CN106807377A - A kind of catalyst for synthesizing hexamethylene diamine - Google Patents

A kind of catalyst for synthesizing hexamethylene diamine Download PDF

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CN106807377A
CN106807377A CN201510846359.5A CN201510846359A CN106807377A CN 106807377 A CN106807377 A CN 106807377A CN 201510846359 A CN201510846359 A CN 201510846359A CN 106807377 A CN106807377 A CN 106807377A
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catalyst
carrier
ammonia
hexamethylene diamine
active component
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严丽
丁云杰
吕元
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—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
    • B01J23/8896—Rhenium
    • 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
    • B01J23/74—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
    • B01J23/78—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 alkali- or alkaline earth metals
    • 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
    • B01J27/24—Nitrogen compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
    • C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
    • C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/023—Preparation; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
    • C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
    • C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical Kinetics & Catalysis (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a kind of catalyst for synthesizing hexamethylene diamine.Catalyst is made up of the part of carrier three that main active component, auxiliary agent and ammoniated treatment are crossed, and main active component is Ni or Co, and auxiliary agent is one or more in the metals such as Fe, Cu, Ru, Re, K, Zn, B or oxide；The carrier that ammoniated treatment is crossed is from the SiO by ammoniated treatment2Or Al2O3.Main active component accounts for 1~40% in total catalyst weight, and auxiliary agent accounts for 0.1~20%.The characteristics of catalyst of the present invention is that used carrier is needed by ammonification specially treated.Using catalyst of the invention carry out hexylene glycol or amino-hexanol or hexylene glycol amino-hexanol mixture aminating reaction, hexamethylene diamine product is synthesized under hydro condition, show high activity, high selectivity and stability.

Description

A kind of catalyst for synthesizing hexamethylene diamine
Technical field
The present invention relates to a kind of catalyst for synthesizing hexamethylene diamine and its application.In more detail, be related to it is a kind of for hexylene glycol under hydro condition or amino-hexanol or hexylene glycol amino-hexanol mixture and ammonia be converted into the catalyst of hexamethylene diamine.
Background technology
Hexamethylene diamine is a kind of important organic chemical industry's intermediate, mainly for the production of polyamide, such as nylon salt, NYLON610, nylon 612 and nylon 69；Can also be used for synthesizing curing agent, organic crosslinking agent of two isocyanates or epoxy resin and arteries and veins urea formaldehyde etc..With continuing to develop for synthetic fiber industry, the demand of hexamethylene diamine class compound is continuously increased in world wide, and price Continued, market supply and demand breach is larger.
The production technology of hexamethylene diamine mainly has caprolactam method, butadiene process, adipic acid method and adiponitrile catalytic hydrogenation method.Caprolactam method and butadiene process are only applicable to small-scale production, and are gradually eliminated because production cost is higher；Adipic acid method is that adipic acid generates adiponitrile with ammonia through amination, dehydration, and adiponitrile repeated hydrogenation obtains hexamethylene diamine, and this method production cost is high, operation is long, in addition unreasonable to the utilization of resources, and its process-technology-evolutions is limited, and has been eliminated at present；Adiponitrile catalytic hydrogenation prepares hexamethylene diamine method and is widely used because process is simple, product quality are high, low production cost.
The production capacity of hexamethylene diamine is about 1,500,000 tons/year in the world at present, is concentrated mainly on North America and West Europe.Adiponitrile catalytic hydrogenation prepares hexamethylene diamine method and is almost monopolized by external large enterprise, and the country only has Henan Shen Ma groups and Sinopec Liao Yang petrochemical company from the external package import technology, and the research to the technique is still in the starting stage at home.Industrial adipic dinitrile hydrogenation process used catalyst is mainly Raney Ni type catalyst, but the mechanical performance of Raney Ni type catalyst is poor, easy spontaneous combustion in atmosphere, there is substantial amounts of alkali lye to discharge in preparation process, and need in the basic conditions be reacted using Raney Ni types catalyst and suppress the generation of secondary amine and tertiary amine so as to improve the selectivity of hexamethylene diamine, the co-catalyst NaOH or KOH of addition are larger to equipment corrosion, it is difficult to separated with product.Raw material adiponitrile all relies on import, and its fancy price has had a strong impact on economic benefit and the competitiveness in the international market of China's nylon industry, constrains the development of China's nylon related industry, therefore, developing new hexamethylene diamine technology has turned into extremely urgent problem.
