variety of aminated compounds, and nitrile adds the product of hydrogen mainly by primary
The mixture of amine, secondary amine and tertiary amine forms.Wherein hexamethylene diamine (HMD) is as a kind of important bifunctional compound, in chemical industry
Field has important application.Due to, containing there are two the amidine functional group with reactivity, can be generated a variety of in its molecule
High valuable chemicals are a kind of important organic chemical industry's intermediates.Meanwhile hexamethylene diamine belongs to strong organic base, energy and electrophilicity
Compound such as H+, alkyl halide, the compounds such as hydroxyl react.Mainly for the production of polyamide, such as respectively by with adipic acid
Nylon -66 is prepared with decanedioic acid polycondensation reaction, nylon-610 is gone forward side by side one-step synthesis nylon resin, nylon fiber and engineering plastics
Equal products.According to statistics, the hexamethylene diamine produced every year in the world about 90% is all used for the production of nylon -66.Hexamethylene diamine can also be used in
Polyimides carboxylic acid ester foamed plastic and production adhesive, the additive of rubber product, epoxy curing agent, polyamine esterification solidification
Agent, organic crosslinking agent etc..In addition to mineral products (oil can be also widely used for synthetic cross-linking agent and nylon resin materials, hexamethylene diamine
Field demulsifier), agriculture (pesticide), building (concrete additive) etc..
In recent years, hexamethylene diamine was by development and application in the primary raw material of production hexa-methylene -1,6- diisocyanate (HDI).
HDI is also important one of the downstream product of hexamethylene diamine, and HDI only has France, Germany, Japan and other countries to have on a small scale in foreign countries at present
Production, domestic demand all rely on import.In addition, hexamethylene diamine can be reacted with phosgene prepares oneself two under ultraviolet light irradiation
Nitrile isocyanates is further continued for carrying out polymerization reaction production polyurethane material, is widely used in space industry.
Chinese patent, publication number: CN103977819A discloses a kind of activation method of adipic dinitrile hydrogenation catalyst.?
Under microwave condition, respectively with the modified Raney's nickel catalyst of the metal promoters such as iron, chromium, molybdenum, bismuth, manganese or tungsten, it is catalyzed for adiponitrile
Hydrogenation reaction, specific surface area of catalyst obtained by the patent is larger, and auxiliary agent is lost smaller, adiponitrile conversion ratio and hexamethylene diamine choosing
Selecting property is higher.But the mechanical performance of Raney's nickel catalyst is poor, unstable easy spontaneous combustion in air, pole during the reaction
Easily broken inactivation, the service life is shorter, needs to be added a large amount of ammonia during the reaction to inhibit the generation of by-product secondary amine and tertiary amine,
And homogeneous catalyst has the disadvantages of industrial last handling process is complicated, and recycling is difficult, economic benefit still has to be hoisted.
Chinese patent, publication number: CN105032433A is disclosed and a kind of is modified using potassium prepared by infusion process and chromium
TiO2Nano tube supported nickel-base catalyst is used for adiponitrile catalytic hydrogenation reaction.Wherein the mass percentage of chromic nitrate is
0-2wt%, the mass percentage of nickel nitrate are 20-30wt%, and the mass percentage of potassium nitrate is 0.05-0.2wt%.Instead
Answering temperature is 75 DEG C, and under conditions of reaction pressure is 2MPa, adiponitrile conversion ratio may be up to 92%, and the selectivity of hexamethylene diamine is
36.3%, 6-aminocapronitrile is selectively 59.2%, and the overall selectivity of hexamethylene diamine and 6-aminocapronitrile nominal primary amine reaches
95.5%.But hexamethylene diamine and 6-aminocapronitrile coexist in product, are unable to reach the highly selective of specific aim product hexamethylene diamine.
In conclusion in view of current adipic dinitrile hydrogenation technology limitation and downstream industry to hexamethylene diamine demand
Sharply increase, develop China's independent research adiponitrile catalytic hydrogenation process it is imperative.How adipic dinitrile hydrogenation is improved
Conversion ratio and control hexamethylene diamine target product it is highly selective most important.
Summary of the invention
Based on some shortcomings of current adiponitrile catalytic hydrogenation research, the present invention provides a kind of rare-earth oxides to change
The adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst of property, with Al2O3Carrier loaded Ni sill is activated centre, is used
Low content (0-10wt%) rare-earth oxide (including CeO2、Sm2O3、Y2O3、Tm2O3Deng) it is auxiliary agent, pass through parallel-flow precipitation
Method develops the Ni-based catalysis material of alumina load, using alcohols as solvent in pressure autoclave type reactor, in the lower (50-120 of temperature
DEG C) under conditions of, hexamethylene diamine is converted by adipic dinitrile hydrogenation, reaches high conversion, high target product selectivity.
