WO2013152548A1

WO2013152548A1 - Catalyst for synthesizing ethylene amine and method for preparing ethylene amine

Info

Publication number: WO2013152548A1
Application number: PCT/CN2012/075989
Authority: WO
Inventors: 严丽; 丁云杰; 吕元; 程显波; 马立新
Original assignee: 中国科学院大连化学物理研究所
Priority date: 2012-04-13
Filing date: 2012-05-24
Publication date: 2013-10-17
Also published as: CN102658162B; IN2014DN07644A; CN102658162A

Abstract

The present invention relates to a catalyst for synthesizing ethylene amine and a method for preparing ethylene amine. The catalyst is formed of a main active component, an auxiliary agent, and a carrier processed by ammonification. The main active component is Ni or Co, the auxiliary agent comprises one or more of Fe, Cu, Ru, Re, K, Zn, B and other metal or oxides thereof, and the ammonified carrier is ammonified SiO₂ or Al₂O₃. In the total weight of the catalyst, the main active component accounts for 1~40%, and the auxiliary agent accounts for 0.1~20%. The catalyst of the present invention is characterized in that the used carrier needs to be ammonified specially. The ethylene amine product synthesized in a hydrogen condition by using the catalyst of the present invention to carry out an ethanolamine ammonification reaction presents high activity, high selectivity and stability.

Description

Catalyst for synthesizing ethyleneamine and method for preparing ethyleneamine

The present invention relates to a catalyst for the synthesis of ethyleneamine and its use. More specifically, it relates to the conversion of ethanolamine (MEA) and ammonia to ethylenediamine (EDA), diethylenetriamine (DETA;), hydroxyethylethylenediamine (AEEA), piperazine under hydrogen conditions. A catalyst for ethyleneamine such as PIP), hydroxyethylpiperazine (HEP) or aminoethylpiperazine (AEP), and a method for producing ethyleneamine. Background technique

Ethyleneamine products are important chemical raw materials and fine chemical intermediates, which mainly include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyethene polyamine, piperazine and other products. Epoxy resin curing agent, emulsifier, antifreeze, organic solvent and chemical analysis reagent; used in the production of pesticides, fungicides, herbicides, fuels, pharmaceuticals, surfactants, metal complexing agents, etc. Additives; also used in the production of chelating agents, corrosion inhibitors, soil improvers, lubricants, lubricant additives and rubber accelerators, as well as textiles, paper, coatings and adhesives.

At present, the industrial synthesis of ethyleneamine is mainly a dichloroethane process and an ethanolamine process.

The process of dichloroethane is severely corrosive to equipment, consumes a lot of energy and causes serious environmental pollution, resulting in high production costs, and the process is gradually being phased out.

The ethanolamine process route has low investment and low environmental pollution. The ethanolamine process is further divided into a reduction process and a condensation process, wherein the reduction process needs to be carried out under high pressure hydrogen conditions, and the product is mostly ethylenediamine; and the condensation process does not require hydrogen, and the reaction product is mainly cyclic amine.

The synthesis process of industrial ethyleneamine was developed earlier in foreign countries. Among them, BASF first developed the ethanolamine process, and realized industrialization in the 1960s. Later, it was adopted by many European and American companies. The ethanolamine process developed by BASF uses metal catalysts such as M, Co and Cu. The reaction temperature is 150~230°C and the pressure is 20.0~30.0MPa. The products are mainly ethylenediamine, diethylenetriamine and hydroxyethylethylene. Amine, piperazine, aminoethylpiperazine, hydroxyethylpiperazine, and the like. However, due to the large gap between production technology and production capacity in the country, most of the current industrial ethyleneamine products rely on imports.

Ethylamine and ammonia are aminated in the presence of a catalyst to form ethylenediamine. Since the intermediate imine has higher reactivity than ammonia, the reaction inevitably produces complex polyalkylene polyamine by-products, resulting in ethylenediamine. Yield Lowering and causing difficulty in product separation. Common methods can increase the selectivity of the product, but the conversion rate is reduced, which affects the production capacity of ethylenediamine. Therefore, there is a need for a catalyst that not only improves the selectivity of the target product, but also maintains a good amination conversion.

