Amination reaction catalyst as well as preparation method and application thereof

Abstract

The invention relates to an amination reaction catalyst and a preparation method and application thereof.According to the catalyst, a metal salt solution and a precipitant are co-precipitated through a co-precipitation method, the precipitation solution is washed and filtered multiple times till the conductivity of filtrate is smaller than 100 microseconds / m, deionized water is added into a filter cake to prepare a solution, and the solution is dried to obtain the amination reaction catalyst. The method comprises the following steps: treating a solution by using ion exchange resin modified by beta-diketone organic matters, adsorbing residual Na < + > in the solution, filtering the solution to obtain a filter cake, and drying and roasting the filter cake to obtain the catalyst. According to the method disclosed by the invention, the Na < + > content in the catalyst can be reduced to below 50ppm; and the catalyst prepared and formed by the method disclosed by the invention has relatively high activity and selectivity when being applied to amination reaction of alcohols or alcamines and liquid ammonia.

Description

Technical Field:

[0001] The present invention relates to the field of catalytic technology, and particularly relates to an amination reaction catalyst, a preparation method thereof, and an application thereof. Background Art:

[0002] Alcohols or alkanolamines react with hydrogen and liquid ammonia under the catalysis of a catalyst to prepare corresponding amine organic compounds, such as diglycol amination, propylene glycol amination, ethanolamine amination, isopropanolamine amination, polyether polyol amination, etc. These products are mainly used in industries such as acid gas treatment agents, surfactants, textile auxiliaries, dye auxiliaries, pharmaceutical intermediates, epoxy resin curing agents, adhesives, fuel additives, etc.

[0003] In the prior art, such amination catalysts mainly use catalysts containing nickel, cobalt, or copper as active components. Currently, most of the catalysts used for amination in industry are prepared by the co-precipitation method, and inexpensive sodium carbonate or hydroxide is often used as a precipitant. During the preparation process, multiple water washes are required to remove sodium. According to literature reports, it is difficult to completely remove sodium or reduce it to meet the requirements through conventional limited water washes. The presence of sodium, on the one hand, easily adsorbs carbon dioxide in the air during the calcination stage, resulting in the formation of partial carbonates on the catalyst, covering the active sites on the catalyst surface, thereby reducing the catalyst activity. On the other hand, the presence of sodium easily causes unnecessary side reactions to occur, thereby reducing the selectivity of the target product.

[0004] CN113731425A discloses a preparation method of a copper-containing catalyst. The catalyst is prepared by the co-precipitation method. After the precipitant is mixed with the copper-containing solution, an aging agent is added again for secondary aging. After aging, water washing, filtration, drying, calcination, and shaping are carried out to obtain the catalyst. The sodium content in the surface layer of the catalyst prepared by this method is less than 200 ppm.

[0005] CN1642638B discloses a preparation method of an amination catalyst. The catalyst is prepared by the co-precipitation method, and the content of alkali metal oxides in the catalyst is controlled below 0.2%.

[0006] CN1042539A discloses a method for synthesizing morpholine and its derivatives from diglycol and ammonia in the presence of a catalyst. The catalyst is prepared by the co-precipitation method, and the active components contain copper oxide, nickel oxide, alumina, and chromium oxide. Under the reaction conditions of a reaction temperature of 200 - 240 °C, a reaction pressure of 1.4 - 2.5 MPa, and a feed molar ratio of diglycol:ammonia:hydrogen of 1:10:5, the single-pass conversion rate of diglycol can reach 99%, and the selectivity of morpholine is higher than 66%. This method has defects such as low yield of the main product.

[0007] US4151204 discloses a method for preparing 1,2 - propanediamine from 1,2 - propanediol and ammonia in the presence of a catalyst. The catalyst is prepared by a co - precipitation method, and the active components are cobalt, nickel, and one or more selected from iron, manganese, zinc, thorium, zirconium, and lanthanum. Under the conditions of a reaction temperature of 160 - 180 °C, a reaction pressure of 5 MPa, and a feed molar ratio of ammonia:1,2 - propanediol of 6:1, the conversion rate of 1,2 - propanediol is 33 - 96%, and the selectivity to 2 - amino - 1 - propanol is 48 - 76%. This method has defects such as relatively low conversion rate and selectivity.

