阅读说明：本技术 一种聚醚多元醇临氢胺化制备聚醚胺的方法 (Method for preparing polyether amine by hydroamination of polyether polyol ) 是由 马雷 丁云杰 严丽 程显波 于 2019-12-03 设计创作，主要内容包括：本发明公开一种聚醚多元醇临氢胺化制备聚醚胺的方法,所述方法中的催化剂主要由多元金属活性组分、助剂及载体组成,其中多元金属活性组分包括M1-M2(M1为过渡金属Ni、Co和Cu的一种或两种以上,M2为过渡金属Re和Ru的一种或两种)。催化剂还可能包括助剂,助剂为Fe、Cr、Mn、B、Mg、Ba、Pt等金属或氧化物的一种或组合。本发明催化剂的特点为,在催化剂制备过程中,需要在配制的多元金属活性组分和助剂的前体液中添加络合剂或稳定剂以提高催化性能。使用本催化剂用于聚醚多元醇临氢胺化制备聚醚胺具有转化率高、催化性能稳定、目标产物选择性高、工艺过程简单,适用于连续式或间歇式反应器,市场前景广阔。(The invention discloses a method for preparing polyether amine by hydroamination of polyether polyol, wherein a catalyst in the method mainly comprises a multi-metal active component, an auxiliary agent and a carrier, wherein the multi-metal active component comprises M1-M2(M1 is one or more than two of transition metals of Ni, Co and Cu, and M2 is one or two of transition metals of Re and Ru). The catalyst may also include assistant, which is one or combination of Fe, Cr, Mn, B, Mg, Ba, Pt and other metal or oxide. The catalyst of the invention is characterized in that complexing agent or stabilizing agent is added into the precursor liquid of the prepared multi-metal active component and auxiliary agent in the preparation process of the catalyst to improve the catalytic performance. The catalyst is used for preparing polyether amine by hydroamination of polyether polyol, has the advantages of high conversion rate, stable catalytic performance, high target product selectivity, simple process, suitability for continuous or intermittent reactors and wide market prospect.)

1. A method for preparing polyether amine by hydrogenating and aminating polyether polyol is characterized in that a catalyst adopted by the method comprises a multi-metal active component, an auxiliary agent and a carrier or the multi-metal active component and the carrier;

the multi-element metal active component is a multi-element active metal element which is M1 and M2 metal elements; wherein M1 is selected from one or the combination of more than two of Co, Ni and Cu, and the mass of the M1 component accounts for 2-50% (preferably 5-25%) of the weight of the catalyst; wherein M2 is selected from one or the combination of more than two of Re and Ru, and the mass of the M2 component accounts for 0.1-30% (preferably 0.5-8%) of the weight of the catalyst;

the catalyst also can comprise an auxiliary agent, the auxiliary agent comprises an auxiliary agent element, the auxiliary agent element comprises one or more of Fe, Cr, Ce, B, Mg, Ba, Mn, La, Pt and Pd, and the auxiliary agent comprises the auxiliary agent element and/or an oxide of the auxiliary agent element; preferably, the auxiliary element is selected from one or more of Fe, B, Mn and Pd; the auxiliary agent accounts for 0-10% (preferably 0.5-4%) of the weight of the catalyst;

in the preparation process of the catalyst, at least one of an impregnation method or a precipitation method is selected in a solution added with a complexing agent or a stabilizing agent, and a multi-metal active component or an auxiliary agent is loaded on a carrier;

the complexing agent or stabilizer can be one or more selected from beta-cyclodextrin, citric acid, ethylenediamine, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), 2-bipyridine, phenanthroline, 1, 10-phenanthroline, and ammonium citrate.

2. The method according to claim 1, wherein the support is an inorganic porous material selected from Al₂O₃、SiO₂、CeO₂Activated carbon, Al₂O₃-SiO₂、TiO₂、ZrO₂One or more than two of H-ZSM-5 or H-beta molecular sieves; the specific surface area of the carrier is 20-800 m²The pore volume is 0.2-5.0 ml/g.

3. The method of claim 1, wherein the catalyst is prepared by a process comprising: impregnating a carrier with a solution containing an active metal element source, an additive element source (preferably, the solution contains the additive element source), a complexing agent or a stabilizing agent, drying and roasting to obtain the catalyst;

or adding a solution containing an active metal element source, an additive element source (preferably, the solution contains the additive element source), a complexing agent or a stabilizing agent and a precipitating agent into a suspension containing a carrier, precipitating, washing, drying and roasting to obtain the catalyst;

the roasting conditions are as follows: the temperature is 200-800 ℃, the time is 0.5-10.0 h, and when the used carrier is activated carbon in air and/or oxygen, the roasting atmosphere is one of nitrogen, argon and helium.

4. The method according to claim 1 or 3, wherein the molar ratio of the complexing agent or stabilizer to the multi-metal active component is 0.05:1 to 5:1 (preferably 0.1:1 to 2: 1).

5. The method of claim 3, wherein the source of the reactive metal element is selected from at least one of soluble salts of the reactive metal element;

the auxiliary element source is selected from at least one of soluble salts of auxiliary elements.

6. The process according to claim 1, characterized in that polyether amine is prepared by reacting raw material polyether polyol and aminating agent in the presence of a catalyst under hydrogen atmosphere;

the raw material polyether polyol comprises polyoxyethylene ether, polyoxypropylene ether or polyoxyethylene-polyoxypropylene ether, and the molecular structure is HO (CH)₂CHR¹O)_nH，R¹Is H or CH₃(ii) a The average molecular weight of the polyether polyol is in the range of 200-5000 g/mol;

the amination agent is selected from one or more than two of liquid ammonia, ammonia gas, ammonia water with the mass concentration of 5-28%, primary amine or tertiary amine, the primary amine comprises one or more than two of methylamine, ethylamine, n-propylamine, isopropylamine, n-pentylamine, n-hexylamine and aniline, and the secondary amine comprises one or more than two of dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, cyclohexylimine, piperidine and morpholine.

7. The method according to claim 6, wherein the reaction conditions are: the reaction temperature is 50-300 ℃, the reaction pressure is 2-30 MPa, and the volume space velocity of polyether polyol is 0.05-10 h^-1The volume space velocity of hydrogen is 10-2000 h^-1The molar ratio of the aminating agent to the polyether polyol is 1: 10-80: 1.

