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

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

A method of preparing monoethanolamine with ammonia complex and reductive amination of liquid ammonia to synthesize ethyleneamine Catalyst and method for its preparation and use

technical field

The invention belongs to the technical field of chemical catalysts, and in particular relates to a catalyst for preparing monoethanolamine from an ammonia complex and reductive amination of liquid ammonia to synthesize ethyleneamine, and a preparation and use method thereof.

Background technique

Ethyleneamine series products refer to the acyclic multi-polymer products of ethylenediamine, including linear amines and cyclic amines. Linear amine products include ethylenediamine, diethylenetriamine, triethylenetetramine, etc.; cyclic amines Amine products include piperazine, aminoethylpiperazine, hydroxyethylpiperazine, etc. The most important product in the series of ethyleneamines is ethylenediamine, which is a chemical raw material in short supply and is widely used in medicine, pesticides, emulsifiers and epoxy resin curing agents. At present, the industrial preparation methods of ethylenediamine mainly include the dichloroethane method (EDC) and the ethanolamine method (MEA), and the output ratio is about 3:2. The characteristics of the dichloroethane method are: low price of raw materials and wide range of sources, serious pollution, easy corrosion of equipment, and high investment costs; the characteristics of the ethanolamine method are: low pollution, no discharge of three wastes, low investment costs, and high additional production costs. The value of cyclic amines is a new direction for the production of ethyleneamines.

The reductive amination process was first developed and industrialized by the German BASF company. The process is: monoethanolamine and ammonia are reacted under high pressure (greater than 20.0MPa) under the action of hydrogen and catalyst. The main product is ethylenediamine, and the parallel production of di Ethylenetriamine, piperazine, aminoethylpiperazine, hydroxyethylpiperazine and hydroxyethylethylenediamine, etc.; the equipment used is: trickle bed reactor; the catalysts are Ni, Co and Cu, etc.

In order to effectively improve the reaction activity and reduce the reaction pressure, the catalysts of the reductive amination process have developed from the early noble metal components such as Ni, Co, and Cu to modified components such as Fe, Ce, Ru, and Re, including Raney Ni (Co) and modified RaneyNi(Co) catalyst, and later developed into a supported catalyst, the carrier is mainly porous materials such as Al ₂ O ₃ , SiO ₂ , TiO ₂ , ZrO ₂ , MgO and aluminosilicate.

Among them, United Carbide uses Ni-Re-B/Al ₂ O ₃ catalyst to make the reaction conditions relatively mild, with a reaction pressure of 15.0-18.0 MPa and a temperature of 140-160°C. US Patent No. 5,750,790 adopts transition phase Al ₂ O ₃ to support Ni and Re catalysts, so that the reaction activity is improved, and the selectivity of ethylenediamine reaches about 60%. US Patent No. 6,534,441 uses the addition of active component B in Ni-Re/Al ₂ O ₃ to increase the selectivity of ethylenediamine to over 70%. Chinese patent CN101875014A adopts Ni-Re-B/Al ₂ O ₃ catalyst, so that the single-pass conversion rate of ethanolamine reaches 50.8%, and the selectivity of ethylenediamine compounds reaches 71.6%. US Patent No. 45,068,330 uses Ir as an auxiliary agent added to the Ni-based catalyst, which also achieves good results.

However, at present, these methods all need to be reacted under high pressure conditions above 8MPa. In order to overcome this shortcoming, the present invention has developed a kind of ammonia complex preparation suitable for use under such relatively low pressure as 1.5-2.0MPa. A catalyst for the reductive amination of monoethanolamine and liquid ammonia to synthesize ethyleneamine.

Contents of the invention

In order to make up for the deficiencies of the prior art, the invention provides a catalyst for preparing monoethanolamine from an ammonia complex and reductive amination of liquid ammonia to synthesize ethyleneamine, as well as its preparation and use methods. Under hydrogen-facing conditions, the catalyst of the invention can be used to synthesize ethylenediamine and other ethyleneamine series products under low pressure conditions, and has the characteristics of mild reaction conditions, low production cost, high yield and the like.