US5068330 uses different nickel-based metal catalysts, adding noble metals such as Ir, Pt, Ru, etc. The conversion of ethanolamine is 20%~45% at 120~300 °C, and the selectivity of ethylenediamine is 15%~55%. And the selectivity of diethylenetriamine is 10% to 20%. The ethanolamine conversion rate and the ethylenediamine selectivity of the catalyst are difficult to meet the requirements, and the precious metal is repeatedly added continuously during the preparation process, which increases the complexity of the process operation and the production cost.

U.S. Patent 4,642,303 discloses that under the action of a Ni-Cu-Cr catalyst, the amination temperature of the ethanolamine is advantageous for the formation of ethylenediamine at a low temperature.

U.S. Patent 4,094,524 reports the effect of nickel loading on catalyst activity, and it has been found that as the nickel loading increases, the conversion of the starting ethanolamine is increasing, but the reaction is more selective for cyclic amines such as piperazine.

US 4,123,462 teaches that the activity of the catalyst is closely related to the support material, wherein changing the surface properties of the surface area, pore size, pore volume and shape of the support will affect the activity of the catalyst to a certain extent.

However, the above prior art catalysts and methods for preparing ethyleneamines require further improvement in one or more aspects of activity, selectivity and stability. Summary of the invention

It is an object of the present invention to provide a catalyst for the synthesis of ethyleneamine and a process for the preparation of ethyleneamine, the catalyst and the process for preparing ethyleneamine can achieve one or more of the following: (1) Ethanolamine The production of ethyleneamine by hydroamination can be achieved at a lower reaction pressure. (2) The reaction conditions can flexibly modulate the composition of ethyleneamine, and (3) reduce the one-time investment and production cost of production equipment. (4) ) Easy to operate, (5) Improve catalyst activity, (6) Improve selectivity to products, (7) Improve conversion of raw materials, and (8) Improve process stability.

The inventors of the present invention found that: the carrier material and the catalyst activity are closely related, and the carrier used for the catalyst is subjected to amination treatment, and the surface of the carrier is acidic due to the presence of a large amount of hydroxyl groups on the surface of the carrier SiO ₂ or A1 ₂ 0 ₃ . Conducive to the polymerization of the intermediate product imine, and after the surface of the carrier is ammoniated, a large amount of hydroxyl groups on the surface are converted into an amine group, so the carrier is in an alkaline environment, which reduces the possibility of polymerization of the imine, improves the activity of the catalyst, and selects Sex and stability; thus one or more of the above objects can be achieved.

Accordingly, in one aspect, the present invention provides a catalyst for synthesizing ethyleneamine, the catalyst comprising three main components: a main active component, an auxiliary agent, and an ammoniated carrier, wherein the main active component Selecting one or more of the group consisting of M and Co selected from the group consisting of Fe, Cu, Ru, Re, K, Zn and PB, and One or more of their respective oxide composition groups; the ammoniated carrier is aminated by one or more carriers selected from the group consisting of SiO ₂ and A1 ₂ 0 ₃ It is obtained that the amination treatment comprises: contacting the carrier with an ammonia source at a temperature of 200 to 400 ° C for 0.5 to 24 hours.

In a preferred embodiment, the support has a specific surface area of from 150 to 350 m ² /g and an average pore diameter of from 8 to 80 nm.

In another preferred embodiment, the ammonia source is selected from one or more of the group consisting of ammonia, liquid ammonia, ammonia, and urea.

In another preferred embodiment, the primary active component comprises from 1 to 40%, preferably from 5 to 30%, based on the total weight of the catalyst.

In another preferred embodiment, the adjuvant comprises from 0.1 to 20%, preferably from 0.1 to 15%, based on the total weight of the catalyst.

In another aspect, the present invention provides a process for the preparation of ethyleneamine from ethanolamine and ammonia, the process comprising: converting ethanolamine and ammonia to ethylene under hydrogen conditions in the presence of a catalyst as described above amine.

In a preferred embodiment, the method is carried out at a temperature of 135 to 200 ° C, a pressure of 6.0 to 22.0 MPa, and a liquid space velocity of ethanolamine of OJ l^h- ¹ .

