CN110201671A - A kind of catalyst and its preparation and application preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex - Google Patents

A kind of catalyst and its preparation and application preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex Download PDF

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CN110201671A
CN110201671A CN201910502479.1A CN201910502479A CN110201671A CN 110201671 A CN110201671 A CN 110201671A CN 201910502479 A CN201910502479 A CN 201910502479A CN 110201671 A CN110201671 A CN 110201671A
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catalyst
monoethanolamine
ethyleneamines
liquefied ammonia
complex
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CN110201671B (en
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张吉波
刘保雷
杨家军
李瑞端
于晓波
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Jilin Institute of Chemical Technology
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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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

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Abstract

The invention discloses a kind of catalyst and its preparation and application that monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex, which is characterized in that the catalyst is the loaded catalyst of carrier loaded active component, and wherein carrier is CaO/Al2O3Compound, active component are made of transition metal CuO and NiO；And the quality of NiO accounts for the quality of 2~3%, the CaO that the quality of 15~17%, CuO of the gross weight accounts for gross weight and accounts for the 2.0% of gross weight, remaining as Al2O3.The beneficial effects of the present invention are: consumption of raw materials and production cost can be significantly reduced in catalyst of the invention, cleans production technology more, and catalyst of the invention can react under conditions of milder, and catalyst service performance is reliable；Under hydro condition, the selectivity of ethanol amine reduction amination synthesis of ethylenediamine is effectively increased, the selectivity of ethylenediamine can be made to reach 69%, the conversion ratio of monoethanolamine reaches 68%.

Description

It is a kind of to prepare monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex Catalyst and its preparation and application
Technical field
The invention belongs to chemical catalyst technical fields, and in particular to a kind of to prepare monoethanolamine and liquefied ammonia with ammino-complex The catalyst and its preparation and application of reduction amination synthesis ethyleneamines.
Background technique
Ethyleneamines series of products refer to the acyclic multi-cluster product of ethylenediamine, including line style amine and cyclic amine, line style amine Product includes ethylenediamine, diethylenetriamine, triethylene tetramine etc.；Cyclic amine product includes piperazine, aminoethyl piperazine, ethoxy Piperazine etc..Most important product is ethylenediamine in ethyleneamines series of products, is the well sold and in short supply industrial chemicals in market, medicine, pesticide, It is widely used in terms of emulsifier and epoxy curing agent.Currently, the preparation method of industrial ethylenediamine mainly has two Two kinds of chloroethanes method (EDC) and Girbotal process (MEA), yield is than being about 3:2.The characteristics of dichloroethane law are as follows: cost of material is low Honest and clean and from a wealth of sources, seriously polluted, equipment is easily corroded, and investment cost is high；Girbotal process the characteristics of are as follows: pollution is small, without three Useless discharge, investment cost is low, produces the cyclic amine of high added value, is the new direction of ethyleneamines production.
Reduction amination technique is developed by BASF Corp. of Germany earliest and realizes industrialization, technical process are as follows: monoethanolamine and Ammonia carries out high pressure (being greater than 20.0MPa) reaction, major product is ethylenediamine, co-production two under the action of hydrogen and catalyst Ethylene triamine, piperazine, aminoethyl piperazine, hydroxyethyl piperazine and hydroxyethyl ethylenediamine etc.；The equipment of use are as follows: drop slips bed reaction Device；Catalyst is Ni, Co and Cu etc..
In order to effectively improve reactivity, reduce reaction pressure, the catalyst of reduction amination technique from Ni, Co of early stage, The noble metal components such as Cu develop to the modified components such as Fe, Ce, Ru, Re, including Raney Ni (Co) and modified RaneyNi (Co) catalyst develops into loaded catalyst again later, and carrier is mainly Al2O3、SiO2、TiO2、ZrO2, MgO and sial The porous materials such as hydrochlorate.