The preparation of hexamethylene diamine production Raney's nickel catalyst has traditional method and high-energy ball milling method etc..Industrial Raney's nickel catalyst is prepared mainly in two steps：One is the preparation of alumel, and two is alkali fusion, also cries activation.Alumel be mainly with smelting prepare, the main thing of alloy mutually be Ni2Al3、NiAl3And a small amount of Al/Ni2Al3.The purpose of alkali fusion is to dissolve away a part of aluminium using the both sexes of aluminium, forms skeleton and hole, makes nickle atom highly exposed.The spongy tissue that the catalyst formed through alkali fusion dealuminzation is made up of nanometer nickel crystallite, thus with hydrogenation activity higher.It is generally believed that different things mutually has different dealuminzation speed, the dealuminzation speed of alloy presses Al/Ni2Al3、NiAl、Ni2Al3Order is successively decreased successively, while having different hydrogenation activities.
CN1139392 discloses a kind of preparation method of the catalyst of nitrile catalytic hydrogenation generation amine, described catalyst is the Raney Raney nickels adulterated with least one additional metal elements, and described at least one additional metal elements are selected from IVb, Vb and VIb race of periodic table.It is characterized in that Raney Raney nickels suspend in the solution, is preferably suspended in the acid solution of additional metal elements.
CN 103977819 discloses a kind of activation method of adipic dinitrile hydrogenation catalyst, and the catalyst is modified Raney's nickel catalyst, is activated with following methods：Iron, chromium, molybdenum, bismuth, manganese or tungsten soluble-salt and NaOH are configured to mixed solution respectively, modified Raney's nickel catalyst and ammonium salt are slowly added to；React and wash in heated under microwave conditions.The preparation method of modified Raney's nickel catalyst is：Nickel-aluminum alloy is milled into powder, be added to dissolves aluminum portions with NaOH, ammonium salt, the ammoniacal liquor mixed solution of certain proportion mixing, with deionized water and absolute ethanol washing；Under microwave condition, above-mentioned powder is added in the mixed solution being made up of ferric nitrate and dressing agent and is reacted, gained solid through drying and roasting, be passed through hydrogen reducing after obtain modified Raney's nickel catalyst
CN 104001516 recently discloses the catalyst that a kind of adiponitrile catalytic hydrogenation prepares hexamethylene diamine, and the catalyst is amorphous nickel alloy catalyst, is made of following methods：(1) preparation of catalyst fines：Ammoniacal liquor and nickel nitrate are configured to nickel ammonium complex solution first, then are mixed and stirred for the dressing agent aqueous solution, through hydrothermal aging, be separated by filtration, after drying and roasting, reduction obtains catalyst fines under being passed through hydrogen high temperature；(2) activation of catalyst：Above-mentioned catalyst fines is slowly added into NaOH solution, under microwave condition, certain hour is heated and stir.After reaction terminates, remove upper strata alkali lye and be washed with deionized to neutrality, then it is standby with absolute ethanol washing.