8. The method of claim 7, wherein the catalyst is subjected to a reduction activation treatment before use: the reducing gas is hydrogen, the pressure is 0.1-3 MPa, the temperature is 200-700 ℃, and the airspeed of the hydrogen is 20-5000 h^-1。

Technical Field

The invention relates to a method for preparing polyether amine by hydroamination of polyether polyol, in particular to a catalyst for mainly producing polyether amine by taking polyether polyol and an aminating agent as raw materials in a reactor under certain temperature, pressure and hydroamination conditions.

Background

The polyether amine is also called amine terminated polyether, and is a polymer with a polyether main chain and an amino terminal functional group. Common polyetheramines are polyoxyethylene diamine, polyoxypropylene diamine, polyoxyethylene-oxypropylene diamine, polytetramethylene ether diamine, and the like. The polyether amine has excellent reaction activity, toughness, viscosity, weather resistance and other performances, and is used as an important fine chemical intermediate and widely applied to the production fields of polyurethane, epoxy resin curing agents, gasoline detergent dispersants and the like.

The raw material for preparing polyether amine is mainly polyether polyol, and is divided into a catalytic amination method (ammonolysis method), a nitro-terminated method, a cyanoalkylation method, a hydrolysis method, an amino phenoxy method and the like according to different production processes. The research of the catalytic amination method starts in the sixties of the twentieth century, and polyether polyol and an aminating agent undergo dehydrogenation-condensation amination-hydrogenation to generate polyether amine under the hydrogen condition by using a transition metal catalyst. The byproduct in the process is only generated by water, the raw material utilization rate is high, the environment is protected, the economical efficiency is good, the process energy consumption is low, the product quality is high, and the method is the mainstream process for producing polyether amine in the world at present. At present, manufacturers for producing polyetheramines are mainly foreign chemical companies, such as basf, germany, hensemei. The domestic development starts late, the production scale is small, the production technology is laggard, and the domestic market needs are difficult to meet.

The catalytic amination method usually adopts transition metal with dehydrogenation-hydrogenation catalytic property as a catalyst active component, and the catalytic systems reported in the current patents comprise Ni supported catalysts, Raney Ni-Al, Ni-Cu-Cr, Ni-Cu-Mo or Co-Ni and the like. U.S. Pat. No. 3236895 discloses the use of Raney Ni to catalyze the formation of polyetheramines from polypropylene glycol (average molecular weight about 400g/mol) in an atmosphere of hydrogen and ammonia, with a polyetheramine yield of only 60% in the product, which catalyst is not suitable for use on high molecular weight polyether polyol substrates. U.S. Pat. No. 3654370 reports that Ni-Cu-Cr catalyst is used in the amination reaction catalyzed by polypropylene glycol (average molecular weight about 400g/mol) in a continuous reactor at 250 deg.C20MPa, the conversion rate is about 93 percent, and the selectivity of primary amine in the product is about 95 percent. U.S. Pat. No. 4766245 uses a Raney Ni-Al system catalyst, and the conversion and primary amine selectivity can reach 98% and 97% respectively when the average molecular weight of substrate polypropylene glycol is about 2000g/mol, the reaction pressure is 14MPa, and the temperature is 230 ℃ in a tank reactor. U.S. Pat. No. 8071814 reports a Raney Co-Al catalyst, a small amount of Cu additive is added in the catalyst, polyethylene glycol (average molecular weight is about 2000g/mol) is used for catalytic amination reaction in a tank reactor, the conversion rate is 94% after reaction for 20h under the conditions of 16MPa and 180 ℃, and the primary amine selectivity is 98%. The Ni-Al amorphous alloy prepared by the Chinese patent 101982482 is used for preparing polyether amine by polyether polyol, the reaction is carried out at the temperature of 200 ℃ in an autoclave and under the pressure of 15MPa, the conversion rate is more than 97 percent, and the primary amine content is more than 99 percent. Chinese patent 102389802 discloses a Ni-ZnO/Al alloy₂O₃The supported catalyst is used for preparing polyether amine, and when polypropylene glycol (average molecular weight is about 230g/mol, PPG230) is used as a substrate, the conversion rate reaches 91% and the purity of primary amine is 96% after the reaction is carried out for 4 hours in a reaction kettle at the temperature of 200 ℃ and under the pressure of 15 MPa.

It can be seen from the above review that the use of the catalysts of the prior art for the production of polyetheramines by the amination of polyether polyols has one or more problems of poor catalyst activity, poor catalyst stability, inability to achieve continuous production, low conversion, low primary amine yield, etc.

Disclosure of Invention

A process for preparing polyetheramines by hydroamination of polyether polyols, the catalyst in the process being capable of effecting one or more of the following: (1) the method comprises the following steps of (1) improving the conversion rate of polyether polyol, (2) improving the yield of polyether amine product, (3) reducing the generation of by-products, (4) inhibiting the occurrence of cracking reaction in the hydroamination reaction process, (5) improving the purity of polyether amine product, (6) reducing the cost of catalyst, (7) improving the stability of catalyst, (8) realizing continuous production operation, and (9) realizing easy operation.

According to one aspect of the application, a method for preparing polyether amine by hydroamination of polyether polyol is provided, wherein the catalyst in the method has high catalytic activity and high selectivity to the product polyether amine.

The catalyst is characterized by comprising a multi-metal active component, an auxiliary agent, a carrier three part or a multi-metal active component and a carrier two part, wherein a complexing agent or a stabilizing agent is required to be added in the preparation process of the catalyst.

The catalyst comprises a multi-metal active component, wherein the multi-metal active component is a multi-metal element, and the multi-metal element is M1 or M2. Wherein M1 is selected from one or more of Ni, Co and Cu; preferably, M1 is Ni, Ni-Co. Wherein M2 is selected from one or more of Re and Ru.

The catalyst may also comprise an auxiliary agent, and the auxiliary agent element comprises one or a combination of more than two of Fe, Cr, Ce, B, Mg, Ba, Mn, La, Pt and Pd; preferably, the auxiliary element is selected from one or a combination of more than two of Fe, B, Mn and Pd. The auxiliary agent comprises the auxiliary agent element and/or an oxide of the auxiliary agent element.