[0008] CN110785400A discloses a method for preparing ethylenediamine by reacting ethylene glycol and / or monoethanolamine with ammonia in the presence of an amination catalyst. The catalyst is prepared by a co - precipitation method and is prepared from a catalyst precursor containing one or more active components of Sn, Cu, and Ni together with Ru and Co. Under the conditions of a reaction temperature of 165 °C, a pressure of 17 MPa, and a feed molar ratio of ammonia:monoethanolamine of 10:1, the conversion rate is 36.4%, and the selectivity to the main product is 95.1%. This method also has defects such as a low conversion rate.

[0009] CN101891628A discloses a method for preparing 1,2 - propanediamine by reacting monoisopropanolamine with ammonia in the presence of a catalyst. The catalyst is prepared by a co - precipitation method, the active components include Cu and Co, and the auxiliary catalyst includes Mg and Cr. Under the conditions of a reaction temperature of 100 - 250 °C, a pressure of 5 - 15 MPa, and a feed molar ratio of monoisopropanolamine:ammonia of 1:(1 - 10), the product selectivity is greater than 70%. This method also has defects such as a low conversion rate.

[0010] During the process of preparing the catalyst by the existing co - precipitation method, the residual Na content in the catalyst cannot be controlled at a low level, thus affecting the activity and selectivity of the catalyst. + content at a low level, thus affecting the activity and selectivity of the catalyst. Summary of the Invention

[0011] In order to solve the problems existing in the prior art, the present invention provides a method for preparing an amination reaction catalyst. The catalyst prepared by using this method can greatly reduce the Na + content in the catalyst. When this catalyst is used in the amination reaction of alcohols or alkanolamines, the conversion rate and selectivity of the reaction can be improved.

[0012] Another object of the present invention is to provide such an amination reaction catalyst and its application.

[0013] To achieve the above - mentioned invention purposes, the present invention adopts the following technical solutions:

[0014] A method for preparing an amination reaction catalyst, comprising the following steps:

[0015] (1) The metal salt solution containing the active component and the precipitant solution are dropped into a container, keeping the pH of the solution stable, and continuously stirred during the dropping process to cause coprecipitation of the metal salt solution and the precipitant solution.

[0016] (2) After the dropping of the metal salt solution is completed, the pH of the mixed solution is adjusted to a specified value using the precipitant solution, and it is allowed to stand and age, then filtered and washed until the conductivity of the filtrate is less than 100 μS / m.

[0017] (3) Water is added to the filter cake obtained by filtration to form a solution, an ion exchange resin modified with a β-diketone organic compound is added to the solution, stirred and heated, adsorbed, the ion exchange resin is filtered to obtain a filtrate, the filtrate is filtered to obtain a filter cake, and the filter cake is dried and calcined to obtain a catalyst.

[0018] In some specific embodiments, the metals of the active component in step (1) include the metals of the main active component and the promoter active component; among them, the metal of the main active component is selected from one or more of Ni, Co, and Cu, and the metal of the promoter active component is selected from one or more of Zn, Zr, Sn, Cr, Mo, Ce, La, and Mg; preferably, the metal salt is a water-soluble metal salt, preferably any one of nitrates, acetates, and oxalates, more preferably nitrates.

[0019] The precipitant solution is an alkaline solution, preferably an aqueous solution of sodium carbonate, sodium bicarbonate, or ammonium carbonate, more preferably an aqueous solution of sodium carbonate.

[0020] In some specific embodiments, during the dropping process of step (1), the reaction temperature is controlled at 50-80 °C, such as 50 °C, 60 °C, 70 °C, 80 °C, etc., preferably 60-70 °C.

[0021] In some specific embodiments, during the dropping process of step (1), the pH of the solution is maintained between 7 and 7.5, such as 7, 7.1, 7.2, 7.3, 7.4, 7.5, etc., preferably 7.1-7.4.

[0022] In some specific embodiments, in the stirring in step (1), the stirring speed is 100-600 revolutions per minute, such as 100 revolutions per minute, 200 revolutions per minute, 300 revolutions per minute, 400 revolutions per minute, 500 revolutions per minute, 600 revolutions per minute, etc., the dropping time is 3-8 h, such as 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, etc., and after the dropping of the metal salt solution is completed, the stirring is stopped.