Numerous studies show, the species and performance of catalyst are the deciding factors for influenceing response path, and this is different mainly due to the own eyeball of 6- amino, cycloheximide and hexamethylene diamine active position on a catalyst and adsorption capacity.From the point of view of current existing document and technology, poor selectivity is there is in the production technology of hexamethylene diamine mostly, product separates difficulty, and severe reaction conditions, the low shortcoming preparation method of yield is unfavorable for extensive continuous industrial production.During industrialized adipic dinitrile hydrogenation prepares hexamethylene diamine route, also in the presence of 2 big fatal problems：One is the Raney Ni catalyst generally used in route, and easy spontaneous combustion in atmosphere has great potential safety hazard in preparation process；Another is raw material adiponitrile dependence on import, and price is high and restricted and people.Therefore, economic development of the synthesis technique of green hexamethylene diamine to China is developed significant.
Hexylene glycol or amino-hexanol or hexylene glycol harm of the amino-hexanol mixture to environment and human body it is smaller, meet the green chemical products that China strongly praises highly and encourages development, therefore, develop that prepare hexamethylene diamine with hexylene glycol as raw material is a path for relative environmental protection, the development of catalyst is the key factor of the technique.
The content of the invention
It is an object of the invention to provide a kind of catalyst for synthesizing hexamethylene diamine, the catalyst can realize it is following in one or more：(1) allow hexylene glycol or amino-hexanol or hexylene glycol amino-hexanol mixture face hydrogen amination production hexamethylene diamine and realized under relatively low reaction pressure, (2) modulation reaction condition can flexible modulation product form, (3) process units one-time investment and production cost are reduced, (4) realize easy to operate, (5) activity of catalyst is improved, (6) selectivity to product is improved, (7) conversion ratio of raw material is improved, (8) improve the stability of method and (9) improve the security of hexamethylene diamine production process.
The present invention provides a kind of catalyst for facing hydrogen amination synthesis hexamethylene diamine for hexylene glycol or amino-hexanol or Ji Erchun amino-hexanol mixtures, the catalyst is made up of the part of carrier three that main active component, auxiliary agent and ammoniated treatment are crossed, wherein described main active component is selected from one or more in the group being made up of Ni and Co, and the auxiliary agent is selected from one or more in the group being made up of Fe, Cu, Ru, Re, K, Zn and B and their own oxide；The carrier that the ammoniated treatment is crossed is by selected from by SiO2And Al2O3One or more carrier in the group of composition is obtained by ammoniated treatment, and the ammoniated treatment includes：Temperature by carrier with ammonia source at 200 to 400 DEG C is contacted 0.5 to 24 hour.
In a preferred embodiment, the specific surface area of the carrier is 150~350m2/ g, and average pore size is 8-80nm.
In another preferred embodiment, the ammonia source is selected from one or more in the group being made up of ammonia, liquefied ammonia, ammoniacal liquor and urea.
In another preferred embodiment, the main active component accounts for 1~40%, preferably 5~30% in the gross weight of the catalyst.
In another preferred embodiment, the auxiliary agent accounts for 0.1~20%, preferably 0.1~15% in the gross weight of the catalyst.
In another preferred embodiment, the catalyst is before the use normal pressure in hydrogen atmosphere and in pressure, and temperature is that 150~400 DEG C and hydrogen gas space velocity are 500~4000h-1Under conditions of reduction activation.
More specifically, the present invention provides a kind of loaded catalyst for synthesizing hexamethylene diamine, the carrier crossed by main active component, auxiliary agent and ammoniated treatment is constituted, main active component is Ni and/or Co, and auxiliary agent is one or more in the group that Fe, Cu, Ru, Re, K, Zn and B and their own oxide are constituted；Carrier selects SiO2And/or Al2O3, and carrier passes through ammonification specially treated.Wherein, catalyst is prepared by infusion process, wherein the solution impregnating carrier of the soluble-salt with Ni and/or Co, the soluble-salt is nitrate, chlorate, acetate, oxalates, sulfate, citrate or other soluble-salts of Ni and/or Co.Main active component accounts for 1~40% in total catalyst weight；Auxiliary agent accounts for 0.1~20% in total catalyst weight；Carrier S iO2Or Al2O3Specific surface area be 150~350m2/ g, average pore size is 8-80nm.Carrier S iO2And/or Al2O3Ammoniated treatment is carried out using ammonia, liquefied ammonia, ammoniacal liquor or urea.