Wherein, union carbide corporation, the U.S. uses Ni-Re-B/Al2O3Catalyst, so that reaction condition becomes relatively mild, reaction Pressure is 15.0~18.0MPa, and temperature is 140~160 DEG C.United States Patent (USP) 5,750,790 uses excessive phase Al2O3Load Ni and Re catalyst, so that reactivity improves, the selectivity of ethylenediamine reaches 60% or so.United States Patent (USP) 6,534,441 uses Ni-Re/Al2O3Middle addition active component B, so that the selectivity of ethylenediamine is increased to 70% or more.Chinese patent CN101875014A uses Ni-Re-B/Al2O3Catalyst, so that ethanol amine conversion per pass reaches 50.8%, ethylenediamines It closes object and selectively reaches 71.6%.United States Patent (USP) 45,068,330 using being added to Ir in Ni base catalyst as auxiliary agent, Achieve good effect.
But be both needed to be reacted under the condition of high voltage of 8MPa or more at present in these methods, to overcome this disadvantage, this Invention develops a kind of ethyl alcohol prepared by ammino-complex for being suitble to use under the such relative lower pressure of 1.5~2.0MPa The catalyst of amine and liquefied ammonia reduction amination synthesis ethyleneamines.
Summary of the invention
In order to make up for the deficiencies of the prior art, monoethanolamine and liquefied ammonia are prepared also with ammino-complex the present invention provides a kind of The catalyst and its preparation and application of former amination synthesis ethyleneamines.It, can using catalyst of the invention under hydro condition With the ethyleneamines series of products such as synthesis of ethylenediamine under lower pressure, have that reaction condition is mild, production cost is low, high income etc. Feature.
A kind of catalyst preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex, is carrier loaded The loaded catalyst of active component, wherein aforementioned bearer is γ-Al2O3The CaO/ formed after the conversion of chemically modified and crystal form Al2O3Compound, foregoing active component are made of transition metal CuO and NiO；With CuO, NiO, CaO and Al2O3The sum of weight Be set as gross weight, then the quality of aforementioned NiO accounts for the 15~17% of aforementioned gross weight, the quality of aforementioned CuO account for aforementioned gross weight 2~ 3%, the quality of aforementioned CaO accounts for the 2.0% of aforementioned gross weight, remaining as aforementioned Al2O3Quality.
A kind of preparation method for the catalyst preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex, The following steps are included:
(1) prepared by carrier: by γ-Al2O3Dry 12h, calcium nitrate is dissolved in the water and prepares 4% under the conditions of 120 DEG C Calcium nitrate aqueous solution；By the aforementioned γ-Al after drying2O3It is put into prepared aforementioned 4% calcium nitrate aqueous solution, in 60 Calcium 4h is soaked under the conditions of DEG C；By the γ-Al after leaching calcium2O3It pulls out and drains, the dry 12h under the conditions of 120 DEG C；It is calcined later；It forges It is naturally cooling to room temperature after the completion of burning, obtains CaO/Al2O3Compound, as carrier；
(2) preparation of catalyst: copper carbonate and nickelous carbonate are weighed respectively according to a certain percentage, is put into container, is stirring Under conditions of be slowly added 27% ammonium hydroxide, until aforementioned copper carbonate and nickelous carbonate all dissolve, obtain nickel ammonia and cupric ammine complex Mix saturated solution；Dry aforementioned bearer is put into steeper, is later mixed aforementioned nickel ammonia and cupric ammine complex Saturated solution is poured slowly into aforementioned impregnation container, until liquid level did not had aforementioned bearer, impregnates 4h under the conditions of 40 DEG C, It pulls out, drain immediately, and dry 12h under the conditions of 120 DEG C；Then it is calcined, Temperature fall after calcining obtains Above-mentioned catalytic Agent.
A kind of catalyst for the catalyst preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex Application method, aforementioned catalytic agent before being catalyzed monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines for needing in hydrogen atmosphere Carry out reduction activation, and aforementioned activation condition be 1.5~1.8MPa of pressure, 300~310 DEG C of reduction temperature, recovery time 36h.