The catalyst carrier is an inorganic porous material selected from Al₂O₃、SiO₂、CeO₂Activated carbon, Al₂O₃-SiO₂、TiO₂、ZrO₂One or the combination of more than two of H-ZSM-5 or H-beta molecular sieve; preferably, the support is selected from Al₂O₃、SiO₂、CeO₂、Al₂O₃-SiO₂One or a combination of more than two.

The catalyst is characterized in that the weight of the multi-metal active component M1 accounts for 2-50% of the weight of the catalyst, preferably 5-25%; the weight of the multi-metal active component M2 accounts for 0.1-30% of the weight of the catalyst, preferably 0.5-8%; the weight of the auxiliary agent accounts for 0-10%, preferably 0.5-4% of the weight of the catalyst; the mol ratio of the complexing agent or the stabilizing agent to the multi-metal active component is 0.05: 1-5: 1, preferably 0.1: 1-2: 1; the specific surface area of the porous inorganic carrier is 20-800 m²A/g, preferably 150 to 500m²(ii)/g; the porous inorganic carrier has a pore volume of 0.2 to 5.0ml/g, preferably 0.4 to 2.0 ml/g.

The catalyst is characterized in that a complexing agent or a stabilizing agent is added into a prepared multi-metal active component and auxiliary agent precursor liquid in the preparation process of the catalyst.

The complexing agent or the stabilizing agent is selected from one or more than two of beta-cyclodextrin, citric acid, ethylenediamine, nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), 2-bipyridine, phenanthroline, 1, 10-phenanthroline, ammonium citrate and the like. Preferably, the complexing agent or stabilizing agent is selected from one or more of beta-cyclodextrin, ethylenediamine, Ethylene Diamine Tetraacetic Acid (EDTA) and ammonium citrate.

The mol ratio of the complexing agent or the stabilizing agent to the multi-metal active component is 0.05: 1-5: 1, and preferably 0.1: 1-2: 1. .

More specifically, the catalyst is characterized by comprising a multi-metal active element, an auxiliary element, a carrier three part or a multi-metal active component and a carrier two part. In the preparation process of the catalyst, a complexing agent or a stabilizing agent is required to be added in precursor liquid for preparing the multi-metal active elements and/or the auxiliary elements.

The complexing agent or the stabilizing agent is selected from one or more than two of beta-cyclodextrin, citric acid, ethylenediamine, nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), 2-bipyridine, phenanthroline, 1, 10-phenanthroline, ammonium citrate and the like.

Preferably, the complexing agent or stabilizing agent is selected from one or more of beta-cyclodextrin, ethylenediamine, Ethylene Diamine Tetraacetic Acid (EDTA) and ammonium citrate.

The mol ratio of the complexing agent or the stabilizing agent to the multi-metal active component is 0.05: 1-5: 1.

Preferably, the molar ratio of the complexing agent or the stabilizing agent to the multi-metal active component is 0.1: 1-2: 1.

The multi-element metal active component comprises two parts of active metal elements M1 and M2. Wherein M1 is selected from one or more of Ni, Co and Cu; m2 is selected from one or the combination of more than two of Re and Ru; the weight of M1 accounts for 2-50% of the weight of the catalyst; the weight of M2 is 0.1-30% of the weight of the catalyst.

Preferably, the weight of the active metal element M1 accounts for 5-25% of the weight of the catalyst.

Preferably, the weight of the active metal element M2 accounts for 0.5-8% of the weight of the catalyst.

Optionally, the catalyst may further comprise an auxiliary agent, wherein the auxiliary agent comprises an auxiliary agent element, and the auxiliary agent element is one or a combination of more than two of Fe, Cr, Ce, B, Mg, Ba, Mn, La, Pt and Pd. The weight of the auxiliary element accounts for 0-10.0% of the weight of the catalyst.

Preferably, the auxiliary element is selected from one or a combination of more than two of Fe, B, Mn and Pd.

Preferably, the weight of the auxiliary element accounts for 0.5-4% of the weight of the catalyst.

The auxiliary agent comprises the auxiliary agent element and/or an oxide of the auxiliary agent element.

The carrier is a porous inorganic material selected from Al₂O₃、SiO₂、CeO₂Activated carbon, Al₂O₃-SiO₂、TiO₂、ZrO₂One or more than two of H-ZSM-5 or H-beta molecular sieve.

Preferably, the support is selected from Al₂O₃、SiO₂、CeO₂、Al₂O₃-SiO₂One or a combination of more than two.

Optionally, the specific surface area of the carrier is 20-800 m²The pore volume is 0.2 to 5.0 ml/g.

Preferably, the specific surface area of the carrier is 150-500 m²The pore volume is 0.4 to 2.0 ml/g.

According to another aspect of the present application, there is provided a method for preparing the catalyst. The preparation method is simple, convenient and easy to operate, and is suitable for large-scale production.

The preparation method of the catalyst is characterized in that the catalyst adopts an impregnation method or a precipitation method, and after a complexing agent or a stabilizing agent is added, a multi-metal active component and/or an auxiliary agent are/is loaded on a carrier.

In a preferred embodiment, the multi-metal active component and/or the auxiliary agent can be loaded on the carrier material by an impregnation method after the complexing agent or the stabilizing agent is added.

Alternatively, in the impregnation method embodiment, a co-impregnation method or a stepwise impregnation method may be adopted, and after adding the complexing agent or the stabilizer, the multi-metal active component and/or the auxiliary agent is/are supported on the carrier.

Alternatively, the impregnation method may include the steps of: preparing an aqueous solution containing active components M1 and M2(M1 comprises Ni, Co and Cu; M2 comprises Re and Ru), an auxiliary agent, a complexing agent or a stabilizing agent, wherein the weight of the active component M1 accounts for 2-50% of the weight of the catalyst, the weight of the active component M2 accounts for 0.1-30% of the weight of the catalyst, the weight of the auxiliary agent accounts for 0-10% of the weight of the catalyst, and the molar ratio of the complexing agent or the stabilizing agent to the multi-element metal active component is 0.05: 1-5: 1. And (3) impregnating the carrier with an aqueous solution containing the multi-metal active component and the auxiliary agent, naturally airing, drying and roasting.

Alternatively, the impregnation method may be one impregnation or stepwise impregnation.