A catalyst for preparing monoethanolamine from ammonia complexes and reductive amination of liquid ammonia to synthesize ethyleneamines. It is a supported catalyst for supporting active components, wherein the aforementioned carrier is γ-Al ₂ O ₃ after chemical modification and crystallization The CaO/Al ₂ O ₃ composite formed after type conversion, the aforementioned active components are composed of transition metals CuO and NiO; the sum of the weights of CuO, NiO, CaO and Al ₂ O ₃ is set as the total weight, then the aforementioned NiO The mass of CuO accounts for 15-17% of the total weight, the mass of CuO accounts for 2-3% of the total weight, the mass of CaO accounts for _2.0 % of the total weight, and the rest is the mass of _Al2O3 .

A preparation method of a catalyst for preparing monoethanolamine and liquid ammonia reductive amination to synthesize ethyleneamine with an ammonia complex, comprising the following steps:

(1) Carrier preparation: dry γ-Al ₂ O ₃ at 120°C for 12 hours, dissolve calcium nitrate in water to prepare a 4% calcium nitrate aqueous solution; put the dried aforementioned γ-Al ₂ O ₃ into the preparation In the above-mentioned 4% calcium nitrate aqueous solution, soak calcium at 60°C for 4 hours; remove and drain the γ-Al ₂ O ₃ after calcium immersion, and dry at 120°C for 12 hours; then calcine; the calcination is complete Then naturally cool down to room temperature to obtain a CaO/Al ₂ O ₃ composite, which is the carrier;

(2) Preparation of catalyst: Weigh copper carbonate and nickel carbonate respectively according to a certain ratio, put them into a container, slowly add 27% ammonia water under stirring conditions, until the aforementioned copper carbonate and nickel carbonate are all dissolved, and obtain nickel ammonia and copper Ammonium complex mixed saturated solution; put the dry aforementioned carrier into the immersion container, then slowly pour the aforementioned mixed nickel ammonia and copper ammonia complex saturated solution into the aforementioned immersion container until the liquid level is below the aforementioned carrier So far, impregnated at 40°C for 4h, then fished out, drained, and dried at 120°C for 12h; then calcined, and the temperature was naturally lowered after calcining to obtain the aforementioned catalyst.

A method for using an ammonia complex to prepare a catalyst for the reductive amination of monoethanolamine and liquid ammonia to synthesize ethyleneamine. The reduction activation is carried out in the middle, and the aforementioned activation conditions are a pressure of 1.5-1.8 MPa, a reduction temperature of 300-310 ° C, and a reduction time of 36 hours.

As a preferred solution, when the aforementioned catalyst is used to catalyze the reductive amination of monoethanolamine and liquid ammonia to synthesize ethyleneamine, it is necessary to control the ratio of the amount of the reaction raw material monoethanolamine to liquid ammonia to 1:6-10, and the reaction conditions The hydrogen partial pressure is 1.5-1.8MPa, the reaction temperature is 200-240°C, the reaction pressure is 1.6-2.0MPa, and the operating space velocity of monoethanolamine is 0.1-0.25h ^-1 .

More preferably, when the aforementioned catalyst is used to catalyze the reductive amination of monoethanolamine and liquid ammonia to synthesize ethyleneamine, the conversion rate of the aforementioned monoethanolamine can reach 68%; the selectivity of ethylenediamine in the aforementioned ethyleneamine series products is the highest 69%, and the rest are ethyleneamine derivatives, including piperazine, diethylenetriamine, etc.

More preferably, the calcination process in the aforementioned step (1) is to first raise the temperature to 200°C at a speed of 50°C/h, then raise the temperature to 960±5°C at a speed of 150°C/h, and finally heat up at 960±5°C Keep for 4h.

More preferably, the aforementioned calcination process in the aforementioned step (2) is to raise the temperature to 420-450 °C at a rate of 50 °C/h, and then keep it at 420-450 °C for 4 hours.