[0023] In some specific embodiments, in step (2), the pH of the mixed solution is adjusted to 7-7.1 using the precipitant solution.

[0024] Preferably, the static aging time is 1-24h, such as 1h, 2h, 4h, 6h, 8h, 9h, 10h, 12h, 15h, 18h, 20h, 22h, 24h, etc., and preferably 6-12h;

[0025] More preferably, the deionized water used to wash the filter cake in step (2) is 3 times the volume of the filtrate, and the washing is stopped until the conductivity of the filtrate is less than 100 μS / m.

[0026] In some specific embodiments, the filter cake obtained by filtering the solution in step (2) is added with water in a volume of 2-10 times the volume of the filter cake to form a solution, such as water in a volume of 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times the volume of the filter cake, and an ion exchange resin modified with a β-diketone organic compound is added to the solution to adsorb the residual Na + ;

[0027] Preferably, the ion exchange resin is an acrylic weakly acidic cation exchange resin, and the resin diameter is 1-3 mm.

[0028] In some specific embodiments, the modification steps of the ion exchange resin modified with a β-diketone organic compound are as follows:

[0029] a. Prepare an alcohol solution of a β-diketone organic compound, place an equal volume of the ion exchange resin in the solution, stir, and graft the β-diketone organic compound onto the ion exchange resin;

[0030] b. Filter the solution to obtain the resin, and dry the resin to obtain the ion exchange resin modified with a β-diketone organic compound.

[0031] In some specific embodiments, the β-diketone organic compound in step a is selected from at least one of acetylacetone, propionyl butanone, benzoylacetone, dibenzoylacetone, thenoyltrifluoroacetone, benzoyltrifluoroacetone;

[0032] In some specific embodiments, the alcohol is any one of methanol, ethanol or isopropanol.

[0033] In some specific embodiments, the mass concentration of the alcohol solution of the β-diketone organic compound is 0.1-1 mol / L, such as 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1 mol / L, etc.;

[0034] In some specific embodiments, the stirring is carried out at 40 - 70 °C, such as 40 °C, 50 °C, 60 °C, 70 °C, at a rotation speed of 100 - 600 revolutions per minute for 1 - 6 h, such as at a rotation speed of 100 revolutions per minute, 200 revolutions per minute, 300 revolutions per minute, 400 revolutions per minute for 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, etc.;

[0035] In some specific embodiments, the drying is carried out at 80 - 120 °C for 1 - 10 h, such as drying at 80 °C, 90 °C, 100 °C, 110 °C, 120 °C for 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, etc.

[0036] In some specific embodiments, the stirring and heating are carried out at a temperature of 50 - 80 °C, such as 50 °C, 60 °C, 70 °C, 80 °C, at a rotation speed of 100 - 800 revolutions per minute, such as 100 revolutions per minute, 200 revolutions per minute, 300 revolutions per minute, 400 revolutions per minute, 500 revolutions per minute, 600 revolutions per minute, 700 revolutions per minute, 800 revolutions per minute, etc., for 1 - 8 h, such as 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h;

[0037] Preferably, after the adsorption is completed, the ion exchange resin is filtered out using a 50 - mesh sieve to obtain a filtrate; the ion exchange resin is washed with deionized water 3 - 5 times, such as 3 times, 4 times, 5 times, to obtain a washing solution;

[0038] More preferably, the filtrate and the washing solution are mixed and then filtered to obtain a filter cake and dried. The drying temperature is 100 - 150 °C, such as 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, etc., for a time of 2 - 12 h, such as 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h, 11 h, 12 h, etc.; the dried filter cake is calcined at 400 - 600 °C for 2 - 8 h, such as calcined at 400 °C, 500 °C, 600 °C for 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, etc.

[0039] On the other hand, for the amination reaction catalyst prepared by the foregoing preparation method, preferably, the content of Na in the powder of the catalyst after calcination + is < 50 ppm.