Optionally, the roasting temperature is usually 200-800 ℃, the heating rate is usually 0.5-20 ℃/min, and the roasting time is usually 0.5-10 h. The roasting atmosphere is air and/or oxygen. When the carrier is active carbon, the roasting atmosphere is one of nitrogen, argon and helium.

Alternatively, the multi-metal active component and/or the auxiliary agent may be supported on the carrier by a precipitation method after addition of the complexing agent or the stabilizer.

Alternatively, the step of preparing the catalyst by the precipitation method can be as follows: the support material is suspended in water, the active components M1 and M2(M1 comprises Ni, Co, Cu; M2 comprises Re, Ru), soluble precursors of the auxiliaries and complexing agents or stabilizers are added, and then the precursors are precipitated on the suspended support by adding a precipitating agent. The weight of the active component M1 accounts for 2-50% of the weight of the catalyst, the weight of the active component M2 accounts for 0.1-30% of the weight of the catalyst, the weight of the auxiliary agent accounts for 0-10% of the weight of the catalyst, and the molar ratio of the complexing agent or the stabilizer to the multi-element metal active component is 0.05: 1-5: 1. And (4) aging, washing, filtering, drying and roasting the precipitated sample.

Optionally, the precipitant is preferably inorganic alkali, ammonium salt, preferably at least one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate, ammonium hydroxide, ammonium halide.

Optionally, the precipitation temperature may be 20 to 90 ℃, preferably 40 to 70 ℃.

Optionally, the roasting temperature is usually 200-800 ℃, the heating rate is usually 0.5-20 ℃/min, and the roasting time is usually 0.5-10 h. The roasting atmosphere is air and/or oxygen. When the carrier is active carbon, the roasting atmosphere is one of nitrogen, argon and helium.

The catalyst is a solid, and optionally, the shape of the catalyst includes powder, microsphere, sphere, granule, tablet, cylinder, ring and the like.

In the preparation process of the catalyst, specifically, the complexing agent or the stabilizing agent is selected from one or more of beta-cyclodextrin, citric acid, ethylenediamine, nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTPA), 2-bipyridine, phenanthroline, 1, 10-phenanthroline, ammonium citrate and the like.

Preferably, the complexing agent or stabilizing agent is selected from one or more of beta-cyclodextrin, ethylenediamine, Ethylene Diamine Tetraacetic Acid (EDTA) and ammonium citrate.

The multi-metal active components M1 and M2(M1 comprises Ni, Co and Cu; M2 comprises Re and Ru) are composed of at least two metal elements.

Optionally, the multi-element metal active component precursor comprises soluble salts of Ni, Co, Cu, Re and Ru.

Optionally, the promoter precursor comprises a soluble precursor of the promoter elements Fe, Cr, Ce, B, Mg, Ba, Mn, La, Pt, Pd.

Preferably, the soluble salt of the active metal element Ni comprises at least one of nickel nitrate, nickel acetate, nickel chloride, nickel sulfate, nickel citrate and nickel acetylacetonate.

Preferably, the soluble salt of the active metal element Co used comprises at least one of cobalt chloride, cobalt nitrate, cobalt acetate, cobalt oxalate, cobalt carbonate and cobalt sulfate.

Preferably, the soluble salt of the active metal element Cu comprises at least one of copper nitrate, copper chloride, copper carbonate and copper sulfate.

Preferably, the soluble salt of the active metal element Re used comprises at least one of ammonium rhenate, perrhenic acid, rhenium chloride.

Preferably, the soluble salt of the active metal element Ru comprises at least one of ruthenium chloride, ruthenium iodide, ruthenium acetate, potassium chlororuthenate, sodium chlororuthenate, ammonium chlororuthenate, ruthenium carbonyl chloride, ruthenium triphenylphosphine chloride and ruthenium p-cymene dichloride.

Preferably, the source of the auxiliary element is selected from at least one of soluble salts of auxiliary elements. Preferably, the soluble salt of the auxiliary metal element comprises at least one of a nitrate, a sulfate or a chloride of the auxiliary element; the assistant element is B, and the assistant element source is boric acid.

According to still another aspect of the present application, a catalyst is provided, which can significantly improve catalytic activity, selectivity and stability when used in the preparation of polyether amine by polyether polyol amination under hydrogen condition.

The catalyst, the catalyst prepared according to the method, needs to be subjected to activation treatment before use.

Specifically, the catalyst prepared by the impregnation method or the precipitation method is usually activated in a reducing atmosphere before use.

The reducing atmosphere can be hydrogen or a mixed gas of hydrogen and other inert gases, and the other inert gases comprise at least one of nitrogen, argon and helium. The reducing atmosphere is preferably hydrogen.

Optionally, the activation treatment is carried out in a hydrogen atmosphere, and the pressure is 0.1-3 MPa, preferably 0.1-0.5 MPa; the volume space velocity of hydrogen gas is 20-5000 h^-1Preferably 100 to 3000 hours^-1(ii) a The temperature is 200-700 ℃, preferably 300-550 ℃; the reduction time is 0.5-10 h, preferably 1.5-6 h.

The method for producing polyether amine by hydroamination of polyether polyol is characterized in that raw materials containing an aminating agent and polyether polyol are introduced into a reactor filled with a catalyst in a hydrogen atmosphere to react to prepare polyether amine.

The catalyst is selected from the group consisting of the catalysts described above, and catalysts prepared according to the methods described above. The catalyst is subjected to the above-mentioned activation treatment before the reaction.

The reactor comprises a continuous reactor and a batch reactor. Wherein the continuous reactor is selected from a fixed bed reactor, a continuous stirred tank reactor, a slurry bed reactor and a fluidized bed reactor; the batch reactor is selected from autoclave reactors. Fixed bed reactors and autoclave reactors are preferred.

In a preferred embodiment, the hydroamination of polyether polyols can be carried out in a fixed-bed reactor.

Alternatively, the amination reaction operating step carried out on a fixed bed reactor may be: a quantity of catalyst is charged to the reactor and activated under selected conditions. And after the activation is finished, adjusting the temperature and the pressure of the reaction system to set values. After the hydrogen flow rate is stabilized, the reaction substrate polyether polyol and aminating agent are pumped into the reactor. The reacted materials include gas phase materials and liquid phase materials. Wherein, the gas-phase material is discharged through a backpressure valve; the liquid phase material flows through the high-pressure tank and the deamination tank and then enters the product tank for storage. The reaction system pressure is controlled by a back pressure valve.