The present invention and existing technology, remarkable effect is:

1. Since the catalyst of the present invention is prepared as a nickel-copper ammonium complex, the waste gas produced in the preparation process is ammonia that is less corrosive and easy to recycle. It only needs water absorption to complete recovery and tail gas purification. The ammonia water obtained by absorption can Further reuse of prepared catalysts can not only significantly reduce raw material consumption and production costs, but also make the catalyst production process cleaner.

②Compared with catalysts impregnated with other inorganic salts such as nitrates, the catalyst of the present invention has more uniform distribution of active metal particles, smaller particle diameter, easy reduction, higher catalytic activity, and is suitable for relatively low reaction pressures of 1.5-3.0 MPa, and The effectively improved conversion rate and selectivity expand the application field of the present invention, and can be widely used in the conversion and transformation of other organic amine production devices such as ethylamine, isopropylamine, and morpholine.

③Calcium oxide is used for chemical modification of the catalyst of the present invention, which shields the acidic center formed by the catalyst carrier, effectively reduces the generation of condensation by-products, improves the conversion rate of ethanolamine, the selectivity and total selectivity of ethylenediamine.

Detailed ways

In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below. Obviously, the described embodiments are part of the embodiments of the present invention, not all Example. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

Example 1

A preparation method of a catalyst for preparing monoethanolamine and liquid ammonia reductive amination to synthesize ethyleneamine with an ammonia complex, comprising the following steps:

(1) Carrier preparation: dry γ-Al ₂ O ₃ at 120°C for 12 hours, dissolve calcium nitrate in water to prepare a 4% calcium nitrate aqueous solution; put the dried γ-Al ₂ O ₃ into the prepared In 4% calcium nitrate aqueous solution, soak calcium at 60°C for 4 hours; remove and drain the γ-Al ₂ O ₃ after calcium immersion, and dry at 120°C for 12 hours; then calcine, the specific calcination process is Firstly, the temperature is raised to 200°C at a rate of 50°C/h, then to 960±5°C at a rate of 150°C/h, and finally kept at 960±5°C for 4 hours; after the calcination is completed, the temperature is naturally cooled to room temperature to obtain CaO/Al ₂ The O ₃ complex is the carrier.

(2) Preparation of catalyst: Weigh nickel carbonate and copper carbonate respectively according to the ratio of 1:0.13, put them into the container, slowly add 27% ammonia water under the condition of stirring, until copper carbonate and nickel carbonate are all dissolved, and obtain nickel ammonia and Mixed saturated solution of cuproammonia complex; put the dry carrier into the immersion container, then slowly pour the mixed saturated solution of nickel ammonia and cuproammonia complex into the immersion container until the liquid surface is covered by the carrier, then Immerse at 40°C for 4 hours, then remove, drain, and dry at 120°C for 12 hours; ℃ and kept for 4 hours; after calcination, the temperature was naturally lowered to obtain a catalyst.

The obtained catalyst for the preparation of monoethanolamine from ammonia complex and the reductive amination of liquid ammonia to synthesize ethyleneamine is a supported catalyst in which active components are supported on a carrier, wherein the carrier is γ-Al ₂ O ₃ which has been chemically modified and crystallized The CaO/Al ₂ O ₃ composite formed after the type conversion, the active component is composed of transition metals CuO and NiO; the weight sum of CuO, NiO, CaO and Al ₂ O ₃ is set as the total weight, then the mass of NiO Accounting for 15% of the total weight, the mass of CuO accounts for 2.0% of the total weight, the mass of CaO accounts for 2.0% of the total weight, and the rest is Al ₂ O ₃ .