As a preferred solution, aforementioned catalytic agent is for being catalyzed monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines When, needing to control the ratio between amount of substance of reaction raw materials monoethanolamine and liquefied ammonia is 1:6~10, and reaction condition is hydrogen partial pressure 1.5~1.8MPa, 200~240 DEG C of reaction temperature, 1.6~2.0MPa of reaction pressure, monoethanolamine operation air speed 0.1~ 0.25h-1。
It is further preferred that when aforementioned catalytic agent is for being catalyzed monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines, it is preceding The conversion ratio of monoethanolamine is stated up to 68%；The selectivity of ethylenediamine is up to 69% in aforementioned ethyleneamines series of products, remaining For ethylene amine derivative, including piperazine, diethylenetriamine etc..
It is further preferred that the calcination process in abovementioned steps (1) is first to be warming up to 200 DEG C with 50 DEG C/h speed, later 960 ± 5 DEG C are warming up to 150 DEG C/h speed, finally keeps 4h under the conditions of 960 ± 5 DEG C.
It is further preferred that aforementioned calcination process in abovementioned steps (2) be warming up to 420 with the speed of 50 DEG C/h~ 450 DEG C, 4h is kept under the conditions of 420~450 DEG C later.
The present invention and prior art, remarkable result are:
1. catalyst of the invention is ambrose alloy ammino-complex due to preparing raw material, the exhaust gas caused by preparation process is rotten Corrosion is small, Yi Huishou ammonia, it is only necessary to which recycling and tail gas clean-up can be completed in water absorption, and the ammonium hydroxide absorbed can be returned further With catalyst is prepared, consumption of raw materials and production cost not only can be significantly reduced, while clean catalysis agent producing process more.
2. catalyst of the invention is compared with the catalyst that other inorganic salts such as nitrate impregnate, active metal particles distribution More uniform, particle diameter is small, easily restores, and catalytic activity is higher, the reaction pressure relatively low suitable for 1.5~3.0MPa, And the conversion ratio and selectivity effectively improved, application field of the invention is expanded, can be widely applied to current ethamine, different The product structure reformation of other organic amine process units such as propylamine, morpholine.
3. catalyst of the invention shields the acidity of catalyst carrier formation due to carrying out chemical modification using calcium oxide Center effectively reduces the generation of condensation by-product, improves the conversion ratio of ethanol amine, the selectivity of ethylenediamine and total selection Property.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in the embodiment of the present invention Technical solution is clearly and completely described, it is clear that described embodiments are some of the embodiments of the present invention, rather than complete The embodiment in portion.Based on the embodiments of the present invention, those of ordinary skill in the art are without creative efforts Every other embodiment obtained, shall fall within the protection scope of the present invention.
Embodiment 1
A kind of preparation method for the catalyst preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex, The following steps are included:
(1) prepared by carrier: by γ-Al2O3Dry 12h, calcium nitrate is dissolved in the water and prepares 4% under the conditions of 120 DEG C Calcium nitrate aqueous solution；By the γ-Al after drying2O3It is put into prepared 4% calcium nitrate aqueous solution, under the conditions of 60 DEG C Soak calcium 4h；By the γ-Al after leaching calcium2O3It pulls out and drains, the dry 12h under the conditions of 120 DEG C；It is calcined later, it is specific calcined Cheng Weixian is warming up to 200 DEG C with 50 DEG C/h speed, 960 ± 5 DEG C is warming up to later with 150 DEG C/h speed, finally at 960 ± 5 DEG C Under the conditions of keep 4h；It is naturally cooling to room temperature after the completion of calcining, obtains CaO/Al2O3Compound, as carrier.
(2) preparation of catalyst: nickelous carbonate and copper carbonate are weighed respectively according to 1:0.13 ratio, is put into container, is being stirred It is slowly added 27% ammonium hydroxide under conditions of mixing, until copper carbonate and nickelous carbonate all dissolve, obtains nickel ammonia and cupric ammine complex is mixed Close saturated solution；Dry carrier is put into steeper, is later delayed nickel ammonia and cupric ammine complex mixing saturated solution Slowly it is poured into steeper, until liquid level did not had carrier, 4h is impregnated under the conditions of 40 DEG C, pulls out, drain immediately, and 12h is dried under the conditions of 120 DEG C；Then calcined, calcination process be warming up to 420~450 DEG C with the speed of 50 DEG C/h, and Under the conditions of 420~450 DEG C and keep 4h；Temperature fall after calcining, obtains catalyst.