In one embodiment, the catalyst is used for producing polyether amine by polyether polyol amination, and is characterized in that a liquid polyether polyol and liquid ammonia mixture is pumped into a preheater, mixed with hydrogen, preheated to 100 ℃ and then fed into a fixed bed reactor. The polyether polyol and the liquid ammonia are dissolved and diluted without adding any solvent.

In the alternative, the polyether polyol amination reaction may be carried out on an autoclave reactor.

Alternatively, the amination reaction operating step carried out on the autoclave reactor may be: taking a certain amount of catalyst for activation treatment, moving the activated catalyst into a high-pressure kettle under the protection of inert atmosphere, adding an aminating agent and a polyether polyol raw material, and sealing the reaction kettle. After repeatedly charging and discharging hydrogen for 3 times, the temperature and the pressure of the reaction kettle are adjusted to selected values. After reacting for a certain time at a certain stirring speed, filtering and vacuum-pumping the reaction product to obtain the polyether amine product.

The raw material polyether polyol is characterized in that the polyether polyol comprises polyoxyethylene ether, polyoxypropylene ether or polyoxyethylene-polyoxypropylene ether, and the molecular structure is HO (CH)₂CHR¹O)_nH，R¹Is H or CH₃。

The average molecular weight of the polyether polyol is 200-5000 g/mol.

Preferably, the polyether polyol is selected from polyoxyethylene ether (average molecular weight about 2000g/mol), polyoxyethylene ether (average molecular weight about 600g/mol), polyoxypropylene ether (average molecular weight about 230g/mol), polyoxypropylene ether (average molecular weight about 400g/mol), polyoxypropylene ether (average molecular weight about 600g/mol), polyoxypropylene ether (average molecular weight about 2000 g/mol).

The aminating agent is selected from liquid ammonia, ammonia gas, ammonia water with the mass concentration of 5-28%, primary amine or tertiary amine.

The primary amine comprises methylamine, ethylamine, n-propylamine, isopropylamine, n-pentylamine, n-hexylamine and aniline.

The secondary amine comprises dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, cyclohexylimine, piperidine and morpholine.

Preferably, the aminating agent is selected from the group consisting of liquid ammonia, methylamine, dimethylamine.

Optionally, the reaction conditions are: the reaction temperature is 50-300 ℃, and preferably 140-240 ℃; the reaction pressure is 2-30 MPa, preferably 6-24 MPa; the volume airspeed of the polyether polyol is 0.05-10 h^-1Preferably 0.3 to 3 hours^-1(ii) a The volume airspeed of the hydrogen is 10-2000 h^-1Preferably 50 to 500 hours^-1(ii) a The molar ratio of the aminating agent to the polyether polyol is 1: 10-80: 1, preferably 5: 1-20: 1.

The amination reaction product is analyzed by a titration method, and the titration method operation process is carried out according to the ASTM D2074-07(2013) standard method.

The catalyst of the invention is characterized in that complexing agent or stabilizing agent is added into the precursor liquid of the prepared multi-metal active component and auxiliary agent in the preparation process of the catalyst to improve the catalytic performance. The catalyst is used for preparing polyether amine by hydroamination of polyether polyol and has the advantages of high conversion rate, stable catalytic performance, high target product selectivity, simple process and the like. The catalyst has simple preparation process, is suitable for a continuous or intermittent reactor, and has wide market prospect.

Detailed Description

Example 1

The catalyst is 10% Co-2% Re/Al₂O₃. Weighing 8.8 g of 20-40 mesh Al₂O₃Drying at 120 deg.C for 4 hr before use, and preparing into 20ml solution containing 4.94 g Co (NO)₃)₂·6H₂O, 0.29 g NH₄ReO₄1.92 g of an aqueous solution of beta-cyclodextrin, by impregnating said Al with this aqueous solution₂O₃And naturally drying the carrier, drying at 100 ℃ for 4h, and roasting at 600 ℃ for 4h, wherein the heating rate is 4 ℃/min.

4g of the catalyst (20-40 meshes) is weighed and placed in the middle of a fixed bed reactor, and the rest space of the reactor is filled with quartz sand. The catalyst activation conditions were: 0.1MPa, 450 ℃ and 500h of hydrogen volume space velocity^-1And the time is 2 h. The reaction conditions are as follows: the pressure is 6MPa, the temperature is 170 ℃, and the volume space velocity of hydrogen is 100h^-1PPG230 (polyoxypropylene ether, average molecular weight: about 230g/mol): NH₃1:10 (molar ratio), PPG230 liquid hourly space velocity 0.6h^-1. After 20h of reaction evaluation, the chemical analysis result of the product is as follows: the reaction conversion rate is 95.2%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 99.1%.

The value of n is about 2 to 3.

Example 2

The catalyst is 10% Ni-10% Co-1% Re-1% Ru-0.5% Ce/Al₂O₃. Weighing 7.8 g of 20-40 mesh Al₂O₃Drying at 120 deg.C for 4 hr before use, and preparing 20ml of the product containing 4.95 g Ni (NO)₃)₂·6H₂O, 4.94 g Co (NO)₃)₂·6H₂O, 0.14 g NH₄ReO₄0.26 g RuCl₃·3H₂O, 0.15 g Ce (NO)₃)₃·6H₂O, 4.08 g of an aqueous solution of ethylenediamine, and Al as defined above impregnated with this aqueous solution₂O₃And naturally drying the carrier, drying at 100 ℃ for 4h, and roasting at 400 ℃ for 6h, wherein the heating rate is 5 ℃/min.

4g of the catalyst (20-40 meshes) is weighed and placed in the middle of a fixed bed reactor, and the rest space of the reactor is filled with quartz sand. The catalyst activation conditions were: 0.1MPa, 400 ℃ and 500h of hydrogen volume space velocity^-1And the time is 2 h. The reaction conditions are as follows: the pressure is 8MPa, the temperature is 200 ℃, and the volume space velocity of hydrogen is 200h^-1PPG230 (polyoxypropylene ether, average molecular weight: about 230g/mol): NH₃1:10 (molar ratio), PPG230 liquid hourly space velocity 0.4h^-1. After 20h of reaction evaluation, the chemical analysis result of the product is as follows: the reaction conversion rate is 98.6%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 99.0%.