Example 2

A preparation method of a catalyst for preparing monoethanolamine and liquid ammonia reductive amination to synthesize ethyleneamine with an ammonia complex, comprising the following steps:

(1) Carrier preparation: dry γ-Al ₂ O ₃ at 120°C for 12 hours, dissolve calcium nitrate in water to prepare a 4% calcium nitrate aqueous solution; put the dried γ-Al ₂ O ₃ into the prepared In 4% calcium nitrate aqueous solution, soak calcium at 60°C for 4 hours; remove and drain the γ-Al ₂ O ₃ after calcium immersion, and dry at 120°C for 12 hours; then calcine, the specific calcination process is Firstly, the temperature is raised to 200°C at a rate of 50°C/h, then to 960±5°C at a rate of 150°C/h, and finally kept at 960±5°C for 4 hours; after the calcination is completed, the temperature is naturally cooled to room temperature to obtain CaO/Al ₂ The O ₃ complex is the carrier.

(2) Preparation of catalyst: Weigh nickel carbonate and copper carbonate respectively according to the ratio of 1:0.14, put them into the container, slowly add 27% ammonia water under the condition of stirring, until copper carbonate and nickel carbonate are all dissolved, and obtain nickel ammonia and Mixed saturated solution of cuproammonia complex; put the dry carrier into the immersion container, then slowly pour the mixed saturated solution of nickel ammonia and cuproammonia complex into the immersion container until the liquid surface is covered by the carrier, then Immerse at 40°C for 4 hours, then remove, drain, and dry at 120°C for 12 hours; ℃ and kept for 4 hours; after calcination, the temperature was naturally lowered to obtain a catalyst.

The obtained catalyst for the preparation of monoethanolamine from ammonia complex and the reductive amination of liquid ammonia to synthesize ethyleneamine is a supported catalyst in which active components are supported on a carrier, wherein the carrier is γ-Al ₂ O ₃ which has been chemically modified and crystallized The CaO/Al ₂ O ₃ composite formed after the type conversion, the active component is composed of transition metals CuO and NiO; the weight sum of CuO, NiO, CaO and Al ₂ O ₃ is set as the total weight, then the mass of NiO Accounting for 15.5% of the total weight, the mass of CuO accounts for 2.21% of the total weight, the mass of CaO accounts for 2.0% of the total weight, and the rest is Al ₂ O ₃ .

Example 3

A preparation method of a catalyst for preparing monoethanolamine and liquid ammonia reductive amination to synthesize ethyleneamine with an ammonia complex, comprising the following steps:

(1) Carrier preparation: dry γ-Al ₂ O ₃ at 120°C for 12 hours, dissolve calcium nitrate in water to prepare a 4% calcium nitrate aqueous solution; put the dried γ-Al ₂ O ₃ into the prepared In 4% calcium nitrate aqueous solution, soak calcium at 60°C for 4 hours; remove and drain the γ-Al ₂ O ₃ after calcium immersion, and dry at 120°C for 12 hours; then calcine, the specific calcination process is Firstly, the temperature is raised to 200°C at a rate of 50°C/h, then to 960±5°C at a rate of 150°C/h, and finally kept at 960±5°C for 4 hours; after the calcination is completed, the temperature is naturally cooled to room temperature to obtain CaO/Al ₂ The O ₃ complex is the carrier.

(2) Preparation of catalyst: Weigh nickel carbonate and copper carbonate respectively according to the ratio of 1:0.15, put them into the container, slowly add 27% ammonia water under the condition of stirring, until copper carbonate and nickel carbonate are all dissolved, and obtain nickel ammonia and Mixed saturated solution of cuproammonia complex; put the dry carrier into the immersion container, then slowly pour the mixed saturated solution of nickel ammonia and cuproammonia complex into the immersion container until the liquid surface is covered by the carrier, then Immerse at 40°C for 4 hours, then remove, drain, and dry at 120°C for 12 hours; ℃ and kept for 4 hours; after calcination, the temperature was naturally lowered to obtain a catalyst.