The catalyst of the invention reduction activation in hydrogen atmosphere before application：Pressure is normal pressure, and temperature is 150~400 DEG C, and hydrogen gas space velocity is 500~4000h-1.Under hydro condition by hexylene glycol or amino-hexanol or hexylene glycol amino-hexanol mixture and ammonia be converted into the reaction condition of hexamethylene diamine product：Temperature is 135~200 DEG C, and pressure is 6.0~22.0MPa, and the liquid air speed of hexylene glycol or amino-hexanol or Ji Erchun amino-hexanol mixtures is 0.3~1.5h-1。
Reactor of the invention can use fixed bed reactors, paste state bed reactor or trickle bed reactor.Wherein preferred trickle bed reactor.
In reaction system of the invention, directly the hexylene glycol or amino-hexanol of liquid or Ji Erchun amino-hexanols mixture and ammonia mixture can be pumped into after being preheated to 135~200 DEG C after mixing with hydrogen in preheater and entered into trickle bed reactor.
This catalyst be applied to hexylene glycol under hydro condition or amino-hexanol or hexylene glycol amino-hexanol mixture and ammonia reaction in, excellent active, selectivity and stability are shown, the hexamethylene diamine series of products of generation are including hexamethylene diamine, cycloheximide, amino-hexanol etc..
In the present invention, hydro condition refers to the presence of under conditions of hydrogen.
Compared with prior art, its significant effect is the present invention：The carrier S iO of catalyst of the invention2Or Al2O3Ammoniated treatment is carried out using ammonia, liquefied ammonia, ammoniacal liquor or urea.Due to carrier S iO2Or Al2O3Surface on there is substantial amounts of hydroxyl and make carrier surface in sour environment, be conducive to intermediate product imines to be polymerized and produce substantial amounts of accessory substance, so as to reduce the selectivity of hexamethylene diamine.And after carrier surface is by ammonification, the substantial amounts of hydroxyl in surface is converted into amido and is in alkalescence, this reduces the possibility of imines polymerization, hexamethylene diamine selectivity and stability are improve.After carrier loaded main active component and auxiliary agent after treatment, be applied under hydro condition hexylene glycol or amino-hexanol or hexylene glycol amino-hexanol mixture face in hydrogen amination and the reaction of ammonia, show excellent active, selectivity and stability, optimize reaction condition, the flexible modulation of hexamethylene diamine product is realized, possibility is provided for industrial production adapts to market fluctuation.The temperature of its operation process conditions, pressure are significantly lower than prior art.Manufacturing condition optimization can reduce the pressure requirements to consersion unit, reduce the one-time investment and production cost of reaction unit, while reducing operation difficulty, improve the security of operating process, reduce pollution.
Specific embodiment
The method of the present invention is described further with reference to embodiment, is not limitation of the invention.Unless otherwise noted, in the application part, percentage and content are by weight.
Embodiment 1：
5%Ni-15%Re-1.2%B/SiO2The preparation and application of catalyst
Weigh 10 grams of carrier S iO2(20-40 mesh), by carrier S iO2Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 10% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 2.477 grams of Ni (NO3)2·6H2O, 2.161 grams of NH4ReO4With 0.686 gram of H3BO3It is dissolved in 12ml deionized waters.The SiO that above-mentioned ammoniated treatment is crossed is impregnated with the half of this aqueous solution2Carrier, dries naturally, subsequent 120 DEG C of dryings 4 hours, and then 500 DEG C are calcined 4 hours.Then, with above-mentioned remaining another semi-aqueous the SiO that above-mentioned ammoniated treatment is crossed is impregnated for the second time2Carrier, then dries naturally, 120 DEG C of dryings 4 hours, and 500 DEG C are calcined 4 hours.Catalyst uses preceding, (normal pressure, 2000h in 375 DEG C of hydrogen streams-1) reduce 4 hours.When reactor temperature Temperature fall is to 160 DEG C, 8MPa is boosted to, after system stabilization, by NH3The liquid of/1,6- hexylene glycol=5 (mol ratio) flows through pump and squeezes into reactor, and the liquid air speed for adjusting 1,6- hexylene glycols is 0.5h-1, H2/NH3/ 1,6-HD=0.25:5:1 (mol ratio), is reacted, 50 hours reaction time, sampling analysis.SE-30 capillary chromatographic columns, fid detector, isobutanol carries out quantitative analysis for internal standard, and reaction result is shown in Table 1.