The value of n is about 2 to 3.

Example 3

The catalyst is 20 percent of Ni-2 percent of Re/SiO₂. Weighing 7.8 g of 100 mesh SiO₂Drying at 120 deg.C for 4 hr before use to remove SiO₂Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. A20 ml aliquot of the mixture containing 9.91 grams of Ni (NO)₃)₂·6H₂O, 0.29 g NH₄ReO₄1.93 grams of beta-cyclodextrin precursor fluid. The precipitant used was a 4mol/L KOH solution. Dripping the precursor liquid and the precipitant into the suspension at the speed of 1mL/min, keeping the pH value at 9 until the precipitate is completely precipitated, washing the precipitate to be neutral by deionized water, filtering, airing, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 6 hours, and increasing the temperature at the speed of 2 ℃/min.

4g of the above catalyst (100 mesh) was weighed out and placed in the middle of a fixed bed reactor, and the remaining space of the reactor was filled with quartz sand. The catalyst activation conditions were: 0.1MPa, 400 ℃ and 300h of hydrogen volume space velocity^-1And the time is 6 h. The reaction conditions are as follows: the pressure is 8MPa, the temperature is 210 ℃, and the volume space velocity of hydrogen is 200h^-1PPG230 (polyoxypropylene ether, Pine)Average molecular weight of about 230g/mol) NH₃1:15 (molar ratio), PPG230 liquid hourly space velocity 0.5h^-1. After 20h of reaction evaluation, the chemical analysis result of the product is as follows: the reaction conversion rate is 99.1%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 98.9%.

The value of n is about 2 to 3.

Example 4

The catalyst is 10 percent of Ni-5 percent of Cu-3 percent of Re-1 percent of B/SiO₂. Weighing 8.1 g of 20-40 mesh SiO₂Drying at 120 deg.C for 4 hr before use, and preparing 20ml of the product containing 4.95 g Ni (NO)₃)₂·6H₂O, 1.48 g Cu (NO)₃)₂0.43 g NH₄ReO₄0.57 g H₃BO₃6.08 g of ammonium citrate in water, impregnating the SiO₂And naturally drying the carrier, drying at 100 ℃ for 4h, and roasting at 400 ℃ for 6h, wherein the heating rate is 5 ℃/min.

4g of the catalyst (20-40 meshes) is weighed and placed in the middle of a fixed bed reactor, and the rest space of the reactor is filled with quartz sand. The catalyst activation conditions were: 0.1MPa, 400 ℃ and 1000h of hydrogen volume space velocity^-1And the time is 8 h. The reaction conditions are as follows: the pressure is 10MPa, the temperature is 230 ℃, and the volume space velocity of hydrogen is 300h^-1PPG2000 (polyoxypropylene ether, average molecular weight: about 2000g/mol): NH₃1:15 (molar ratio), PPG2000 liquid hourly space velocity 0.3h^-1. After 20h of reaction evaluation, the chemical analysis result of the product is as follows: the reaction conversion rate is 98.3%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 99.2%.

The value of n is about 30 to 37.

Example 5

The catalyst is 10 percent of Co-5 percent of Ni-5 percent of Cu-2 percent of Ru/SiO₂. Weighing 7.8 g of 40-60 mesh SiO₂Drying at 120 deg.C for 4 hr before use, and preparing into 20ml solution containing 4.94 g Co (NO)₃)₂·6H₂O, 2.48 g Ni (N)O₃)₂·6H₂O, 1.48 g Cu (NO)₃)₂0.52 g RuCl₃·3H₂O, 9.91 g of an aqueous solution of ethylenediaminetetraacetic acid, impregnating the SiO₂And naturally drying the carrier, drying at 100 ℃ for 4h, and roasting at 500 ℃ for 8h, wherein the heating rate is 10 ℃/min.

4g of the catalyst (40-60 meshes) is weighed and placed in the middle of a fixed bed reactor, and the rest space of the reactor is filled with quartz sand. The catalyst activation conditions were: 0.1MPa, 450 ℃ and 600h of hydrogen volume space velocity^-1And the time is 4 h. The reaction conditions are as follows: the pressure is 10MPa, the temperature is 250 ℃, and the volume space velocity of hydrogen is 300h^-1PPG2000 (polyoxypropylene ether, average molecular weight: about 2000g/mol): NH₃1:15 (molar ratio), PPG2000 liquid hourly space velocity 1.0h^-1. After 20h of reaction evaluation, the chemical analysis result of the product is as follows: the reaction conversion rate is 97.7%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 99.4%.

The value of n is about 30 to 37.

Example 6

The catalyst is 20 percent of Cu-2 percent of Re-2 percent of Ru/Al₂O₃. Weighing 7.6 g of 40-60 mesh Al₂O₃Drying at 120 deg.C for 4 hr before use, and preparing 20ml solution containing 5.90 g Cu (NO)₃)₂0.29 g NH₄ReO₄0.52 g RuCl₃·3H₂O, 7.42 g of an aqueous solution of ethylenediaminetetraacetic acid, impregnating the Al mentioned above₂O₃And naturally drying the carrier, drying at 100 ℃ for 4h, and roasting at 700 ℃ for 2h, wherein the heating rate is 10 ℃/min.

Weighing 4g of the catalyst (40-60 meshes) and placing the catalyst in a tube furnace for reduction and activation. The catalyst activation conditions were: 0.1MPa, 500 ℃ and 1000h of hydrogen volume space velocity^-1And the time is 8 h. Transferring the activated catalyst into an autoclave reactor in inert atmosphere, weighing 50g PPG2000 (polyoxypropylene ether, average molecular weight of about 2000g/mol) in a high-pressure reactor, adding 20g liquid ammonia into the reactor, charging hydrogen to 10MPa, stirring at 250 deg.C and stirring speedReacting for 6 hours at 2000 r/min, and filtering to obtain the product after reaction. Chemical analysis of the product: the reaction conversion rate is 99.5%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 99.0%.

The value of n is about 30 to 37.