[0040] On yet another aspect, the application of the amination reaction catalyst prepared by the foregoing preparation method or the foregoing amination reaction catalyst in the amination reaction of alcohols or alkanolamines with liquid ammonia;

[0041] Preferably, before use, the catalyst powder is tableted to obtain a cylindrical or spherical catalyst with a diameter of 3-5 mm, and then the catalyst is loaded into a tubular reactor. Before use, the catalyst needs to be reduced and activated with hydrogen. The activation treatment method can refer to the prior art. For example, the activation temperature is 200-400 °C, the hydrogen flow rate is 0.005-0.05 g H2 / (g catalyst·h), and the activation time is 8-48 h.

[0042] Preferably, an alcohol or an alcoholamine, liquid ammonia, and hydrogen are fed together and react in the presence of the amination reaction catalyst;

[0043] More preferably, the alcohol or alcoholamine is selected from at least one of propylene glycol, dipropylene glycol, diethylene glycol, monoisopropanolamine, ethanolamine, and polyether polyol;

[0044] The space velocity of the alcohol or alcoholamine is 0.2-2 h -1 , such as 0.2 h -1 , 0.4 h -1 , 0.5 h -1 , 0.6 h -1 , 0.8 h -1 , 1 h -1 , 1.2 h -1 , 1.5 h -1 , 1.6 h -1 , 1.8 h -1 , 2 h -1 etc. The mass flow ratio of liquid ammonia, hydrogen, and the alcohol or alcoholamine is (1.2-6.4):(0.01-0.131):1, such as 1.2:0.01:1, 1.5:0.02:1, 2:0.05:1, 3:0.1:1, 5:0.12:1, 6:0.13:1, etc.;

[0045] The reaction temperature is 160-220 °C, such as 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, etc., and the absolute reaction pressure is 5-14 MPa, such as 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa, 10 MPa, 11 MPa, 12 MPa, 13 MPa, 14 MPa, etc.

[0046] Compared with the prior art, the present invention has the following beneficial effects:

[0047] By introducing a β-diketone organic compound to modify the ion exchange resin, the purpose is to rely on the chelation of β-diketone to bind with ions, thereby achieving the effect of extracting ions. The chelation mainly occurs through the carbonyl group and Na + to act. Generally, it is considered that due to the keto-enol tautomerism structure in β-diketone, it can form sp with Na + and3 Hybrid orbitals reduce energy and form a more stable chelation structure, which is beneficial for the adsorption of Na + .

[0048] By improving the method for preparing the catalyst, the present invention greatly reduces the content of Na in the catalyst raw powder + , thereby reducing the content of Na in the catalyst formed body + , reducing the coverage of the active centers of the catalyst by Na + and enabling the catalyst to have higher activity. Specific Embodiments

[0049] The present invention will be further described below through specific examples. The examples described in the present invention are only for the illustration of the present invention and do not limit the scope of the present invention.

[0050] Gas chromatograph: Shimadzu GC-2014 (FID) detector, SE-30 capillary column inlet at 280 °C, detector at 300 °C; temperature programming: 80 °C, hold for 5 min, then increase to 280 °C at a rate of 30 °C / min and hold for 10 min.

[0051] The content of Na in the catalyst powder + was detected using Agilent 5100 ICP-OES: plasma gas flow rate (L / min): 15.0; auxiliary gas flow rate (L / min): 1.50; nebulizer gas flow rate (L / min): 0.80; primary reading time (S): 5.00; instrument stabilization delay (S): 15; injection delay (S): 60; pump speed (rpm): 15; cleaning time (S): 30; number of readings: 3; slope deviation 10%; correlation coefficient limit value: 0.995.

[0052] Example 1

[0053] Weigh 291.0 g of Ni(NO3)2·6H2O, 7.4 g of Zn(NO3)2·6H2O and 8.2 g of Zr(CH3COO)4 respectively, and add them to 2 L of deionized water to obtain a metal salt solution. Weigh another 116.6 g of Na2CO3 and add it to 2 L of deionized water to prepare a precipitant solution. Slowly drip the precipitant solution into the salt solution, control the reaction temperature at 50 °C, the stirring speed at 600 revolutions per minute, keep the pH of the mixed solution at 7.5, and after dripping for 8 h, stop stirring. Let the precipitate stand and age at 50 °C for 24 h

[0054] After the aging is completed, filter the obtained suspension, separate the precipitate, wash it with water until the conductivity of the filtrate is 80 μS / cm, and perform suction filtration to obtain a filter cake.