Embodiment 2：
15%Ni-3.6%Re-1.2%B/SiO2The preparation and application of catalyst
Weigh 10 grams of carrier S iO2(20-40 mesh), by carrier S iO2Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 7.432 grams of Ni (NO3)2·6H2O, 0.518 gram of NH4ReO4With 0.686 gram of H3BO3It is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 3：
30%Ni-0.2%Re-15%K/SiO2The preparation and application of catalyst
Weigh 10 grams of carrier S iO2(20-40 mesh), by carrier S iO2Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 50% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 14.864 grams of Ni (NO3)2·6H2O, 0.029 gram of NH4ReO4With 3.879 grams of KNO3It is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 4：
15%Ni-3.6%Cu-1.2%B/SiO2The preparation and application of catalyst
Weigh 10 grams of carrier S iO2(20-40 mesh), by carrier S iO2Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 7.432 grams of Ni (NO3)2·6H2O, 1.369 grams of Cu (NO3)2·3H2O and 0.686 gram of H3BO3It is dissolved in 12ml deionized waters.Reaction raw materials are 6- amino -1- hexanols, NH3/ 6- amino -1- hexanol=10 (mol ratio).Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 5：
15%Co-3.6%Re-1.2%B/SiO2The preparation and application of catalyst
Weigh 10 grams of carrier S iO2(20-40 mesh), by carrier S iO2Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 7.408 grams of Co (NO3)2·H2O, 0.518 gram of NH4ReO4With 0.686 gram of H3BO3It is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 6：
5%Ni-8%Re-1.2%B/Al2O3The preparation and application of catalyst
Weigh 10 grams of carrier Al2O3(20-40 mesh), by carrier Al2O3Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 10% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 2.477 grams of NiCl2·6H2O, 1.152 grams of NH4ReO4With 0.686 gram of H3BO3It is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 7：
15%Ni-2%Re-1.2%B/Al2O3The preparation and application of catalyst
Weigh 10 grams of carrier Al2O3(20-40 mesh), by carrier Al2O3Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 7.432 grams of Ni (NO3)2·6H2O, 0.288 gram of NH4ReO4With 0.686 gram of H3BO3It is dissolved in 12ml deionized waters.Reaction raw materials are 1,6- hexylene glycols and 6- amino -1- hexanol mixtures (1：1 mol ratio), NH3Hydroxyl=10 (mol ratio) in/1,6- hexylene glycol and 6- amino -1- hexanol mixtures.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 8：
30%Ni-2%Re-1.2%B/Al2O3The preparation and application of catalyst
Weigh 10 grams of carrier Al2O3(20-40 mesh), by carrier Al2O3Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 50% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 12.712 grams of Ni (CH3COO)2·6H2O, 0.288 gram of NH4ReO4With 0.686 gram of H3BO3It is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 9：
15%Ni-0.2%Re-10%Zn/Al2O3The preparation and application of catalyst
Weigh 10 grams of carrier Al2O3(20-40 mesh), by carrier Al2O3Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas, and ammonification temperature is 200 DEG C, 5 hours ammonification time.By 6.356 grams of Ni (CH3COO)2·6H2O, 0.029 gram of NH4ReO4With 4.549 grams of Zn (NO3)2·6H2O is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 10：
15%Ni-3.6%Re-0.2%Zn/Al2O3The preparation and application of catalyst
Weigh 10 grams of carrier Al2O3(20-40 mesh), by carrier Al2O3Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 7.432 grams of Ni (NO3)2·6H2O, 0.518 gram of NH4ReO4With 0.091 gram of Zn (NO3)2·6H2O is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 11：