A kind of obtained catalyst that monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex is load The loaded catalyst of body load active component, wherein carrier is γ-Al2O3It is formed after the conversion of chemically modified and crystal form CaO/Al2O3Compound, active component are made of transition metal CuO and NiO；With CuO, NiO, CaO and Al2O3The sum of weight It is set as gross weight, then the quality for 2.0%, the CaO that the quality that the quality of NiO accounts for 15%, CuO of gross weight accounts for gross weight accounts for gross weight 2.0%, remaining as Al2O3。
Embodiment 2
A kind of preparation method for the catalyst preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex, The following steps are included:
(1) prepared by carrier: by γ-Al2O3Dry 12h, calcium nitrate is dissolved in the water and prepares 4% under the conditions of 120 DEG C Calcium nitrate aqueous solution；By the γ-Al after drying2O3It is put into prepared 4% calcium nitrate aqueous solution, under the conditions of 60 DEG C Soak calcium 4h；By the γ-Al after leaching calcium2O3It pulls out and drains, the dry 12h under the conditions of 120 DEG C；It is calcined later, it is specific calcined Cheng Weixian is warming up to 200 DEG C with 50 DEG C/h speed, 960 ± 5 DEG C is warming up to later with 150 DEG C/h speed, finally at 960 ± 5 DEG C Under the conditions of keep 4h；It is naturally cooling to room temperature after the completion of calcining, obtains CaO/Al2O3Compound, as carrier.
(2) preparation of catalyst: nickelous carbonate and copper carbonate are weighed respectively according to 1:0.14 ratio, is put into container, is being stirred It is slowly added 27% ammonium hydroxide under conditions of mixing, until copper carbonate and nickelous carbonate all dissolve, obtains nickel ammonia and cupric ammine complex is mixed Close saturated solution；Dry carrier is put into steeper, is later delayed nickel ammonia and cupric ammine complex mixing saturated solution Slowly it is poured into steeper, until liquid level did not had carrier, 4h is impregnated under the conditions of 40 DEG C, pulls out, drain immediately, and 12h is dried under the conditions of 120 DEG C；Then calcined, calcination process be warming up to 420~450 DEG C with the speed of 50 DEG C/h, and Under the conditions of 420~450 DEG C and keep 4h；Temperature fall after calcining, obtains catalyst.
A kind of obtained catalyst that monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex is load The loaded catalyst of body load active component, wherein carrier is γ-Al2O3It is formed after the conversion of chemically modified and crystal form CaO/Al2O3Compound, active component are made of transition metal CuO and NiO；With CuO, NiO, CaO and Al2O3The sum of weight It is set as gross weight, then the quality for 2.21%, the CaO that the quality that the quality of NiO accounts for 15.5%, CuO of gross weight accounts for gross weight accounts for gross weight 2.0%, remaining as Al2O3。
Embodiment 3
A kind of preparation method for the catalyst preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex, The following steps are included:
(1) prepared by carrier: by γ-Al2O3Dry 12h, calcium nitrate is dissolved in the water and prepares 4% under the conditions of 120 DEG C Calcium nitrate aqueous solution；By the γ-Al after drying2O3It is put into prepared 4% calcium nitrate aqueous solution, under the conditions of 60 DEG C Soak calcium 4h；By the γ-Al after leaching calcium2O3It pulls out and drains, the dry 12h under the conditions of 120 DEG C；It is calcined later, it is specific calcined Cheng Weixian is warming up to 200 DEG C with 50 DEG C/h speed, 960 ± 5 DEG C is warming up to later with 150 DEG C/h speed, finally at 960 ± 5 DEG C Under the conditions of keep 4h；It is naturally cooling to room temperature after the completion of calcining, obtains CaO/Al2O3Compound, as carrier.