In another preferred embodiment, the catalyst is reductively activated under a hydrogen atmosphere and at a pressure of atmospheric pressure at a temperature of 150 to 400 ° C and a hydrogen space velocity of 500 to 4000 h" ¹ prior to use. detailed description

More specifically, the present invention provides a supported catalyst for synthesizing an ethyleneamine product, which is composed of a main active component, an auxiliary agent and an ammoniated carrier, and the main active component is Ni and/or Co. The auxiliary agent is one or more of the group consisting of Fe, Cu, Ru, Re, K, Zn and B and their respective oxides; the carrier is selected from Si0 ₂ and/or A1 ₂ 0 ₃ , and the carrier has passed Special treatment for ammoniation. Wherein the catalyst is prepared by an impregnation method in which the support is impregnated with a solution of a soluble salt of M and/or Co, which is a nitrate, a chloride, an acetate, an oxalate or a sulfuric acid of M and/or Co. Salt, citrate or other soluble salt. The main active component accounts for 1~40% of the total weight of the catalyst; the auxiliary agent accounts for 0.1-20% of the total weight of the catalyst; the carrier Si0 ₂ or A1 ₂ 0 _{3 has} a specific surface area of 150-350 m ² /g, and the average pore diameter is 8-80 nm. The carrier Si0 ₂ and/or A1 ₂ 0 ₃ are subjected to ammoniation treatment using ammonia gas, liquid ammonia, ammonia water or urea.

The catalyst of the invention is reductively activated in a hydrogen atmosphere before application: the pressure is normal pressure, the temperature is 150-400 ° C, the space velocity of hydrogen is SOO ^OO h^, and the conversion of ethanolamine and ammonia to ethyleneamine under hydrogen conditions Product Reaction conditions: temperature is 135~200 °C, pressure is 6.0~22.0MPa, liquid air velocity of ethanolamine is

The reactor of the present invention may employ a fixed bed reactor, a slurry bed reactor or a trickle bed reactor. Among them, a trickle bed reactor is preferred.

In the reaction system of the present invention, the liquid ethanolamine and ammonia mixture can be directly pumped into the preheater and mixed with hydrogen, and then preheated to 135 to 200 ° C and then introduced into the trickle bed reactor.

The catalyst is applied to the reaction of ethanolamine and ammonia under hydrogen conditions, and exhibits excellent activity, selectivity and stability. The ethyleneamine product formed includes ethylenediamine, diethylenetriamine and hydroxyethylethylenediamine. Ethyleneamine such as piperazine, aminoethylpiperazine or hydroxyethylpiperazine.

In the present invention, the hydrogen-producing condition means that hydrogen is present.

Compared with the prior art, the present invention has a remarkable effect that the carrier of the catalyst of the present invention, SiO ₂ or A1 ₂ 0 ₃ , is subjected to ammoniation treatment using ammonia gas, liquid ammonia, ammonia water or urea. Due to the presence of a large amount of hydroxyl groups on the surface of the carrier SiO ₂ or A1 ₂ 0 _{3 to make} the surface of the carrier acidic, it is advantageous to polymerize the intermediate product imine to produce a large amount of by-products, thereby reducing the selectivity of ethylenediamine. After the surface of the carrier is ammoniated, a large amount of hydroxyl groups on the surface are converted into an amine group to be alkaline, which lowers the possibility of polymerization of the imine and improves selectivity and stability. After the treated carrier is loaded with the main active component and the auxiliary agent, it is applied to the reaction of ethanolamine and ammonia under the hydrogen condition, and exhibits excellent activity, selectivity and stability, optimizes the reaction conditions, and realizes the B. The flexible modulation of the amine products provides the possibility for industrial production to adapt to market fluctuations. The temperature and pressure of the reaction process conditions are significantly lower than those of the prior art. Optimization of production process conditions will reduce the pressure requirements on the reaction equipment, reduce the one-time investment and production costs of the reaction unit, and reduce the difficulty of operation. Example

The method of the present invention will be further described below in conjunction with the examples, which are not intended to limit the invention. Parts, percentages and amounts in this application are by weight unless otherwise indicated. Example 1