The obtained catalyst for the preparation of monoethanolamine from ammonia complex and the reductive amination of liquid ammonia to synthesize ethyleneamine is a supported catalyst in which active components are supported on a carrier, wherein the carrier is γ-Al ₂ O ₃ which has been chemically modified and crystallized The CaO/Al ₂ O ₃ composite formed after the type conversion, the active component is composed of transition metals CuO and NiO; the weight sum of CuO, NiO, CaO and Al ₂ O ₃ is set as the total weight, then the mass of NiO Accounting for 16% of the total weight, the mass of CuO accounts for 2.47% of the total weight, the mass of CaO accounts for 2.0% of the total weight, and the rest is Al ₂ O ₃ .

Example 4

A preparation method of a catalyst for preparing monoethanolamine and liquid ammonia reductive amination to synthesize ethyleneamine with an ammonia complex, comprising the following steps:

(1) Carrier preparation: dry γ-Al ₂ O ₃ at 120°C for 12 hours, dissolve calcium nitrate in water to prepare a 4% calcium nitrate aqueous solution; put the dried γ-Al ₂ O ₃ into the prepared In 4% calcium nitrate aqueous solution, soak calcium at 60°C for 4 hours; remove and drain the γ-Al ₂ O ₃ after calcium immersion, and dry at 120°C for 12 hours; then calcine, the specific calcination process is Firstly, the temperature is raised to 200°C at a rate of 50°C/h, then to 960±5°C at a rate of 150°C/h, and finally kept at 960±5°C for 4 hours; after the calcination is completed, the temperature is naturally cooled to room temperature to obtain CaO/Al ₂ The O ₃ complex is the carrier.

(2) Preparation of catalyst: Weigh nickel carbonate and copper carbonate respectively according to the ratio of 1:0.16, put them into the container, slowly add 27% ammonia water under stirring conditions, until copper carbonate and nickel carbonate are all dissolved, and obtain nickel ammonia and Mixed saturated solution of cuproammonia complex; put the dry carrier into the immersion container, then slowly pour the mixed saturated solution of nickel ammonia and cuproammonia complex into the immersion container until the liquid surface is covered by the carrier, then Immerse at 40°C for 4 hours, then remove, drain, and dry at 120°C for 12 hours; ℃ and kept for 4 hours; after calcination, the temperature was naturally lowered to obtain a catalyst.

The obtained catalyst for the preparation of monoethanolamine from ammonia complex and the reductive amination of liquid ammonia to synthesize ethyleneamine is a supported catalyst in which active components are supported on a carrier, wherein the carrier is γ-Al ₂ O ₃ which has been chemically modified and crystallized The CaO/Al ₂ O ₃ composite formed after the type conversion, the active component is composed of transition metals CuO and NiO; the weight sum of CuO, NiO, CaO and Al ₂ O ₃ is set as the total weight, then the mass of NiO Accounting for 16.5% of the total weight, the mass of CuO accounts for 2.75% of the total weight, the mass of CaO accounts for 2.0% of the total weight, and the rest is Al ₂ O ₃ .

Example 5

A preparation method of a catalyst for preparing monoethanolamine and liquid ammonia reductive amination to synthesize ethyleneamine with an ammonia complex, comprising the following steps:

(1) Carrier preparation: dry γ-Al ₂ O ₃ at 120°C for 12 hours, dissolve calcium nitrate in water to prepare a 4% calcium nitrate aqueous solution; put the dried γ-Al ₂ O ₃ into the prepared In 4% calcium nitrate aqueous solution, soak calcium at 60°C for 4 hours; remove and drain the γ-Al ₂ O ₃ after calcium immersion, and dry at 120°C for 12 hours; then calcine, the specific calcination process is Firstly, the temperature is raised to 200°C at a rate of 50°C/h, then to 960±5°C at a rate of 150°C/h, and finally kept at 960±5°C for 4 hours; after the calcination is completed, the temperature is naturally cooled to room temperature to obtain CaO/Al ₂ The O ₃ complex is the carrier.