30%Ni-2%Re/Al2O3The preparation and application of catalyst
Weigh 10 grams of carrier Al2O3(20-40 mesh), by carrier Al2O3Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 50% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 14.864 grams of Ni (NO3)2·6H2O and 0.288 gram of NH4ReO4It is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 12：
15%Ni-2%Re-12%B/Al2O3The preparation and application of catalyst
Weigh 10 grams of carrier Al2O3(20-40 mesh), by carrier Al2O3Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 7.432 grams of Ni (NO3)2·6H2O, 0.288 gram of NH4ReO4With 6.86 grams of H3BO3It is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 13：
5%Co-15%Cu-1.2%K/Al2O3The preparation and application of catalyst
Weigh 10 grams of carrier Al2O3(20-40 mesh), by carrier Al2O3Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 10% ammonia-hydrogen mixed gas, and ammonification temperature is 200 DEG C, 5 hours ammonification time.By 2.469 grams of Co (NO3)2·H2O, 5.703 grams of Cu (NO3)2·3H2O and 0.310 gram of KNO3It is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 14：
15%Co-3.6%Re-1.2%B/Al2O3The preparation and application of catalyst
Weigh 10 grams of carrier Al2O3(20-40 mesh), by carrier Al2O3Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 7.408 grams of Co (NO3)2·H2O, 0.518 gram of NH4ReO4With 0.686 gram of H3BO3It is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 15：
30%Co-2%Re-1.2%B/Al2O3The preparation and application of catalyst
Weigh 10 grams of carrier Al2O3(20-40 mesh), by carrier Al2O3Loaded in quartz ampoule, under inert atmosphere, then 200 DEG C of dryings 5 hours introduce 50% ammonia-hydrogen mixed gas, and ammonification temperature is 300 DEG C, 5 hours ammonification time.By 14.816 grams of Co (NO3)2·H2O, 0.288 gram of NH4ReO4With 0.686 gram of H3BO3It is dissolved in 12ml deionized waters.Remaining preparation process and evaluating catalyst scheme are referring to embodiment 1.Reaction result is shown in Table 1.
Embodiment 16：
The stability test of catalyst, by the catalyst of the method for preparing catalyst preparation in embodiment 7 in fixed bed reactors, reaction condition：Temperature is 160 DEG C, and pressure is 8MPa, and the liquid air speed of 1,6- hexylene glycol is 0.5h-1, H2/NH3/ 1,6-HD=0.25:5:1 (mol ratio), is reacted, every 24 hours sampling analyses of reaction.SE-30 capillary chromatographic columns, fid detector, isobutanol carries out quantitative analysis for internal standard, and the reaction result of 1000 hours shows that the activity and selectivity of catalyst is essentially identical.
Comparative example 1：
15%Ni-3.6%Re-1.2%B/SiO of the carrier without ammoniated treatment2The preparation and application of catalyst
Weigh 10 grams of carrier S iO2(20-40 mesh), by carrier S iO2Loaded in quartz ampoule, under inert atmosphere, 200 DEG C of dryings 5 hours.By 7.432 grams of Ni (NO3)2·6H2O, 0.518 gram of NH4ReO4With 0.686 gram of H3BO3It is dissolved in 12ml deionized waters.Above-mentioned SiO is impregnated with the half of this aqueous solution2Carrier, dries naturally, subsequent 120 DEG C of dryings 4 hours, and then 500 DEG C are calcined 4 hours.Then, with above-mentioned remaining another semi-aqueous the above-mentioned SiO for being loaded with metal is impregnated for the second time2Carrier, then dries naturally, 120 DEG C of dryings 4 hours, and 500 DEG C are calcined 4 hours.Evaluating catalyst scheme is referring to embodiment 1.