Technical solution of the present invention:
A kind of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, with Al2O3Carrier is negative
The Ni sill of load is activated centre, using parallel flow precipitation by low content rare-earth oxide to the nickel of alumina load
Base catalyst is modified, and is directly catalyzed adipic dinitrile hydrogenation under lower temperature and without alkaline reagent conditions using tank reactor
It is highly selective to prepare hexamethylene diamine.
The rare-earth oxide is one or more of cerium oxide, samarium oxide, yttrium oxide, thulium oxide
Combination.
The mass fraction of the low content rare-earth oxide is the not more than 10wt% of catalyst.
A kind of preparation method of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, is adopted
It is prepared with co-precipitation method, steps are as follows:
It is uniform by ultrasonic mixing using aluminum nitrate, nickel nitrate and corresponding rare earth metal salt presoma, prepare mixed solution
A；Natrium carbonicum calcinatum is dissolved in deionized water, sodium carbonate liquor B is configured to；At a certain temperature, by mixed solution A and carbonic acid
Sodium solution B cocurrent is slowly dropped into deionized water, and it is 8.0-11.0 that sodium carbonate liquor control solution final ph, which is persistently added dropwise,；Always
It is filtered after changing 6-12 hours by deionized water and methanol, washs, dries, by the powder after grinding, one in tube furnace
Determine roasting temperature 2-6h and obtains catalyst precursor；By catalyst precursor in H2It is restored under certain temperature in/Ar gaseous mixture
2-8h obtains catalyst fines.
The rare earth metal salt presoma includes nitrate, sulfate, acetate, oxalates and acetylacetonate.
The nickel-base catalyst of the alumina load of the rare-earth oxide modification, wherein Ni is activated centre, is urged
The content of Ni is 10-40wt% in agent.
The natrium carbonicum calcinatum opposing metallic total ion concentration stoichiometric ratio is 0.5-3.0.
The parallel flow precipitation operation temperature is 25-90 DEG C.
The nickel-base catalyst maturing temperature is 300-800 DEG C.
The nickel-base catalyst presoma is in H2Reduction temperature is 300-800 DEG C in/Ar gaseous mixture.
A kind of highly selective Ni base catalyst for adipic dinitrile hydrogenation preparing hexanediamine, steps are as follows:
Rare-earth oxide modification type nickel-base material after using prereduction for catalyst, using certain catalyst with
Adiponitrile mass ratio (0.05-0.5), in tank reactor, using the alcohols with adiponitrile certain mass ratio as solvent (adiponitrile
It is 10-30% with alcohols mass percent), in 50-120 DEG C of lower temperature and without alkaline reagent, Hydrogen Vapor Pressure 1-9MPa condition
Under, 1-6h is reacted, adipic dinitrile hydrogenation is highly selective prepares target product hexamethylene diamine for catalysis.
Beneficial effects of the present invention: the present invention provides a kind of loading type nickel-based catalysts, with Al2O3For carrier, with rare earth
Metal oxide is prepared as auxiliary agent using co-precipitation method.The present invention is compared to Raney's nickel catalyst, in reaction process not
Need to add any basic solvent or NH3The generation for inhibiting side reaction, reduces environmental pollution, and catalytic mechanical intensity is big, instead
Answer last handling process simple, reaction condition is more mild, can obtain higher adiponitrile conversion ratio and hexamethylene diamine target product
It is highly selective.Method according to the present invention, in section Example, according to set response parameter, the conversion of adiponitrile
Rate is up to 100%, product hexamethylene diamine selectively up to 90%.
Detailed description of the invention
Fig. 1 is 2wt%CeO2X-ray diffraction (XRD) map of modified nickel-base catalyst.
Fig. 2 is 2wt%CeO2Modified nickel-base catalyst sample is in NH3Temperature programmed desorption curve under atmosphere.
Fig. 3 is the Ni/CeO of 2wt% after pretreatment using 50nm as scale2/Al2O3The transmission electron microscope of catalyst shines
Piece.
Fig. 4 is the Ni/CeO of 2wt% after pretreatment using 20nm as scale2/Al2O3The transmission electron microscope of catalyst shines
Piece.
Fig. 5 is Ni/Al2O3The EDX element Surface scan analysis chart of catalyst.
Specific embodiment
Below in conjunction with attached drawing and technical solution, a specific embodiment of the invention is further illustrated.