[0055] Prepare a methanol solution of acetylacetone with a mass concentration of 0.1 mol / L. Place an equal volume of ion exchange resin in the solution and stir at 70 °C at a speed of 600 revolutions per minute for 6 h. Filter the solution to obtain the resin, and dry the resin at 120 °C for 10 h to obtain the acetylacetone-modified ion exchange resin.

[0056] Add the filter cake to water with a volume twice that of the filter cake to form a solution. Add acetylacetone-modified ion exchange resin with the same mass as the filter cake to the solution. The diameter of the resin is 1 mm. Stir the solution at 50 °C at a speed of 800 revolutions per minute for 8 h to adsorb Na + in it. Filter out the ion exchange resin using a 50-mesh sieve to obtain the filtrate. Wash the ion exchange resin 5 times with deionized water to obtain the washing solution. After mixing the filtrate and the washing solution, filter to obtain the filter cake. Dry the filter cake at 150 °C for 2 h and calcine it at 400 °C for 8 h. Test the Na + content in the powder, which is 20 ppm. Press the obtained catalyst powder into 3-mm cylindrical tablets, load the catalyst into a tubular reactor, and activate the catalyst with hydrogen. The activation temperature is 200 °C, the hydrogen flow rate is 0.05 g H2 / (g catalyst·h), and activate for 48 h.

[0057] Use the catalyst for the amination reaction of 1,2-propanediol and liquid ammonia. The space velocity of 1,2-propanediol is 0.2 h -1 . The mass flow ratio of liquid ammonia, hydrogen and 1,2-propanediol is 5.3:0.105:1. The reaction temperature is 160 °C, and the absolute reaction pressure is 5 MPa. After the product is vacuum-deammoniated and dehydrated, it is analyzed by gas chromatography. The conversion rate of 1,2-propanediol is 95.8%, and the selectivity of 1,2-propanediamine is 88.3%.

[0058] Comparative Example 1

[0059] The difference from Example 1 is that after the precipitation solution is washed until the conductivity of the filtrate is less than 100 μS / cm, the filter cake is not treated with unmodified ion exchange resin, and other conditions remain unchanged. After analysis, the Na + content in the catalyst powder is 1000 ppm. Under the same reaction conditions as in Example 1, after the product is analyzed by gas chromatography, the conversion rate of 1,2-propanediol is 65.2%, and the selectivity of 1,2-propanediamine is 72.8%.

[0060] Example 2

[0061] Weigh 291.0 g of Co(NO3)2·6H2O, 2.6 g of SnCl4 and 4.0 g of Cr(NO3)3·9H2O separately, and add them to 2 L of deionized water to obtain a metal salt solution. Weigh another 108.1 g of Na2CO3 and add it to 2 L of deionized water to prepare a precipitant solution. Slowly add the precipitant solution to the salt solution, control the reaction temperature at 80 °C, the stirring speed at 100 revolutions per minute, and keep the pH of the mixed solution at 7.0. After adding for 3 h, stop stirring. Let the precipitate solution stand and age at 80 °C for 1 h,

[0062] After the aging is completed, filter the obtained suspension, separate the precipitate, and wash it with water until the conductivity of the filtrate is 85 μS / cm, and then perform suction filtration to obtain a filter cake.

[0063] Prepare an ethanol solution of propionyl butanone with a mass concentration of 0.6 mol / L. Place an equal volume of ion exchange resin in the solution, stir at 50 °C at a speed of 300 revolutions per minute for 3 h, filter the solution to obtain the resin, and dry the resin at 100 °C for 5 h to obtain the ion exchange resin modified with propionyl butanone.

[0064] Add the filter cake to water with a volume 10 times that of the filter cake to form a solution. Add the ion exchange resin modified with propionyl butanone with the same mass as the filter cake to the solution. The diameter of the resin is 3 mm. Stir the solution at 80 °C at a speed of 100 revolutions per minute for 1 h to adsorb Na + , filter out the ion exchange resin using a 50-mesh sieve to obtain a filtrate. Wash the ion exchange resin with deionized water 3 times to obtain a washing solution. Mix the filtrate and the washing solution, filter to obtain a filter cake, dry the filter cake at 100 °C for 12 h, and calcine it at 600 °C for 2 h. Test the Na + content in the powder is 30 ppm. