CN107899587A - A kind of catalyst for fatty alcohol amination amine and preparation method thereof - Google Patents

A kind of catalyst for fatty alcohol amination amine and preparation method thereof Download PDF

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Publication number
CN107899587A
CN107899587A CN201711169632.0A CN201711169632A CN107899587A CN 107899587 A CN107899587 A CN 107899587A CN 201711169632 A CN201711169632 A CN 201711169632A CN 107899587 A CN107899587 A CN 107899587A
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catalyst
preparation
active component
carrier
presoma
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CN107899587B (en
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杜宝磊
李雪
付志凯
侯红霞
王建伟
王胜伟
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Shandong Yuhuang Chemical Co Ltd
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Shandong Yuhuang Chemical Co Ltd
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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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • 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
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    • B01J23/8896—Rhenium
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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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble 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
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal 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
    • 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
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8986—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with manganese, technetium or 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
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Abstract

The present invention provides a kind of catalyst for fatty alcohol amination amine and preparation method thereof, belong to chemical field, catalyst includes carrier, auxiliary agent and active component, and active component includes at least one of Ni, Co and Cu, and active component accounts for 5~50wt% of the gross weight of catalyst；Auxiliary agent includes at least one of K, Na, Pd, Pt, Re, Ru, Cr and B, and auxiliary agent accounts for 1~10wt% of the gross weight of catalyst；The preparation method of the catalyst includes：Using drying after steam treatment carrier and carry out first time roasting；And impregnation.The conversion ratio and selectivity of this catalyst stability and catalysis are higher, available in the preparation of low-grade aliphatic amine.

Description

A kind of catalyst for fatty alcohol amination amine and preparation method thereof
Technical field
The present invention relates to chemical field, in particular to a kind of catalyst and its system for fatty alcohol amination amine Preparation Method.
Background technology
Organic amine refers to that what the hydrogen on ammonia formed after being substituted by organic group has amino (- NH2,-NHR and-NR2) feature A kind of material of functional group, belongs to the derivative of ammonia.Organic amine can simply be divided into fatty amine and aromatic amine.Fatty amine includes low Level fatty amine and high fatty amine, low-grade aliphatic amine refer mainly to the organic amine compound of C1-C6.The purposes of amine is quite varied, Available for the production of medicine, pesticide, rubber, surfactant, crosslinking agent, curing agent, occupy an important position in the industry.
Organic amine can be produced by a variety of methods, and such as the preparation of alkyl halide ammonolysis, alcohol reduction amination prepares and nitro reduction system It is standby etc..Prepared by the ammonolysis of alkyl halide, cost of material is cheap, technical maturity, but produces substantial amounts of halogen waste water, seriously corroded, At present under the overall background of environmental protection, development prospect is unknown.The reduction of nitro prepares the preparation that organic amine is mainly used for aromatic amine, low The production of level fatty amine very uses less.With the fast development of petrochemical industry and coal chemical industry, the source of alcohol is more and more extensive, example Such as, existing fischer-tropsch reaction can produce the alcohols that carbon number is more than 2.Comprehensive production cost and technique, the reduction amine of alcohol It is current most widely used method that change, which prepares organic amine, and the key of the technique industrialization is the need for suitable catalyst.So And the selectivity and conversion ratio of the catalyst of existing fatty alcohol reduction amination are relatively low, it is difficult to meet industrialized production Need.
The content of the invention
The first object of the present invention is to provide a kind of preparation method of the catalyst for fatty alcohol amination amine, the party Method pre-processes carrier using water vapour, can change aperture and the acidity of carrier, improves turning for obtained catalyst Rate, selectivity and stability.
The second object of the present invention is to provide a kind of catalyst for fatty alcohol amination amine, this catalyst stabilization Property and catalysis conversion ratio and selectivity it is higher, available in the preparation of low-grade aliphatic amine.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
A kind of preparation method of catalyst for fatty alcohol amination amine, it includes carrier, auxiliary agent and active component, living Property component include at least one of Ni, Co and Cu, and active component accounts for 5~50wt% of the gross weight of catalyst；Auxiliary agent bag At least one of K, Na, Pd, Pt, Re, Ru, Cr and B are included, and auxiliary agent accounts for 1~10wt% of the gross weight of catalyst；
The preparation method of catalyst includes：
Using drying after steam treatment carrier and carry out first time roasting；And
Carrier after processing and maceration extract are mixed with dipping, obtain catalyst precarsor, wherein, auxiliary agent is dissolved with maceration extract Presoma, active component presoma and ethylenediamine；Dried catalyst precarsor is carried out second again to roast.
A kind of catalyst for fatty alcohol amination amine as obtained by above-mentioned preparation method.
Compared with prior art, beneficial effect in the present disclosure for example including：
The preparation method of this catalyst provided by the invention, pre-processes carrier using water vapour, can change load Average pore size, specific surface area and the acidity of body, can further improve the conversion ratio and stability of obtained catalyst. Meanwhile carrier is handled using the maceration extract containing auxiliary agent presoma, active component presoma and ethylenediamine, in supported on carriers Active component and auxiliary agent, by the complexing between ethylenediamine and metal, the acid-base property on control vector surface, improves gained catalyst Selectivity.
As this catalyst obtained by above-mentioned preparation method stability and catalysis conversion ratio and selectivity compared with Height, corresponding alkylamine, alcohol are prepared available in the preparation of low-grade aliphatic amine, such as available for C1~C6 alcohols material aminations Class material includes methanol, ethanol, ethylene glycol, monoethanolamine, butanol, 1,4-butanediol, amylalcohol, pentanediol, hexanol etc., preferred alcohol Amine.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific Condition person, the condition suggested according to normal condition or manufacturer carry out.Reagents or instruments used without specified manufacturer, is The conventional products that can be obtained by commercially available purchase.
Present embodiment provides a kind of catalyst for fatty alcohol amination amine, it includes carrier, auxiliary agent and activearm Point.
Wherein, active component includes at least one of Ni, Co and Cu, active component account for the gross weight of catalyst 5~ 50wt% is either 5~30% or is 15~20%.The active component for example can be：The group of Ni, Co, Cu, Ni and Co Close, Ni and the combination of Cu, the combination of Co and Cu or be Ni, Co and Cu combination.
Wherein, auxiliary agent includes at least one of K, Na, Pd, Pt, Re, Ru, Cr and B, and auxiliary agent accounts for the gross weight of catalyst 1~10wt%, be either 1~6% or be 3~5%.The auxiliary agent for example can be：K, Na, Pd, Pt, Re, Ru, Cr and B In any one, or the combination of Re, Ru and B, or the combination of Pt and K, or the combination of Re and B, either The combination of Ru and B, or the combination of Pd and Ru, or the combination of Re and Cr, or the combination of Re and K.
Wherein, carrier includes aluminium oxide or sieve and silica-sesquioxide, this two classes carrier has loose structure and larger ratio table Area, is conducive to the load of active component and auxiliary agent.
The preparation method of this catalyst includes：
Step S1:Using drying after steam treatment carrier and carry out first time roasting.
Further, included using the method for steam treatment carrier：Carrier is placed in reaction vessel, control reaction is held Device is under 100~900 DEG C (being preferably 500~800 DEG C), 0.1~3MPa (being preferably 0.1~1MPa), by vapor and nitrogen Mixed gas be passed through reaction vessel, handle 10~24h.Further, the content of water vapour is 10-100% in mixed gas, It is either 20~80% to be either 30~60% or be 40~50%.
Using the method for above-mentioned steam treatment carrier, different treatment temperatures and processing time are selected, is aoxidized with sial Exemplified by thing, the surface nature of carrier under the conditions of different disposal is analyzed, as shown in table 1：
The surface nature of carrier under the conditions of 1. different disposal of table
It can see from table 1, compared to the sieve and silica-sesquioxide carrier of before processing, after steam treatment, carrier Specific surface area decreases, and average pore size becomes larger, and pore-size distribution is more concentrated, thus, it is possible to further improve obtained catalysis Conversion ratio, selectivity and the stability of agent.
Further, the specific surface area of the sieve and silica-sesquioxide after steam treatment is 60-300 m2/ g, average pore size are 6-90nm；The specific surface area of aluminium oxide after steam treatment is 50-380m2/ g, average pore size 5-80nm.
By the carrier after steam treatment, it is dried, and is roasted under air or inert atmosphere.Wherein, it is dry Temperature is 80~150 DEG C, drying time is 2~6h；Calcination temperature is 300~800 DEG C, and roasting time is 2~6h.
Step S2:Carrier after processing and maceration extract are mixed with dipping, obtain catalyst precarsor, then by dried catalysis Agent precursor carries out second and roasts.
Carrier after processing is mixed with maceration extract, is stirred in dipping process, and obtained catalyst precarsor is placed in room temperature In dry after, be dried, can use and spontaneously dry, oven drying, vacuum drying, microwave drying or freeze-drying, dry temperature It is 2~6h to spend for 80~150 DEG C, drying time；Then, dried catalyst precarsor is roasted, calcination temperature is 300-800 DEG C, roasting time is 2~6h.If the active component of required load and the amount of auxiliary agent are larger, can repeat The circulation of above-mentioned dipping process, i.e. " dipping-drying-roasting-impregnate again ", until reaching required load capacity.
Wherein, auxiliary agent presoma, active component presoma and ethylenediamine are dissolved with maceration extract.The preparation side of maceration extract Method includes：Auxiliary agent presoma, active component presoma, ethylenediamine are mixed with water or alcohols solvent, and be heated to 40~90 DEG C, it is completely dissolved it.
Further, the presoma of Ni is included in nickel nitrate, nickel chloride, nitric acid conjunction nickel and nickel sulfate extremely in active component Few one kind.The presoma can use anhydrous or hydration alkaline organic metal salt, such as can be Ni (NO3)2·6H2O、 NiCl2·6H2O, ethylenediamine nitric acid closes nickel [Ni (en)3(NO3)2] or Ni (SO4)2·6H2O etc..
Preferably, the presoma of Co is included in cobalt nitrate, cobalt chloride, nitric acid conjunction cobalt and cobaltous sulfate at least in active component It is a kind of.The presoma can use anhydrous or hydration alkaline organic metal salt, such as can be Co (NO3)2·6H2O、C℃l2· 6H2O, ethylenediamine nitric acid closes cobalt [Co (en)3(NO3)2] or Co (SO4)2·6H2O etc..
Preferably, the presoma of Cu is included in copper nitrate, copper chloride, nitric acid conjunction copper and copper sulphate at least in active component It is a kind of.The presoma can use anhydrous or hydration alkaline organic metal salt, such as can be Cu (NO3)2·3H2O、CuCl2· 2H2O, ethylenediamine nitric acid closes copper [3 (NO3) 2 of Cu (en)] or Co (SO4)2·5H2O etc..
Further, the presoma of Ru includes RuCl in auxiliary agent3, the presoma can with it is anhydrous or hydration it is alkaline organic Metal salt, such as can be RuCl3·3H2O etc..
Preferably, the presoma of Re includes ammonium perrhenate [NH4ReO4] or perrhenic acid [HReO4]。
Preferably, the presoma of B includes boric acid [H3BO3] or boron oxide [B2O3]。
As this catalyst obtained by above-mentioned preparation method stability and catalysis conversion ratio and selectivity compared with Height, for the catalyst before use, needing to be activated catalyst, the temperature of activation is 200-600 DEG C, pressure 0.1-3MPa, Air speed is 100-2500h-1。
The catalyst can be used in the preparation of low-grade aliphatic amine, such as be prepared accordingly available for the amination of C1~C6 alcohols materials Alkylamine, alcohols material include methanol, ethanol, ethylene glycol, monoethanolamine, butanol, 1,4-butanediol, amylalcohol, pentanediol, hexanol Deng preferred alcohol amine.
When the catalyst is faced in the reaction of hydrogen amination generation vinylamine for monoethanolamine, feed ethanol amine is mixed with ammonia Close uniform, after preheating, liquid is driven into by high-pressure pump and is fixed with the reactor of above-mentioned catalyst, reactor can be with For fixed bed or trickle bed, preferably trickle bed.Reaction temperature is 100-170 DEG C, pressure 7-13MPa, ammonia and monoethanolamine rub You are than being 1：20~30, the molar concentration of hydrogen is 1-90%.Reaction result shows, conversion ratio >=40% of monoethanolamine, second two Selectivity >=60% of amine, selectivity >=10% of diethylenetriamine, catalyst keep stablizing in the evaluation time of 600h.
The feature and performance of the present invention are described in further detail with reference to embodiments：
Embodiment 1
The present embodiment provides a kind of catalyst for fatty alcohol amination amine, it is：10%Ni-10%Co-2.5% Re-0.5%Ru-1.5%B；
The preparation method of above-mentioned catalyst is：
Sieve and silica-sesquioxide carrier is placed in reaction vessel, the reaction vessel is controlled under 650 DEG C, 0.5MPa, by water The mixed gas of steam and nitrogen (content of water vapour is 45%) is passed through the reaction vessel, handles 18h, dry after 550 4h is roasted at DEG C, the silica-alumina supports after being handled.
The treated silica-alumina supports of 5g are weighed, by six water nickel nitrates of 2.47g, 2.47g cobalt nitrate hexahydrates, 3.0ml second Diamines and 0.18g ammonium perrhenates, 0.05g ruthenic chlorides, 0.43g boric acid are dissolved in 10ml water, in 50 DEG C of dissolvings, are impregnated Liquid；The half of maceration extract is uniformly added into silica-alumina supports, after room temperature dries, is placed in the dry 4h of 120 DEG C of baking oven, be placed on Muffle 550 DEG C of roasting 4h of stove.Process made above is repeated, until reaching the upper carrying capacity of requirement.
Embodiment 2
The present embodiment provides a kind of catalyst for fatty alcohol amination amine, it is：10%Ni-15%Cu-2.5% Pt-1.5%K；
The preparation method of above-mentioned catalyst is：
Sieve and silica-sesquioxide carrier is placed in reaction vessel, the reaction vessel is controlled under 500 DEG C, 0.1MPa, by water The mixed gas of steam and nitrogen (content of water vapour is 40%) is passed through the reaction vessel, handles 16h, dry after 400 5h is roasted at DEG C, the silica-alumina supports after being handled.
The treated silica-alumina supports of 5g are weighed, by six water nickel nitrates of 2.47g, 2.9g nitrate trihydrate copper, 3.6ml second Diamines and 0.22g platinum chlorides, 0.19g potassium nitrate are dissolved in 10ml water, in 40~90 DEG C of dissolvings, obtain maceration extract；Will dipping The half of liquid is uniformly added into silica-alumina supports, after room temperature dries, is placed in the dry 6h of 80 DEG C of baking oven, be placed on the roasting of 300 DEG C of Muffle furnace Burn 6h.Process made above is repeated, until reaching the upper carrying capacity of requirement.
Embodiment 3
The present embodiment provides a kind of catalyst for fatty alcohol amination amine, it is：10%Co-10%Cu-2.5% Re-1.5%B；
The preparation method of above-mentioned catalyst is：
Sieve and silica-sesquioxide carrier is placed in reaction vessel, controls the reaction vessel to steam water under 800 DEG C, 1MPa The mixed gas of gas and nitrogen (content of water vapour is 50%) is passed through the reaction vessel, handles 20h, dry after 600 DEG C Lower roasting 3h, the silica-alumina supports after being handled.
The treated silica-alumina supports of 5g are weighed, by 2.47g cobalt nitrate hexahydrates, 1.9g nitrate trihydrate copper, 2.9ml second Diamines and 0.18g ammonium perrhenates, 0.43g boric acid are dissolved in 10 ml water, in 40~90 DEG C of dissolvings, obtain maceration extract；Will dipping The half of liquid is uniformly added into silica-alumina supports, after room temperature dries, is placed in the dry 2h of 150 DEG C of baking oven, be placed on 800 DEG C of Muffle furnace Roast 2h.Process made above is repeated, until reaching the upper carrying capacity of requirement.
Embodiment 4
The present embodiment provides a kind of catalyst for fatty alcohol amination amine, it is：5%Ni-10%Co-1.5% Ru-1.2%B；
The preparation method of above-mentioned catalyst is：
Sieve and silica-sesquioxide carrier is placed in reaction vessel, controls the reaction vessel to steam water under 900 DEG C, 3MPa The mixed gas of gas and nitrogen (content of water vapour is 10%) is passed through the reaction vessel, handles 10h, dry after 800 DEG C Lower roasting 2h, the silica-alumina supports after being handled.
The silica-alumina supports after 5g processing are weighed, by six water nickel nitrates of 1.24g, 2.47g cobalt nitrate hexahydrates, 2.3ml ethylenediamines And 0.15g ruthenic chlorides, 0.34g boric acid are dissolved in 10ml water, in 40~90 DEG C of dissolvings, maceration extract is obtained；By the one of maceration extract Semi-homogeneous adds silica-alumina supports, after room temperature dries, is placed in the dry 5h of 100 DEG C of baking oven, 400 DEG C of the Muffle furnace of being placed on roast 5h. Process made above is repeated, until reaching the upper carrying capacity of requirement.
Embodiment 5
The present embodiment provides a kind of catalyst for fatty alcohol amination amine, it is：5%Co-10%Cu-0.5% Pd-0.5%Ru；
The preparation method of above-mentioned catalyst is：
Sieve and silica-sesquioxide carrier is placed in reaction vessel, the reaction vessel is controlled under 100 DEG C, 0.1MPa, by water Steam is passed through the reaction vessel, handles 24h, dry after roasting 6h at 300 DEG C, the silica-alumina supports after being handled.
Weigh the silica-alumina supports after 5g processing, by 1.24g cobalt nitrate hexahydrates, 1.9g nitrate trihydrate copper, 2.2ml ethylenediamines with And 0.042g palladium bichlorides, 0.05g ruthenic chlorides, are dissolved in 10ml water, in 40~90 DEG C of dissolvings, obtain maceration extract；By maceration extract Half is uniformly added into silica-alumina supports, after room temperature dries, is placed in the dry 3h of 130 DEG C of baking oven, be placed on the roasting of 700 DEG C of Muffle furnace 3h.Process made above is repeated, until reaching the upper carrying capacity of requirement.
Embodiment 6
The present embodiment provides a kind of catalyst for fatty alcohol amination amine, it is：5%Ni-10%Cu-0.5% Re-5%Cr；
The preparation method of above-mentioned catalyst is：
Sieve and silica-sesquioxide carrier is placed in reaction vessel, controls the reaction vessel to steam water under 550 DEG C, 2MPa The mixed gas of gas and nitrogen (content of water vapour is 80%) is passed through the reaction vessel, handles 10h, dry after 400 DEG C Lower roasting 4h, the silica-alumina supports after being handled.
Weigh the silica-alumina supports after 5g processing, by 1.24g cobalt nitrate hexahydrates, 1.9g nitrate trihydrate copper, 2.2ml ethylenediamines with And 0.036g ammonium perrhenates, 1.9 9 water chromic nitrates, are dissolved in 10ml water, in 40~90 DEG C of dissolvings, obtain maceration extract；Will dipping The half of liquid is uniformly added into silica-alumina supports, after room temperature dries, is placed in the dry 3h of 110 DEG C of baking oven, be placed on the roasting of 500 DEG C of Muffle furnace Burn 3h.Process made above is repeated, until reaching the upper carrying capacity of requirement.
Embodiment 7
The present embodiment provides a kind of catalyst for fatty alcohol amination amine, it is：15%Ni-5%Cu-1.0% Re-0.5%K；
The preparation method of above-mentioned catalyst is：
Sieve and silica-sesquioxide carrier is placed in reaction vessel, controls the reaction vessel to steam water under 750 DEG C, 3MPa The mixed gas of gas and nitrogen (content of water vapour is 40%) is passed through the reaction vessel, handles 24h, dry after 450 DEG C Lower roasting 5h, the silica-alumina supports after being handled.
The silica-alumina supports after 5g processing are weighed, by 3.72g cobalt nitrate hexahydrates, 0.95g nitrate trihydrate copper, 3.3ml ethylenediamines And 0.072g ammonium perrhenates, 0.065 potassium nitrate, it is dissolved in 10 ml water, in 40~90 DEG C of dissolvings, obtains maceration extract；Will dipping The half of liquid is uniformly added into silica-alumina supports, after room temperature dries, is placed in the dry 4h of 115 DEG C of baking oven, be placed on 400 DEG C of Muffle furnace Roast 4h.Process made above is repeated, until reaching the upper carrying capacity of requirement.
Comparative example 1
This comparative example provides a kind of catalyst for fatty alcohol amination amine, it is：10%Ni-10%Co-2.5% Re-0.5%Ru-1.5%B；
The preparation method of above-mentioned catalyst is：
Silica-alumina supports of the 5g without Steam treatment are weighed, by six water nickel nitrates of 2.47g, 2.47 g cobalt nitrate hexahydrates, 3.0ml ethylenediamines, 0.18g ammonium perrhenates, 0.05g ruthenic chlorides, 0.43 g boric acid are dissolved in 10ml water, are dissolved at 40~90 DEG C, Obtain maceration extract；Other preparation process are the same as embodiment 1.
Comparative example 2
This comparative example provides a kind of catalyst for fatty alcohol amination amine, it is：10%Ni-10%Co-2.5% Re-0.5%Ru-1.5%B；
The preparation method of above-mentioned catalyst is：
Silica-alumina supports are handled using the method for same embodiment 1；The silica-alumina supports of 5g processing are weighed, by six water nitric acid of 2.47g Nickel, 2.47g cobalt nitrate hexahydrates, 0.18g ammonium perrhenates, 0.05g ruthenic chlorides, 0.43g boric acid are dissolved in 10ml water, other were prepared Journey is the same as embodiment 1.
Experimental example
This experimental example is intended to investigate catalytic performance of the catalyst provided by the invention in the reaction of fatty alcohol ammonification amine：
By taking monoethanolamine faces the reaction of hydrogen amination generation vinylamine as an example, reaction process is：
Feed ethanol amine is uniformly mixed with ammonia, after preheating, liquid is driven into by reactor drip by high-pressure pump In bed, the catalyst of the offer of embodiment 1~7 and the catalyst of the offer of comparative example 1 and 2 are respectively fixed with the trickle bed.Instead To answer temperature be 130 DEG C, the molar ratio of pressure 10MPa, ammonia and monoethanolamine is 1：25, the molar concentration of hydrogen is 50%.
Monoethanolamine faces hydrogen amination generation vinylamine, and the reaction is relatively complicated, and final obtained vinylamine is second two Amine, diethylenetriamine, piperazine, the mixture of hydroxyethyl ethylenediamine, the reaction being directed to are shown below.
After reaction, the monoethanolamine conversion ratio of each reaction, and respectively main reaction in the prepared vinylamine of reaction are calculated Selectivity, the selectivity of side reaction product (diethylenetriamine, piperazine, hydroxyethyl ethylenediamine) of product (ethylenediamine), calculate public Formula is as follows, as a result as shown in table 2：
Wherein, monoethanolamine conversion ratio=[(mole of monoethanolamine in unstripped gas)-(mole of monoethanolamine in product)]/ (mole of monoethanolamine in unstripped gas) × 100%
Total carbon mole × 100% in carbon mole/product in selectivity=ethylenediamine of ethylenediamine
Total carbon mole × 100% in carbon mole/product in piperazine selectivity=piperazine
Total carbon mole × 100% in mole/product in diethylenetriamine selectivity=diethylenetriamine
Total carbon mole × 100% in mole/product in hydroxyethyl ethylenediamine selectivity=hydroxyethyl ethylenediamine
2. reaction evaluating result of table
As can be seen from Table 2, ethylenediamine, monoethanolamine are added by the Steam treatment to silica-alumina supports and in maceration extract Conversion ratio have largely raising (reaching as high as 66.8%), the selectivity of ethylenediamine slightly lowers.To embodiment 1 Catalyst carries out estimation of stability, and in 600h, the conversion ratio and selectivity of catalyst are basically unchanged.
Although being illustrated and the invention has been described with specific embodiment, but will be appreciated that without departing substantially from the present invention's Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims Including belonging to all such changes and modifications in the scope of the invention.

Claims (10)

  1. A kind of 1. preparation method of catalyst for fatty alcohol amination amine, it is characterised in that the catalyst include carrier, Auxiliary agent and active component, the active component includes at least one of Ni, Co and Cu, and the active component accounts for the catalysis 5~50wt% of the gross weight of agent；The auxiliary agent includes at least one of K, Na, Pd, Pt, Re, Ru, Cr and B, and described helps Agent accounts for 1~10wt% of the gross weight of the catalyst；
    The preparation method of the catalyst includes：
    Using drying after carrier described in steam treatment and carry out first time roasting；And
    The carrier after processing and maceration extract are mixed with dipping, obtain catalyst precarsor, wherein, it is dissolved with the maceration extract The auxiliary agent presoma, the active component presoma and ethylenediamine；The dried catalyst precarsor is carried out the again After baking.