Preparation and application of 5% Ni-15% Re-1.2% B/SiO ₂ catalyst

Weigh 10 g of carrier SiO ₂ (20-40 mesh), install the carrier SiO ₂ in a quartz tube, dry at 200 ° C for 5 hours under an inert atmosphere, and then introduce a 10% ammonia-hydrogen gas mixture (molar content). The ammoniation temperature was 300 ° C and the ammoniation time was 5 hours. 2.477 g of Μ(Ν0 ₃ ) ₂ ·6Η ₂ 0, 2.161 g of H ₄ Re0 ₄ and 0.686 g of H ₃ B0 _{3 were} dissolved in 12 ml of deionized water. The ammoniated SiO ₂ carrier was impregnated with half of the aqueous solution and allowed to dry naturally, followed by It was dried at 120 ° C for 4 hours and then calcined at 500 ° C for 4 hours. Then, the ammoxidation-treated SiO ₂ carrier was impregnated a second time with the remaining remaining half of the aqueous solution, followed by natural drying, drying at 120 ° C for 4 hours, and calcination at 500 ° C for 4 hours. The catalyst was reduced in a hydrogen stream at 375 ° C (atmospheric pressure, ZOOOh- ¹ ) for 4 hours before use. When the temperature inside the reactor naturally drops to 160 °C, the pressure is increased to 8 MPa. After the system is stabilized, the liquid with H ₃ /ethanolamine = 10 is pumped into the reactor to adjust the liquid space velocity of ethanolamine to O h , H . ₂ /NH ₃ /ethanolamine = 0.25: 10:1 (molar ratio), the reaction was carried out, the reaction time was 50 hours, and the sample was analyzed. SE-30 capillary column, FID detector, hydrazine, hydrazine-dimethylformamide were used for internal quantitative analysis. The reaction results are shown in Table 1. Example 2:

Preparation and Application of 15% Ni-3.6% Re-1.2% B/Si0 ₂ Catalyst

Weigh 10 g of carrier SiO ₂ (20-40 mesh), install the carrier SiO ₂ in a quartz tube, dry at 200 ° C for 5 hours under an inert atmosphere, and then introduce a 20% ammonia-hydrogen gas mixture (molar content). The ammoniation temperature was 300 ° C and the ammoniation time was 5 hours. 7.432 g of Μ(Ν0 ₃ ) ₂ ·6Η ₂ 0, 0.518 g of NH ₄ Re0 ₄ and 0.686 g of H ₃ B0 _{3 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 3:

Preparation and application of 30% Ni-0.2% Re-15% K/SiO ₂ catalyst

Weigh 10 g of carrier SiO ₂ (20-40 mesh), install the carrier SiO ₂ in a quartz tube, dry at 200 ° C for 5 hours under an inert atmosphere, and then introduce a 50% ammonia-hydrogen mixture (molar content). The ammoniation temperature was 300 ° C and the ammoniation time was 5 hours. 14.864 g of Μ(ΝΟ ₃ ) ₂ ·6Η ₂ Ο, 0.029 g of H ₄ Re0 ₄ and 3.879 g of KN0 _{3 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 4:

Preparation and Application of 15% Ni-3.6% Cu-1.2% B/Si0 ₂ Catalyst

Weigh 10 g of carrier SiO ₂ (20-40 mesh), install the carrier SiO ₂ in a quartz tube, dry at 200 ° C for 5 hours under an inert atmosphere, and then introduce a 20% ammonia-hydrogen gas mixture (molar content). The ammoniation temperature was 300 ° C and the ammoniation time was 5 hours. 7.432 g of Μ(Ν0 ₃ ) ₂ ·6Η ₂ 0, 1.369 g of Νι(Ν0 ₃ ) ₂ ·3Η ₂ 0 and 0.686 g of H ₃ B0 _{3 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 5:

Preparation and Application of 15% Co-3.6% Re- 1.2% B/Si0 ₂ Catalyst

Weigh 10 g of carrier SiO ₂ (20-40 mesh), install the carrier SiO ₂ in a quartz tube, dry at 200 ° C for 5 hours under an inert atmosphere, and then introduce a 20% ammonia-hydrogen gas mixture (molar content). The ammoniation temperature was 300 ° C and the ammoniation time was 5 hours. 7.408 g of Co(N0 ₃ ) 2'3⁄40, 0.518 g of H ₄ Re0 ₄ and 0.686 g of H ₃ B0 _{3 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 6

Preparation and Application of 5% Ni-8% Re-1.2% B/Al ₂ 0 ₃ Catalyst

10 g of the carrier A1 ₂ 0 ₃ (20-40 mesh) was weighed, and the carrier A1 ₂ 0 _{3 was} placed in a quartz tube, dried under an inert atmosphere at 200 ° C for 5 hours, and then a 10% ammonia-hydrogen gas mixture was introduced ( Molar content), the ammoniation temperature was 300 ° C, and the amination time was 5 hours. 2.477 grams of MC1 ₂ '6H ₂ 0, 1.152 grams of H ₄ Re0 ₄ and 0.686 grams of H ₃ B0 _{3 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 7