(2) Preparation of catalyst: Weigh nickel carbonate and copper carbonate respectively according to the ratio of 1:0.17, put them into the container, slowly add 27% ammonia water under the condition of stirring, until copper carbonate and nickel carbonate are all dissolved, and obtain nickel ammonia and Mixed saturated solution of cuproammonia complex; put the dry carrier into the immersion container, then slowly pour the mixed saturated solution of nickel ammonia and cuproammonia complex into the immersion container until the liquid surface is covered by the carrier, then Immerse at 40°C for 4 hours, then remove, drain, and dry at 120°C for 12 hours; ℃ and kept for 4 hours; after calcination, the temperature was naturally lowered to obtain a catalyst.

The obtained catalyst for the preparation of monoethanolamine from ammonia complex and the reductive amination of liquid ammonia to synthesize ethyleneamine is a supported catalyst in which active components are supported on a carrier, wherein the carrier is γ-Al ₂ O ₃ which has been chemically modified and crystallized The CaO/Al ₂ O ₃ composite formed after the type conversion, the active component is composed of transition metals CuO and NiO; the weight sum of CuO, NiO, CaO and Al ₂ O ₃ is set as the total weight, then the mass of NiO Accounting for 17% of the total weight, the mass of CuO accounts for 3.0% of the total weight, the mass of CaO accounts for 2.0% of the total weight, and the rest is Al ₂ O ₃ .

Comparative Example 1

Weigh nickel carbonate and copper carbonate respectively according to the ratio of 1:0.17, put them into the container, slowly add 27% ammonia water under the condition of stirring, until the copper carbonate and nickel carbonate are completely dissolved, and the nickel ammonia and copper ammonia complexes are mixed and saturated solution; put the dry carrier into the impregnation container, then slowly pour the saturated solution of nickel ammonia and copper ammonia complex into the impregnation container until the liquid surface is submerged in the carrier, and then immerse at 40°C for 4 hours. Then remove, drain, and dry at 120°C for 12 hours; then calcine, the calcination process is to raise the temperature to 420-450°C at a rate of 50°C/h, and keep it at 420-450°C for 4 hours; After calcination, the temperature is naturally lowered to obtain a catalyst. The active component is made up of transition metal CuO and NiO; With CuO, NiO and Al2O3 The weight sum is set as gross weight, then the quality of NiO accounts for 17% of gross weight, the mass of CuO accounts for 3.0% of gross weight, and the remainder is Al2O3.

Performance evaluation of the catalysts prepared in Examples 1-5 and Comparative Example 1: A single-tube fixed-bed reactor was used to prepare a catalyst for the preparation of monoethanolamine from ammonia complexes and the reductive amination of liquid ammonia to synthesize ethyleneamines. . Before the reaction, the catalyst is first reduced and activated in a hydrogen atmosphere, and the activation conditions are pressure 1.5-1.8MPa, reduction temperature 300-310°C, and reduction time 36h; then the liquid raw material-ethanolamine and liquid ammonia are mixed according to the amount of the substance Mixed at a ratio of 1:8, pumped into the preheater, preheated with hydrogen to 200°C, and then entered into a single-tube fixed-bed reactor for reaction. The catalyst loading was 10mL, and the reaction condition was controlled at a pressure of 1.8 during the reaction. MPa, reaction temperature 220°C, monoethanolamine operating space velocity 0.15h ^-1 , reaction time 168h.

After the reaction, the reaction product was analyzed by gas chromatography, using polyethylene glycol 20,000 as a packed column, an FID detector, and dimethylformamide (DMFA) as an internal standard for quantitative analysis and detection. The test results are shown in Table 1.

Table 1 Catalyst evaluation results

Compared with Example 1, the catalyst of the present invention has been significantly improved due to the chemical modification and physical modification, the MEA conversion rate has been improved from 55% to 68%, and the selectivity of ethylenediamine has also been increased by 36%. increased to 69%. The total selectivity increased from 74% to 97%, and with the increase of copper content, the selectivity of cyclic ethyleneamine and polyethylene polyamine increased, while the selectivity of ethylenediamine decreased.

It should be understood that the specific embodiments described above are only used to explain the present invention, not to limit the present invention. Obvious changes or variations derived from the spirit of the present invention are still within the protection scope of the present 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.