  2. 2. the preparation method of catalyst according to claim 1, it is characterised in that the carrier includes aluminium oxide or silicon Aluminum oxide.
  3. 3. the preparation method of catalyst according to claim 2, it is characterised in that the oxidation after steam treatment The specific surface area of aluminium is 50-380m2/ g, average pore size 5-80nm.
  4. 4. the preparation method of catalyst according to claim 2, it is characterised in that the sial oxygen after steam treatment The specific surface area of compound is 60-300m2/ g, average pore size 6-90nm.
  5. 5. the preparation method of catalyst according to claim 1, it is characterised in that using carrier described in steam treatment Method includes：Carrier is placed in reaction vessel, controls the reaction vessel to steam water under 100~900 DEG C, 0.1~3MPa The mixed gas of gas and nitrogen is passed through the reaction vessel, handles 10~24h.
  6. 6. the preparation method of catalyst according to claim 5, it is characterised in that water vapour described in the mixed gas Content be 10~100%.
  7. 7. the preparation method of catalyst according to claim 1, it is characterised in that described in the active component before Ni Driving body includes nickel nitrate, nickel chloride, nitric acid conjunction at least one of nickel and nickel sulfate；
    Preferably, the presoma of Co described in the active component is included in cobalt nitrate, cobalt chloride, nitric acid conjunction cobalt and cobaltous sulfate It is at least one；
    Preferably, the presoma of Cu described in the active component is included in copper nitrate, copper chloride, nitric acid conjunction copper and copper sulphate It is at least one.
  8. 8. the preparation method of catalyst according to claim 1, it is characterised in that the presoma of Ru described in the auxiliary agent Including RuCl3；
    Preferably, the presoma of the Re includes ammonium perrhenate or perrhenic acid；
    Preferably, the presoma of the B includes boric acid or boron oxide.
  9. 9. the preparation method of catalyst according to claim 1, it is characterised in that the first time roasting and described second The temperature of secondary roasting is 300~800 DEG C.
  10. A kind of 10. catalysis for fatty alcohol amination amine as obtained by claim 1~9 any one of them preparation method Agent.
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CN109569653A (en) * 2018-12-19 2019-04-05 山东玉皇化工有限公司 It is a kind of for synthesizing the preparation method and application of the catalyst of amine terminated polyether
CN109847758A (en) * 2019-01-15 2019-06-07 宁波工程学院 The n-butanol amination catalysis and catalyst application method of mechanochemical reaction preparation
CN111072486B (en) * 2019-12-19 2023-01-31 浙江建业化工股份有限公司 Method for synthesizing lower aliphatic amine based on ultrasonic deoxygenation ethanol
CN111072486A (en) * 2019-12-19 2020-04-28 浙江建业化工股份有限公司 Method for synthesizing lower aliphatic amine based on ultrasonic deoxygenation ethanol
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
CN112044447A (en) * 2020-08-18 2020-12-08 西安近代化学研究所 Catalyst for synthesizing monoethylamine, preparation method and application
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CN114433086A (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 catalyzing alcohol hydroamination to synthesize organic amine, and preparation method and application thereof
CN114433086B (en) * 2020-10-30 2024-03-29 中国石油化工股份有限公司 Catalyst and carrier with function of catalyzing hydro-ammonification of alcohol to synthesize organic amine, and preparation method and application thereof
CN113698303A (en) * 2021-08-04 2021-11-26 江苏万盛大伟化学有限公司 Production method of fatty tertiary amine
CN113698303B (en) * 2021-08-04 2024-01-30 江苏万盛大伟化学有限公司 Production method of fatty tertiary amine
CN114315613A (en) * 2021-12-27 2022-04-12 江苏康恒化工有限公司 Synthesis process of hydroxyethyl ethylenediamine
CN114315613B (en) * 2021-12-27 2024-03-19 江苏康恒化工有限公司 Synthesis process of hydroxyethyl ethylenediamine
CN114713224A (en) * 2022-04-02 2022-07-08 厦门大学 Catalyst for preparing ethylamine by catalyzing ethanol amination and preparation method and application thereof

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