Example 7

The catalyst is 25 percent of Ni-2 percent of Ru-1 percent of Pd/Al₂O₃. Weighing 7.3 g of 100 mesh Al₂O₃Drying at 120 deg.C for 4 hr before use, and mixing Al₂O₃Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. A20 ml aliquot of the mixture containing 12.39 g of Ni (NO)₃)₂·6H₂O, 0.52 g RuCl₃·3H₂O, 0.17 g PdCl₂5.07 g of ammonium citrate. The precipitant used was a 4mol/L KOH solution. Dripping the precursor liquid and the precipitant into the suspension at the speed of 1mL/min, keeping the pH value at 9 until the precipitate is completely precipitated, washing the precipitate to be neutral by deionized water, filtering, airing, drying at 120 ℃ for 4 hours, roasting at 450 ℃ for 6 hours, and increasing the temperature at the speed of 1 ℃/min.

4g of the catalyst (100 mesh) was weighed and placed in a tube furnace for reduction activation. The catalyst activation conditions were: 0.1MPa, 450 ℃ and 1500h of hydrogen volume space velocity^-1And the time is 6 h. The activated catalyst is moved into an autoclave reactor in inert atmosphere, 100g of PEG400 (polyoxyethylene ether, average molecular weight is about 400g/mol) is weighed and placed into a high-pressure reaction kettle, 170g of liquid ammonia is added into the reaction kettle, hydrogen is filled into the reaction kettle to 8MPa, the reaction is carried out for 8h at the reaction temperature of 210 ℃ and the stirring speed of 2000 r/min, and the product is obtained by filtration after the reaction. Chemical analysis of the product: the reaction conversion rate is 98.3%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 99.3%.

The value of n is about 3 to 4.

Example 8

Catalyst and process for preparing same10% Co-5% Cu-2% Re/Al₂O₃-SiO₂. Weighing 8.3 g of 40-60 mesh Al₂O₃-SiO₂Drying at 120 deg.C for 4 hr before use, and preparing into 20ml solution containing 4.94 g Co (NO)₃)₂·6H₂O, 1.47 g Cu (NO)₃)₂0.29 g NH₄ReO₄2.23 g of an aqueous solution of ethylenediamine, impregnated with Al as described above₂O₃-SiO₂And naturally drying the carrier, drying at 100 ℃ for 4h, and roasting at 500 ℃ for 5h, wherein the heating rate is 10 ℃/min.

4g of the catalyst (40-60 meshes) is weighed and placed in the middle of a fixed bed reactor, and the rest space of the reactor is filled with quartz sand. The catalyst activation conditions were: 0.1MPa, 350 ℃ and 300h of hydrogen volume space velocity^-1And the time is 4 h. The reaction conditions are as follows: the pressure is 10MPa, the temperature is 200 ℃, and the volume space velocity of hydrogen is 150h^-1PEG400 (polyoxyethylene ether, average molecular weight about 400g/mol): NH₃1:20 (molar ratio), PEG400 liquid hourly space velocity of 1.5h^-1. Chemical analysis results of the product after 500h of reaction evaluation: the reaction conversion rate is 93.8%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 98.7%.

The value of n is about 3 to 4.

Example 9

The catalyst is 20 percent of Ni-1 percent of Re-3 percent of Re/Al₂O₃. Weighing 7.6 g of 100 mesh Al₂O₃Drying at 120 deg.C for 4 hr before use, and mixing Al₂O₃Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. A20 ml aliquot of the mixture containing 9.91 grams of Ni (NO)₃)₂·6H₂O, 0.14 g NH₄ReO₄0.52 g RuCl₃·3H₂O, 3.86 grams of beta-cyclodextrin precursor fluid. The precipitant used was a 4mol/L NaOH solution. Dripping precursor solution and precipitant into the above suspension at a rate of 1mL/min, maintaining pH at 8 until precipitation is complete, washing precipitate with deionized water to neutrality, filtering, air drying, oven drying at 120 deg.C for 4 hr, baking at 550 deg.C for 4 hr, and heating to literThe temperature rate was 5 ℃/min.

4g of the above catalyst (100 mesh) was weighed out and placed in the middle of a fixed bed reactor, and the remaining space of the reactor was filled with quartz sand. The catalyst activation conditions were: 0.1MPa, 450 ℃ and 600h of hydrogen volume space velocity^-1And the time is 8 h. The reaction conditions are as follows: the pressure is 12MPa, the temperature is 230 ℃, and the volume space velocity of hydrogen is 150h^-1PEG2000 (polyoxyethylene ether, average molecular weight about 2000g/mol): NH₃1:30 (molar ratio), PEG2000 liquid hourly space velocity of 0.8h^-1. After 20h of reaction evaluation, the chemical analysis result of the product is as follows: the reaction conversion rate is 98.5%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 99.1%.

The value of n is about 40 to 49.

Example 10

The catalyst is 5% Co-10% Ni-2% Re-2% Fe/Al₂O₃-SiO₂. Weighing 7.6 g of 20-40 mesh Al₂O₃-SiO₂Dried at 120 ℃ for 4 hours before use to prepare 20ml of a solution containing 2.47 g of Co (NO)₃)₂·6H₂O, 4.95 g Ni (NO)₃)₂·6H₂O, 0.29 g NH₄ReO₄0.87 g Fe (NO)₃)₃5.79 g of an aqueous solution of beta-cyclodextrin, impregnated with Al as defined above₂O₃-SiO₂And naturally drying the carrier, drying at 100 ℃ for 4h, and roasting at 600 ℃ for 3h, wherein the heating rate is 5 ℃/min.

4g of the catalyst (20-40 meshes) is weighed and placed in the middle of a fixed bed reactor, and the rest space of the reactor is filled with quartz sand. The catalyst activation conditions were: 0.1MPa, 550 ℃ and 1000h of hydrogen volume space velocity^-1And the time is 10 h. The reaction conditions are as follows: the pressure is 12MPa, the temperature is 250 ℃, and the volume space velocity of hydrogen is 150h^-1PEG2000 (polyoxyethylene ether, average molecular weight about 2000g/mol): NH₃1:30 (molar ratio), PEG2000 liquid hourly space velocity of 0.5h^-1. After 20h of reaction evaluation, the chemical analysis result of the product is as follows: the reaction conversion rate is 99.2%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 98.2%.

The value of n is about 40 to 49.