Embodiment 1
Certain density nickel nitrate, aluminum nitrate and cerous nitrate metal salt presoma are prepared, configuration uniform by ultrasonic mixing
At mixed solution A, while the natrium carbonicum calcinatum of 1.1 times of stoichiometric ratios of opposing metallic total ion concentration being taken to be dissolved in a certain amount of deionization
In water, it is configured to the sodium carbonate liquor B of pH=11.Under 45 DEG C of constant temperature and stirring condition, simultaneously by two kinds of clear solutions of above-mentioned A, B
Stream instills in deionized water, and control drop speed is 3s/ drop.It is persistently adjusted using sodium carbonate liquor until pH=10.After aging 8 hours
It is filtered, washed by deionized water and methanol, is 10 hours dry at 110 DEG C, by the powder after grinding, in tube furnace
4h is roasted at 400 DEG C obtains catalyst precursor.By catalyst precursor in H26h is restored in/Ar gaseous mixture at 400 DEG C to obtain
Catalyst fines.Fig. 1 shows 2wt%CeO2X-ray diffraction (XRD) map of modified nickel-base catalyst.Fig. 2 shows 2wt%
CeO2Modified nickel-base catalyst sample (2%) is in NH3Temperature programmed desorption curve under atmosphere.
Embodiment 2
By the 0.5g CeO of 2.5g adiponitrile, the dehydrated alcohol of 25ml and reduction pretreatment2Mass percent be 2wt%
Ni/CeO2/Al2O3Catalyst is added in the high-pressure sealed reaction kettle of 50ml, with air 2-3 times in hydrogen displacement kettle.Using stirring
Speed 800rpm, when reaction a length of 3h.Fig. 3 and Fig. 4 shows 2wt%CeO after pretreatment2Modified Ni/CeO2/Al2O3Catalyst
Transmission electron microscope photo.The following table 1 is shown in Ni/CeO under the conditions of differential responses2/Al2O3The catalysis of liquid-phase catalysis adiponitrile is added
The test result of hydrogen.
2wt%CeO at a temperature of 1 differential responses of table2Modified Ni/CeO2/Al2O3Survey to liquid phase adiponitrile catalytic hydrogenation
Test result
Embodiment 3
By 2.5g adiponitrile, the 0.5gCeO of the dehydrated alcohol of 25ml and reduction pretreatment2Mass percent is 1wt%'s
Ni/CeO2/Al2O3Catalyst agent is added in 50ml autoclave, with air 2-3 times in hydrogen displacement kettle.Using stirring
Speed 800rpm, when reaction a length of 3h, reaction temperature is 90 DEG C, Hydrogen Vapor Pressure 7MPa, and adiponitrile conversion ratio is 100%, oneself
The selectivity of diamines is 70%.The hexamethylene diamine of high-purity is obtained after vacuum distillation purification.
Embodiment 4
The 0.5gCeO that 2.5g adiponitrile, the dehydrated alcohol of 25ml and reduction are obtained2Mass percent is the Ni/ of 3wt%
CeO2/Al2O3Catalyst is added in the high-pressure sealed reaction kettle of 50ml, with air 2-3 times in hydrogen displacement kettle.Using mixing speed
800rpm, when reaction a length of 3h, reaction temperature is 90 DEG C,
Hydrogen Vapor Pressure is 7MPa, and adiponitrile conversion ratio is 100, and the selectivity of hexamethylene diamine is 90%.It is refined through vacuum distillation
The hexamethylene diamine of high-purity is obtained afterwards.
Embodiment 5
The 0.5g CeO that 2.5g adiponitrile, the dehydrated alcohol of 25ml and reduction are obtained2Mass percent is 5wt%'s
Ni/CeO2/Al2O3Catalyst is added in 50ml autoclave, with air 2-3 times in hydrogen displacement kettle.Using mixing speed
800rpm, when reaction a length of 3h, reaction temperature is 90 DEG C, Hydrogen Vapor Pressure 7MPa, and adiponitrile conversion ratio is 100%, hexamethylene diamine
Selectivity be 84%.The hexamethylene diamine of high-purity is obtained after vacuum distillation purification.
Embodiment 6
By 2.5g adiponitrile, the 0.5gNi/Al of the dehydrated alcohol of 25ml and reduction pretreatment2O350ml high is added in catalyst
It presses in closed reactor, using air 2-3 times in hydrogen displacement kettle.Fig. 5 is Ni/Al2O3The EDX element Surface scan of catalyst point
Analysis figure.Using mixing speed 800rpm, when reaction a length of 3h, reaction temperature is 90 DEG C, Hydrogen Vapor Pressure 7MPa, adiponitrile conversion
Rate is 100%, and the selectivity of hexamethylene diamine is 64%.
Claims (5)
1. a kind of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, which is characterized in that with
Al2O3Carrier loaded Ni sill is activated centre, using parallel flow precipitation by low content rare-earth oxide to oxidation
What the nickel-base catalyst of aluminium load was modified；
The rare-earth oxide is the group of one or more of cerium oxide, samarium oxide, yttrium oxide, thulium oxide
It closes；
The mass fraction of the low content rare-earth oxide is the not more than 10wt% of catalyst；
The content of Ni is 10-40wt% in the catalyst.
2. a kind of preparation method of rare earth oxide-modified adipic dinitrile hydrogenation preparing hexanediamine high-selectivity catalyst, special
Sign is that steps are as follows using the preparation of co-precipitation method:
It is uniform by ultrasonic mixing using aluminum nitrate, nickel nitrate and corresponding rare earth metal salt presoma, prepare mixed solution A；It will
Natrium carbonicum calcinatum is dissolved in deionized water, is configured to sodium carbonate liquor B；Under the conditions of 25-90 DEG C of temperature, by mixed solution A and
Sodium carbonate liquor B cocurrent is slowly dropped into deionized water, and it is 8.0- that sodium carbonate liquor control solution final ph, which is persistently added dropwise,
11.0；It is filtered after aging 6-12 hours by deionized water and methanol, washs, dries, by the powder after grinding, in tubular type
2-6h is roasted in furnace under the conditions of 300-800 DEG C of temperature and obtains catalyst precursor；By catalyst precursor in H2In/Ar gaseous mixture
Reductase 12-8h obtains catalyst fines under the conditions of 300-800 DEG C of temperature.
3. preparation method according to claim 2, which is characterized in that the rare earth metal salt presoma includes nitric acid
Salt, sulfate, acetate, oxalates and acetylacetonate.
4. preparation method according to claim 2 or 3, which is characterized in that the natrium carbonicum calcinatum opposing metallic ion
Total amount stoichiometric ratio is 0.5-3.0.
5. a kind of highly selective Ni base catalyst for adipic dinitrile hydrogenation preparing hexanediamine, which is characterized in that steps are as follows:
Rare-earth oxide modification type nickel-base material after using prereduction controls the matter of catalyst and adiponitrile for catalyst
Amount is than being 0.05-0.5；In tank reactor, using alcohols as solvent, adiponitrile and alcohols mass percent are 10-30%；?
Under the conditions of temperature is 50-120 DEG C and is 1-9MPa without alkaline reagent and Hydrogen Vapor Pressure, 1-6h is reacted, catalysis adipic dinitrile hydrogenation is high
Selectivity prepares target product hexamethylene diamine.
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| CN111151256A (en) * | 2020-01-20 | 2020-05-15 | 山东玉皇化工有限公司 | Catalyst for synthesizing hexamethylene diamine |
| CN111644196A (en) * | 2020-06-17 | 2020-09-11 | 山东达民化工股份有限公司 | High-selectivity preparation method of methylpentamethylenediamine by adopting composite catalytic system |
| CN113231069A (en) * | 2021-04-15 | 2021-08-10 | 云南大为恒远化工有限公司 | Composite efficient catalyst for preparing succinic anhydride by maleic anhydride body hydrogenation and preparation method thereof |
| CN114249656A (en) * | 2022-01-10 | 2022-03-29 | 万华化学集团股份有限公司 | Preparation method of hexamethylene diamine |
| CN114425347A (en) * | 2020-10-29 | 2022-05-03 | 中国石油化工股份有限公司 | Selective ammoniation hydrogenation catalyst, preparation method thereof and synthesis method of cycloheximide |
| CN114471582A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalyst for preparing diamine by hydrogenation of dinitrile, method and application |
| CN114797880A (en) * | 2022-06-23 | 2022-07-29 | 北京弗莱明科技有限公司 | Composite metal oxide catalyst and preparation method and application thereof |
| CN115430456A (en) * | 2022-09-28 | 2022-12-06 | 河南省化工研究所有限责任公司 | Catalyst for synthesizing hexamethylene diamine and preparation method and application thereof |
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| CN115894253A (en) * | 2022-11-10 | 2023-04-04 | 山东阳谷华泰化工股份有限公司 | Production process for synthesizing hexamethylene diamine by catalytic hydrogenation of adiponitrile |
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| CN115646508A (en) * | 2022-10-13 | 2023-01-31 | 厦门大学 | Supported Ni-Ru catalyst, preparation method and application |
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Application publication date: 20190419 |