(2) preparation of catalyst: nickelous carbonate and copper carbonate are weighed respectively according to 1:0.15 ratio, is put into container, is being stirred It is slowly added 27% ammonium hydroxide under conditions of mixing, until copper carbonate and nickelous carbonate all dissolve, obtains nickel ammonia and cupric ammine complex is mixed Close saturated solution；Dry carrier is put into steeper, is later delayed nickel ammonia and cupric ammine complex mixing saturated solution Slowly it is poured into steeper, until liquid level did not had carrier, 4h is impregnated under the conditions of 40 DEG C, pulls out, drain immediately, and 12h is dried under the conditions of 120 DEG C；Then calcined, calcination process be warming up to 420~450 DEG C with the speed of 50 DEG C/h, and Under the conditions of 420~450 DEG C and keep 4h；Temperature fall after calcining, obtains catalyst.
A kind of obtained catalyst that monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex is load The loaded catalyst of body load active component, wherein carrier is γ-Al2O3It is formed after the conversion of chemically modified and crystal form CaO/Al2O3Compound, active component are made of transition metal CuO and NiO；With CuO, NiO, CaO and Al2O3The sum of weight It is set as gross weight, then the quality for 2.47%, the CaO that the quality that the quality of NiO accounts for 16%, CuO of gross weight accounts for gross weight accounts for gross weight 2.0%, remaining as Al2O3。
Embodiment 4
A kind of preparation method for the catalyst preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex, The following steps are included:
(1) prepared by carrier: by γ-Al2O3Dry 12h, calcium nitrate is dissolved in the water and prepares 4% under the conditions of 120 DEG C Calcium nitrate aqueous solution；By the γ-Al after drying2O3It is put into prepared 4% calcium nitrate aqueous solution, under the conditions of 60 DEG C Soak calcium 4h；By the γ-Al after leaching calcium2O3It pulls out and drains, the dry 12h under the conditions of 120 DEG C；It is calcined later, it is specific calcined Cheng Weixian is warming up to 200 DEG C with 50 DEG C/h speed, 960 ± 5 DEG C is warming up to later with 150 DEG C/h speed, finally at 960 ± 5 DEG C Under the conditions of keep 4h；It is naturally cooling to room temperature after the completion of calcining, obtains CaO/Al2O3Compound, as carrier.
(2) preparation of catalyst: nickelous carbonate and copper carbonate are weighed respectively according to 1:0.16 ratio, is put into container, is being stirred It is slowly added 27% ammonium hydroxide under conditions of mixing, until copper carbonate and nickelous carbonate all dissolve, obtains nickel ammonia and cupric ammine complex is mixed Close saturated solution；Dry carrier is put into steeper, is later delayed nickel ammonia and cupric ammine complex mixing saturated solution Slowly it is poured into steeper, until liquid level did not had carrier, 4h is impregnated under the conditions of 40 DEG C, pulls out, drain immediately, and 12h is dried under the conditions of 120 DEG C；Then calcined, calcination process be warming up to 420~450 DEG C with the speed of 50 DEG C/h, and Under the conditions of 420~450 DEG C and keep 4h；Temperature fall after calcining, obtains catalyst.
A kind of obtained catalyst that monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex is load The loaded catalyst of body load active component, wherein carrier is γ-Al2O3It is formed after the conversion of chemically modified and crystal form CaO/Al2O3Compound, active component are made of transition metal CuO and NiO；With CuO, NiO, CaO and Al2O3The sum of weight It is set as gross weight, then the quality for 2.75%, the CaO that the quality that the quality of NiO accounts for 16.5%, CuO of gross weight accounts for gross weight accounts for gross weight 2.0%, remaining as Al2O3。
Embodiment 5
A kind of preparation method for the catalyst preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex, The following steps are included:
(1) prepared by carrier: by γ-Al2O3Dry 12h, calcium nitrate is dissolved in the water and prepares 4% under the conditions of 120 DEG C Calcium nitrate aqueous solution；By the γ-Al after drying2O3It is put into prepared 4% calcium nitrate aqueous solution, under the conditions of 60 DEG C Soak calcium 4h；By the γ-Al after leaching calcium2O3It pulls out and drains, the dry 12h under the conditions of 120 DEG C；It is calcined later, it is specific calcined Cheng Weixian is warming up to 200 DEG C with 50 DEG C/h speed, 960 ± 5 DEG C is warming up to later with 150 DEG C/h speed, finally at 960 ± 5 DEG C Under the conditions of keep 4h；It is naturally cooling to room temperature after the completion of calcining, obtains CaO/Al2O3Compound, as carrier.