Comparative example 2：
15%Co-3.6%Re-1.2%B/Al of the carrier without ammoniated treatment2O3The preparation and application of catalyst.
Weigh 10 grams of carrier Al2O3(20-40 mesh), by carrier Al2O3Loaded in quartz ampoule, under inert atmosphere, 200 DEG C of dryings 5 hours.By 7.408 grams of Co (NO3)2·H2O, 0.518 gram of NH4ReO4With 0.686 gram of H3BO3It is dissolved in 12ml deionized waters.Above-mentioned Al is impregnated with the half of this aqueous solution2O3Carrier, dries naturally, subsequent 120 DEG C of dryings 4 hours, and then 500 DEG C are calcined 4 hours.Then, with above-mentioned remaining another semi-aqueous the above-mentioned Al for being loaded with metal is impregnated for the second time2O3Carrier, then dries naturally, 120 DEG C of dryings 4 hours, and 500 DEG C are calcined 4 hours.Referring to embodiment 1, reaction result is shown in Table 1 to evaluating catalyst scheme.
Embodiment 2 is identical with the catalytic component of reference examples 1, the difference is that the carrier of embodiment 2 is by ammoniated treatment, the carrier of reference examples 1 is not by ammoniated treatment, comparative result, it is seen that, the conversion ratio of 1,6- hexylene glycol improves 10.22 percentage points, the selectivity of 1,6- hexamethylene diamine improves 9.59 percentage points.
Embodiment 14 is identical with the catalytic component of reference examples 2, the difference is that the carrier of embodiment 14 passes through Ammoniated treatment, the carrier of reference examples 2 not by ammoniated treatment, comparative result, it is seen that, the conversion ratio of 1,6- hexylene glycol improves 13.26 percentage points, and the selectivity of 1,6- hexamethylene diamine improves 12.05 percentage points.
Comparative analysis result above synthesis can be assumed that, catalyst carrier using after ammoniated treatment, can in the catalyst and prepare realize in the method for hexamethylene diamine below in one or more：(1) realized under relatively low reaction pressure, (2) modulation reaction condition can flexible modulation ethyleneamines composition, (3) process units one-time investment and production cost are reduced, (4) realize easy to operate, (5) activity of catalyst is improved, (6) selectivity to product is improved, (7) conversion ratio of raw material is provided, (8) improve the stability of method and (9) improve the security of hexamethylene diamine production process.
Under the hydro condition of the embodiment of table 1 hexylene glycol or amino-hexanol or hexylene glycol amino-hexanol mixture aminating reaction data
。

Claims (6)

1. a kind of catalyst for synthesizing hexamethylene diamine, the catalyst is by main active component, auxiliary agent and ammonia Change the treated part of carrier three composition, wherein the main active component is selected from the group being made up of Ni and Co One kind or two kinds, the auxiliary agent is selected from by Fe, Cu, Ru, Re, K, Zn and B and their own Oxide composition group in one or two or more kinds；The carrier that the ammoniated treatment is crossed is by selected from SiO2With Al2O3In one kind or two kinds of carriers obtained by ammoniated treatment, the ammoniated treatment includes：By carrier with Ammonia source contacts 0.5 to 15 hour in 150 to 400 DEG C of temperature；
Main active component accounts for 1~40% in the gross weight of the catalyst；
The auxiliary agent accounts for 0.1~20% in the gross weight of the catalyst.
2. according to the catalyst described in claim 1, wherein the specific surface area of the carrier is 150~350m2/ g, And average pore size is 8-80nm.
3. according to the catalyst described in claim 1, wherein the ammonia source is selected from by ammonia, liquefied ammonia, ammoniacal liquor With one or two or more kinds in the group of urea composition.