Comparative example 1

The catalyst is 20 percent of Co-2 percent of Fe/Al₂O₃. Weighing 7.8 g of 100 mesh Al₂O₃Drying at 120 deg.C for 4 hr before use, and mixing Al₂O₃Dispersing in water to form a suspension, and stirring at a constant temperature of 50 deg.C with medium speed. A20 ml aliquot of the mixture containing 9.88 g of Co (NO)₃)₂·6H₂O, 0.87 g Fe (NO)₃)₃The precursor liquid of (4). The precipitant used was 6mol/L NaOH solution. Dripping the precursor liquid and the precipitant into the suspension at the speed of 1mL/min, keeping the pH value at 8 until the precipitate is completely precipitated, washing the precipitate to be neutral by deionized water, filtering, airing, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 4 hours, and increasing the temperature at the speed of 5 ℃/min.

4g of the above catalyst (100 mesh) was weighed out and placed in the middle of a fixed bed reactor, and the remaining space of the reactor was filled with quartz sand. The catalyst activation conditions were: 0.1MPa, 450 ℃ and 500h of hydrogen volume space velocity^-1And the time is 10 h. The reaction conditions are as follows: the pressure is 10MPa, the temperature is 200 ℃, and the volume space velocity of hydrogen is 200h^-1PEG400 (polyoxyethylene ether, average molecular weight about 400g/mol): NH₃1:20 (molar ratio), PEG400 liquid hourly space velocity of 0.6h^-1. After 20h of reaction evaluation, the chemical analysis result of the product is as follows: the reaction conversion rate is 66.7%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 78.9%.

The value of n is about 3 to 4.

Comparative example 2

The catalyst was commercial raney Ni.

4g of the above catalyst (40-60 mesh) was weighed into the middle of a fixed bed reactor, and the remaining space of the reactor was filled with quartz sand. The catalyst activation conditions were: 0.1MPa, 400 ℃ and 1000h of hydrogen volume space velocity^-1And the time is 5 h. The reaction conditions are: the pressure is 12MPa, the temperature is 220 ℃, and the volume space velocity of hydrogen is 150h^-1PPG230 (polyoxypropylene ether, average molecular weight: about 230g/mol): NH₃1:30 (molar ratio), PPG230 liquid hourly space velocity 0.6h^-1. After 20h of reaction evaluation, the chemical analysis result of the product is as follows: the reaction conversion rate is 34.1%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 85.6%.

The value of n is about 2 to 3.

Comparative example 3

The catalyst is 20 percent of Ni-1 percent of Re-2 percent of Fe/Al₂O₃. Weighing 7.7 g of 20-40 mesh Al₂O₃Dried at 120 ℃ for 4 hours before use, and prepared into 20ml containing 9.91 g of Ni (NO)₃)₂·6H₂O, 0.14 g NH₄ReO₄0.87 g Fe (NO)₃)₃14.28 g of an aqueous solution of ethylenediamine, impregnated with Al as described above₂O₃And naturally drying the carrier, drying at 100 ℃ for 4h, and roasting at 500 ℃ for 3h, wherein the heating rate is 5 ℃/min.

4g of the catalyst (20-40 meshes) is weighed and placed in the middle of a fixed bed reactor, and the rest space of the reactor is filled with quartz sand. The catalyst activation conditions were: 0.1MPa, 450 ℃ and 1000h of hydrogen volume space velocity^-1And the time is 10 h. The reaction conditions are as follows: the pressure is 12MPa, the temperature is 250 ℃, and the volume space velocity of hydrogen is 150h^-1PEG2000 (polyoxyethylene ether, average molecular weight about 2000g/mol): NH₃1:30 (molar ratio), PEG2000 liquid hourly space velocity of 0.7h^-1. After 20h of reaction evaluation, the chemical analysis result of the product is as follows: the reaction conversion rate is 49.2%, the structural formula of the main product polyether amine is as follows, and the selectivity of the main product is 78.2%.

The value of n is about 40 to 49.

Comparative example 4

The catalyst is 15 percent of Cu-2 percent of Re-2 percent of Ru/SiO₂. Weighing 8.1 g of 40-60 mesh SiO₂Drying at 120 deg.C for 4 hr before use20ml of a solution containing 4.43 g of Cu (NO)₃)₂0.29 g NH₄ReO₄0.52 g RuCl₃·3H₂O, 0.96 g of an aqueous solution of potassium sodium tartrate, impregnating the SiO₂And naturally drying the carrier, drying at 100 ℃ for 4h, and roasting at 500 ℃ for 2h, wherein the heating rate is 10 ℃/min.

Weighing 4g of the catalyst (40-60 meshes) and placing the catalyst in a tube furnace for reduction and activation. The catalyst activation conditions were: 0.1MPa, 500 ℃ and 1000h of hydrogen volume space velocity^-1And the time is 8 h. The activated catalyst is moved into an autoclave reactor in inert atmosphere, 50g of PPG2000 (polyoxypropylene ether, average molecular weight is about 2000g/mol) is weighed and placed into a high-pressure reaction kettle, 20g of liquid ammonia is added into the reaction kettle, hydrogen is filled into the reaction kettle to 10MPa, the reaction is carried out for 6h at the reaction temperature of 250 ℃ and the stirring speed of 2000 r/min, and the product is obtained after the reaction and filtration. Chemical analysis of the product: the reaction conversion rate is 63.2%, the structural formula of the main product polyether amine is shown as follows, and the selectivity of the main product is 79.1%.

The value of n is about 30 to 37.

The evaluation results show that: when the supported multi-metal M1-M2 catalyst (M1 is one or more than two of transition metals of Ni, Co and Cu, and M2 is one or two of transition metals of Re and Ru) is used for preparing polyether amine by hydroamination of polyether polyol, the conversion rate of the polyether polyol and the yield of the target product polyether amine can be improved, and better stability is shown. As can be seen from the comparative examples, the catalysts prepared with the single metal catalyst, without or with an excess of stabilizer or complexing agent, for hydroamination of polyether polyols, have one or more disadvantages of poor activity, poor polyetheramine selectivity, susceptibility to deactivation, etc. In conclusion, the catalyst prepared by the method has excellent reaction catalytic performance when used for preparing polyether amine by hydroamination of polyether polyol, and has wide industrial application prospect.