(2) preparation of catalyst: nickelous carbonate and copper carbonate are weighed respectively according to 1:0.17 ratio, is put into container, is being stirred It is slowly added 27% ammonium hydroxide under conditions of mixing, until copper carbonate and nickelous carbonate all dissolve, obtains nickel ammonia and cupric ammine complex is mixed Close saturated solution；Dry carrier is put into steeper, is later delayed nickel ammonia and cupric ammine complex mixing saturated solution Slowly it is poured into steeper, until liquid level did not had carrier, 4h is impregnated under the conditions of 40 DEG C, pulls out, drain immediately, and 12h is dried under the conditions of 120 DEG C；Then calcined, calcination process be warming up to 420~450 DEG C with the speed of 50 DEG C/h, and Under the conditions of 420~450 DEG C and keep 4h；Temperature fall after calcining, obtains catalyst.
A kind of obtained catalyst that monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex is load The loaded catalyst of body load active component, wherein carrier is γ-Al2O3It is formed after the conversion of chemically modified and crystal form CaO/Al2O3Compound, active component are made of transition metal CuO and NiO；With CuO, NiO, CaO and Al2O3The sum of weight It is set as gross weight, then the quality for 3.0%, the CaO that the quality that the quality of NiO accounts for 17%, CuO of gross weight accounts for gross weight accounts for gross weight 2.0%, remaining as Al2O3。
Comparative example 1
Nickelous carbonate and copper carbonate are weighed respectively according to 1:0.17 ratio, are put into container, are slowly added under stirring conditions Add 27% ammonium hydroxide, until copper carbonate and nickelous carbonate all dissolve, obtains nickel ammonia and cupric ammine complex mixing saturated solution；It will dry Carrier be put into steeper, nickel ammonia and cupric ammine complex mixing saturated solution are poured slowly into steeper later It is interior, until liquid level did not had carrier, 4h is impregnated under the conditions of 40 DEG C, pulls out, drain immediately, and is dried under the conditions of 120 DEG C 12h；Then it is calcined, calcination process is with the speed of 50 DEG C/h to be warming up to 420~450 DEG C, and in 420~450 DEG C of conditions It descends and keeps 4h；Temperature fall after calcining, obtains catalyst.Active component is made of transition metal CuO and NiO；With CuO, The sum of the weight of NiO and Al2O3 is set as gross weight, then the quality that the quality of NiO accounts for 17%, CuO of gross weight accounts for gross weight 3.0%, remaining as Al2O3.
Performance evaluation is carried out to embodiment 1-5 and comparative example 1 catalyst prepared: using single tube fixed bed reactors Carry out a kind of reaction of catalyst that monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex.It is first before reaction Catalyst first carries out to reduction activation in hydrogen atmosphere, and activation condition is 1.5~1.8MPa of pressure, reduction temperature 300~ 310 DEG C, recovery time 36h；Liquid material monoethanolamine will be mixed with liquefied ammonia by the ratio between the amount of substance 1:8, and pumped later Enter into preheater, enters in single tube fixed bed reactors after being preheated to 200 DEG C with hydrogen and reacted, loaded catalyst is 10mL, and control reaction condition in reaction process and operate air speed for pressure 1.8MPa, 220 DEG C of reaction temperature, monoethanolamine 0.15h-1, reaction time 168h.
Reaction product is analyzed with gas-chromatography after reaction, is packed column, FID detection with polyethylene glycol 20,000 Device, dimethylformamide (DMFA) are that internal standard carries out quantitative analysis detection.Testing result is shown in Table 1.
1 evaluating catalyst result of table
With comparative example 1, catalyst of the invention has due to having carried out chemical modification and physical modification, catalytic activity Apparent to improve, MEA conversion ratio is increased to 68% by 55%, and the selectivity of ethylenediamine is also increased to 69% by 36%.Total selection Property by 74% be increased to 97%, and as the raising ring-type ethyleneamines and polyethylene polyamine of copper content selectivity are with raising, and The selectivity of ethylenediamine declines therewith.