Preparation and application of 15% Ni-2% Re- 1.2% B/A1 ₂ 0 ₃ catalyst

10 g of the carrier A1 ₂ 0 ₃ (20-40 mesh) was weighed, and the carrier A1 ₂ 0 _{3 was} placed in a quartz tube, dried under an inert atmosphere at 200 ° C for 5 hours, and then a 20% ammonia-hydrogen gas mixture was introduced ( Molar content), the ammoniation temperature was 300 ° C, and the amination time was 5 hours. 7.432 g of Μ(Ν0 ₃ ) ₂ ·6Η ₂ 0, 0.288 g of NH ₄ Re0 ₄ and 0.686 g of H ₃ B0 _{3 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 8

Preparation and Application of 30% Ni-2% Re-1.2% B/Al ₂ O ₃ Catalyst

10 g of the carrier A1 ₂ 0 ₃ (20-40 mesh) was weighed, and the carrier A1 ₂ 0 _{3 was} placed in a quartz tube, dried under an inert atmosphere at 200 ° C for 5 hours, and then a 50% ammonia-hydrogen gas mixture was introduced ( Molar content), the ammoniation temperature was 300 ° C, and the amination time was 5 hours. 12.712 grams of M(CH ₃ COO) 2'6H ₂ 0, 0.288 grams of H ₄ Re0 ₄ and 0.686 grams of H ₃ B0 _{3 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 9 Preparation and Application of 15% Ni-0.2% Re-10%Zn/Al ₂ O ₃ Catalyst

10 g of the carrier A1 ₂ 0 ₃ (20-40 mesh) was weighed, and the carrier A1 ₂ 0 _{3 was} placed in a quartz tube, dried under an inert atmosphere at 200 ° C for 5 hours, and then a 20% ammonia-hydrogen gas mixture was introduced ( Molar content), the amination temperature was 200 ° C, and the amination time was 5 hours. 6.356 g of Ni(CH ₃ COO) 2'6H ₂ O, 0.029 g of H ₄ Re0 ₄ and 4.549 g of Ζη(Ν0 ₃ ) ₂ ·6Η ₂ 0 were dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 10:

Preparation and Application of 15% Ni-3.6% Re-0.2% Zn/Al ₂ O ₃ Catalyst

10 g of the carrier A1 ₂ 0 ₃ (20-40 mesh) was weighed, and the carrier A1 ₂ 0 _{3 was} placed in a quartz tube, dried under an inert atmosphere at 200 ° C for 5 hours, and then a 20% ammonia-hydrogen gas mixture was introduced ( Molar content), the ammoniation temperature was 300 ° C, and the amination time was 5 hours. 7.432 g of Νί(Ν0 ₃ ) ₂ ·6Η ₂ 0, 0.518 g of H ₄ Re0 ₄ and 0.091 g of Ζη(Ν0 ₃ ) ₂ ·6Η ₂ 0 were dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 11:

Preparation and Application of 30% Ni-2%Re/Al ₂ O ₃ Catalyst

10 g of the carrier A1 ₂ 0 ₃ (20-40 mesh) was weighed, and the carrier A1 ₂ 0 _{3 was} placed in a quartz tube, dried under an inert atmosphere at 200 ° C for 5 hours, and then a 50% ammonia-hydrogen gas mixture was introduced ( Molar content), the ammoniation temperature was 300 ° C, and the amination time was 5 hours. 14.864 g of Μ(Ν0 ₃ ;) ₂ ·6Η ₂ 0 and 0.288 g of H ₄ Re0 _{4 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 12

Preparation and application of 15% Ni-2% Re-12% B/A1 ₂ 0 ₃ catalyst

10 g of the carrier A1 ₂ 0 ₃ (20-40 mesh) was weighed, and the carrier A1 ₂ 0 _{3 was} placed in a quartz tube, dried under an inert atmosphere at 200 ° C for 5 hours, and then a 20% ammonia-hydrogen gas mixture was introduced ( Molar content), the ammoniation temperature was 300 ° C, and the amination time was 5 hours. 7.432 g of Μ(Ν0 ₃ ) ₂ ·6Η ₂ 0, 0.288 g of NH ₄ Re0 ₄ and 6.86 g of H ₃ B0 _{3 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 13: Preparation and Application of 5% Co- 15% Cu- 1.2% K/A1 ₂ 0 ₃ Catalyst

10 g of the carrier A1 ₂ 0 ₃ (20-40 mesh) was weighed, and the carrier A1 ₂ 0 _{3 was} placed in a quartz tube, dried under an inert atmosphere at 200 ° C for 5 hours, and then a 10% ammonia-hydrogen gas mixture was introduced ( Molar content), the amination temperature was 200 ° C, and the amination time was 5 hours. 2.469 g of Co(N0 ₃ ) ₂ 'H ₂ 0, 5.703 g of Οι(Ν0 ₃ ) ₂ ·3Η ₂ 0 and 0.310 g of KN0 _{3 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 14

Preparation and application of 15% Co-3.6% Re- 1.2% B/A1 ₂ 0 ₃ catalyst

10 g of the carrier A1 ₂ 0 ₃ (20-40 mesh) was weighed, and the carrier A1 ₂ 0 _{3 was} placed in a quartz tube, dried under an inert atmosphere at 200 ° C for 5 hours, and then a 20% ammonia-hydrogen gas mixture was introduced ( Molar content), the ammoniation temperature was 300 ° C, and the amination time was 5 hours. 7.408 g of Co(N0 ₃ ) 2'3⁄40, 0.518 g of H ₄ Re0 ₄ and 0.686 g of H ₃ B0 _{3 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 15:

Preparation and Application of 30% Co-2% Re-1.2% B/Al ₂ 0 ₃ Catalyst

10 g of the carrier A1 ₂ 0 ₃ (20-40 mesh) was weighed, and the carrier A1 ₂ 0 _{3 was} placed in a quartz tube, dried under an inert atmosphere at 200 ° C for 5 hours, and then a 50% ammonia-hydrogen gas mixture was introduced ( Molar content), the ammoniation temperature was 300 ° C, and the amination time was 5 hours. 14.816 grams of Co(NO ₃ ) 2'H ₂ O, 0.288 grams of H ₄ Re0 ₄ and 0.686 grams of H ₃ B0 _{3 were} dissolved in 12 ml of deionized water. See Example 1 for the rest of the preparation steps and catalyst evaluation protocol. The reaction results are shown in Table 1. Example 16:

Catalyst stability test, the catalyst prepared by the catalyst preparation method of Example 7 was placed in a fixed bed reactor under the reaction conditions: temperature was 160 ° C, pressure was 8 MPa, and liquid air velocity of ethanolamine was O h- ¹ , H ₂ /NH ₃ /ethanolamine = 0.25: 10: 1 (molar ratio), the reaction was carried out, and the analysis was carried out every 24 hours. SE-30 capillary column, FID detector, hydrazine, hydrazine-dimethylformamide were used for internal quantitative analysis. The results of 1000 hours showed that the activity and selectivity of the catalyst were basically the same. Comparative example 1:

Preparation and application of 15% M-3.6% Re-1.2% B/SiO ₂ catalyst without carrier ammoniation

Weigh 10 g of carrier SiO ₂ (20-40 mesh), and install the carrier SiO ₂ in a quartz tube under an inert atmosphere at 200 ° C. Dry for 5 hours. 7.432 g Μ (Ν0 ₃ ;> ₂ ·6Η ₂ 0, 0.518 g H ₄ Re0 ₄ and 0.686 g H ₃ B0 _{3 were} dissolved in

12ml deionized water. The above SiO ₂ carrier was impregnated with half of this aqueous solution, dried naturally, followed by drying at 120 ° C for 4 hours, followed by calcination at 500 ° C for 4 hours. Then, the metal-loaded SiO ₂ carrier was impregnated a second time with the remaining remaining half of the aqueous solution, followed by natural drying, drying at 120 ° C for 4 hours, and calcination at 500 ° C for 4 hours. See Example 1 for the catalyst evaluation scheme. Comparative example 2:

Preparation and application of 15% Co-3.6% Re-1.2% B/Al ₂ O ₃ catalyst without carrier amination.

10 g of the carrier A1 ₂ 0 ₃ (20-40 mesh) was weighed, and the carrier A1 ₂ 0 _{3 was} placed in a quartz tube and dried at 200 ° C for 5 hours under an inert atmosphere. 7.408 g of Co(N0 ₃ ;> H ₂ 0, 0.518 g of H ₄ Re0 ₄ and 0.686 g of H ₃ B0 _{3 were} dissolved in 12 ml of deionized water. The above A1 ₂ 0 ₃ carrier was impregnated with half of the aqueous solution, and dried naturally. It was then dried at 120 ° C for 4 hours and then calcined at 500 ° C for 4 hours. Then, the metal-loaded A1 ₂ 0 ₃ carrier was secondarily impregnated with the remaining remaining half of the aqueous solution, followed by drying naturally, and drying at 120 ° C. The hour was calcined at 500 ° C for 4 hours. See Table 1 for the catalyst evaluation scheme and Table 1 for the reaction results.

The molar conversion of ethanolamine and the molar selectivity of the product are calculated as follows:

Conversion of ethanolamine: Conv. (%) = (l- NEDA XCEDA / (N _E DA >< C _EDA + ∑ NixCi)) x 100%

Product selectivity: Si=(NixCi/∑NixCi)x 100%

among them:

NEDA: the number of moles of ethanolamine in the product;

C _EDA : the number of carbon atoms of ethanolamine;

Ni: the number of moles of product i in the product;

Ci: The number of carbon atoms of the product i in the product. The catalyst components of Example 2 and Comparative Example 1 were the same, except that the carrier of Example 2 was subjected to ammoniation treatment, and the carrier of Comparative Example 1 was not subjected to ammoniation treatment. As a result of comparison, it was found that the conversion of ethanolamine was improved. 31%, the selectivity of ethylenediamine increased by 32%.

The catalyst components of Example 14 and Comparative Example 2 were the same, except that the carrier of Example 14 was subjected to ammoniation treatment, and the carrier of Comparative Example 2 was not subjected to ammoniation treatment. As a result of comparison, it was found that the conversion of ethanolamine was improved. 34%, the selectivity of ethylenediamine increased by 27%.

Based on the above comparative analysis results, it can be concluded that after the catalyst carrier is treated with ammoniation, The agent and the method for preparing ethyleneamine realize one or more of the following: (1) being realized at a lower reaction pressure, and (2) modulating the reaction condition to flexibly modulate the composition of the ethyleneamine, 3) Reduce the one-time investment and production costs of the production equipment, (4) to achieve easy operation, (5) to improve the activity of the catalyst, (6) to improve the selectivity of the product, (7) to provide conversion rate of raw materials, and (8) Improve the stability of the method.

Table 1 Example of ethanolamine amination reaction under hydrogen conditions in the examples

Claims

Rights request

A catalyst for synthesizing ethyleneamine, the catalyst comprising three main components: a main active component, an auxiliary agent, and an ammoniated carrier, wherein the main active component is selected from the group consisting of M and Co. One or more of the group consisting of one or more selected from the group consisting of Fe, Cu, Ru, Re, K, Zn, and B, and their respective oxides; The carrier is obtained by subjecting one or more carriers selected from the group consisting of SiO ₂ and A1 ₂ 0 _{3 to} amination treatment, and the amination treatment comprises: subjecting the carrier to an ammonia source at 150 to 400 ° C The temperature is in contact for 0.5 to 15 hours.

2. The catalyst according to claim 1, wherein the carrier has a specific surface area of from 150 to 350 m ² /g and an average pore diameter of from 8 to 80 nm.

3. The catalyst according to claim 1, wherein the ammonia source is selected from one or more of the group consisting of ammonia gas, liquid ammonia, ammonia water, and urea.

The catalyst according to claim 1, wherein the main active component accounts for 1 to 40% of the total weight of the catalyst.

The catalyst according to claim 1, wherein the main active component accounts for 5 to 30% of the total weight of the catalyst.

6. The catalyst according to claim 1, wherein the auxiliary agent accounts for 0.1 to 20% by weight of the total weight of the catalyst.

7. The catalyst according to claim 1, wherein the auxiliary agent accounts for 0.1 to 15% of the total weight of the catalyst.

A method for producing ethyleneamine from ethanolamine and ammonia, the method comprising: converting ethanolamine and ammonia to ethyleneamine under hydrogen conditions in the presence of the catalyst of claim 1.

9. The method according to claim 8, wherein the method is carried out at a temperature of 135 to 200 ° C, a pressure of 6.0 to 22.0 MPa, and a liquid space velocity of ethanolamine of OJ l.Sh- ¹ .

10. The method according to claim 8, wherein the catalyst is used in a hydrogen atmosphere and at a pressure of normal pressure, a temperature of 150 to 400 ° C, and a hydrogen space velocity of 500 to 4000 h" ¹ before use. Reductive activation.