4. according to the catalyst described in claim 1, wherein the main active component is in the total of the catalyst 5~30% are accounted in weight.
5. according to the catalyst described in claim 1, wherein the auxiliary agent is in the gross weight of the catalyst Account for 0.1~15%.
6. a kind of application of any catalyst of claim 1-5, the catalyst is used for hexylene glycol or ammonia The method that one kind or two kinds of mixture and ammonia in base hexanol prepare hexamethylene diamine, described in claim 1 In the presence of catalyst, under hydro condition by the one kind in hexylene glycol or amino-hexanol or two kinds of mixture and Ammonia is converted into hexamethylene diamine.
CN201510846359.5A 2015-11-27 2015-11-27 A kind of catalyst for synthesizing hexamethylene diamine Pending CN106807377A (en)

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CN111196763A (en) * 2018-11-16 2020-05-26 中国科学院大连化学物理研究所 Catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile and preparation method thereof
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CN113713853A (en) * 2021-09-16 2021-11-30 中触媒新材料股份有限公司 Method for preparing aliphatic diamine from cyclic imine and catalyst used in method
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
CN114433087A (en) * 2020-10-30 2022-05-06 中国石油化工股份有限公司 Catalyst and carrier with function of preparing amine by alcohol hydroamination, and preparation method and application thereof
CN114433113A (en) * 2020-10-30 2022-05-06 中国石油化工股份有限公司 Catalyst and carrier with alcohol catalytic ammoniation function, and preparation method and application thereof
CN114433121A (en) * 2020-10-30 2022-05-06 中国石油化工股份有限公司 Catalyst and carrier with function of preparing amine by catalytic ammoniation and preparation method and application thereof
CN114539069A (en) * 2020-11-24 2022-05-27 中国科学院大连化学物理研究所 Method for preparing 1, 5-pentanediamine by taking 1, 5-glutaric acid as raw material
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CN111196763B (en) * 2018-11-16 2021-06-01 中国科学院大连化学物理研究所 Catalyst for producing 3-aminopropanol by hydrogenating 3-hydroxypropionitrile and preparation method thereof
CN111151256A (en) * 2020-01-20 2020-05-15 山东玉皇化工有限公司 Catalyst for synthesizing hexamethylene diamine
CN111151256B (en) * 2020-01-20 2023-03-24 山东玉皇化工有限公司 Catalyst for synthesizing hexamethylene diamine
CN113262797B (en) * 2020-02-17 2022-12-27 上海迅凯新材料科技有限公司 Nickel-based catalyst, preparation method and application of nickel-based catalyst in vanillin hydrogenation synthesis of vanillyl alcohol
CN113262797A (en) * 2020-02-17 2021-08-17 上海迅凯新材料科技有限公司 Nickel-based catalyst, preparation method and application of nickel-based catalyst in vanillin hydrogenation synthesis of vanillyl alcohol
CN114425347B (en) * 2020-10-29 2023-08-08 中国石油化工股份有限公司 Process for synthesizing cyclohexylimine
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
CN114433113A (en) * 2020-10-30 2022-05-06 中国石油化工股份有限公司 Catalyst and carrier with alcohol catalytic ammoniation function, and preparation method and application thereof
CN114433121A (en) * 2020-10-30 2022-05-06 中国石油化工股份有限公司 Catalyst and carrier with function of preparing amine by catalytic ammoniation and preparation method and application thereof
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CN114539069B (en) * 2020-11-24 2023-05-16 中国科学院大连化学物理研究所 Method for preparing 1, 5-pentanediamine by taking 1, 5-pentanedioic acid as raw material
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CN113713853A (en) * 2021-09-16 2021-11-30 中触媒新材料股份有限公司 Method for preparing aliphatic diamine from cyclic imine and catalyst used in method
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Application publication date: 20170609