It should be appreciated that described above, the specific embodiments are only for explaining the present invention, is not intended to limit the present invention.By The obvious changes or variations that spirit of the invention is extended out are still in the protection scope of this invention.

Claims (7)

1. a kind of catalyst for preparing monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines with ammino-complex, which is characterized in that The catalyst is the loaded catalyst of carrier loaded active component, wherein the carrier is γ-Al2O3It is chemically modified and The CaO/Al formed after crystal form conversion2O3Compound, the active component are made of transition metal CuO and NiO；With CuO, NiO, CaO and Al2O3The sum of weight be set as gross weight, then the quality of the NiO accounts for the 15~17% of the gross weight, the matter of the CuO Amount accounts for the 2~3% of the gross weight, and the quality of the CaO accounts for the 2.0% of the gross weight, remaining as Al2O3Quality.
2. according to claim 1 a kind of monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex The preparation method of catalyst, which comprises the following steps:
(1) prepared by carrier: by γ-Al2O3The dry 12h under the conditions of 120 DEG C, calcium nitrate is dissolved in the water prepare 4% nitric acid Calcium aqueous solution；By the γ-Al after drying2O3It is put into prepared described 4% calcium nitrate aqueous solution, in 60 DEG C of items Calcium 4h is soaked under part；By the γ-Al after leaching calcium2O3It pulls out and drains, the dry 12h under the conditions of 120 DEG C；It is calcined later；It has calcined It is naturally cooling to room temperature after, obtains CaO/Al2O3Compound, as carrier；
(2) preparation of catalyst: copper carbonate and nickelous carbonate are weighed respectively according to a certain percentage, is put into container, in the item of stirring It is slowly added 27% ammonium hydroxide under part, until the copper carbonate and nickelous carbonate all dissolve, obtains nickel ammonia and cupric ammine complex mixing Saturated solution；The dry carrier is put into steeper, the nickel ammonia and cupric ammine complex are mixed into saturation later Solution is poured slowly into the steeper, until liquid level did not had the carrier, 4h is impregnated under the conditions of 40 DEG C, immediately It pulls out, drain, and dry 12h under the conditions of 120 DEG C；Then it is calcined, Temperature fall after calcining obtains the catalyst.
3. according to claim 1 a kind of monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex The application method of catalyst, which is characterized in that the catalyst is for being catalyzed monoethanolamine and liquefied ammonia reduction amination synthesis ethylene Need to carry out reduction activation before amine in hydrogen atmosphere, and the activation condition is 1.5~1.8MPa of pressure, reduction temperature 300 ~310 DEG C, recovery time 36h.
4. according to claim 3 a kind of monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex The application method of catalyst, which is characterized in that the catalyst is for being catalyzed monoethanolamine and liquefied ammonia reduction amination synthesis ethylene When amine, needing to control the ratio between amount of substance of reaction raw materials monoethanolamine and liquefied ammonia is 1:6~10, and reaction condition is hydrogen partial pressure 1.5~1.8MPa, 200~240 DEG C of reaction temperature, 1.6~2.0MPa of reaction pressure, monoethanolamine operation air speed 0.1~ 0.25h-1。
5. according to claim 1 a kind of monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex Catalyst, which is characterized in that when the catalyst is for being catalyzed monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines, described one The conversion ratio of ethanol amine is up to 45.4%；The selectivity of ethylenediamine is up to 66.4% in the ethyleneamines series of products, remaining For ethylene amine derivative, including piperazine, diethylenetriamine etc..
6. according to claim 2 a kind of monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex The preparation method of catalyst, which is characterized in that the calcination process in the step (1) is first to be warming up to 200 with 50 DEG C/h speed DEG C, 960 ± 5 DEG C are warming up to 150 DEG C/h speed later, finally keeps 4h under the conditions of 960 ± 5 DEG C.
7. according to claim 2 a kind of monoethanolamine and liquefied ammonia reduction amination synthesis ethyleneamines are prepared with ammino-complex The preparation method of catalyst, which is characterized in that the calcination process in the step (2) is to be warming up to the speed of 50 DEG C/h 420~450 DEG C, 4h is kept under the conditions of 420~450 DEG C later.
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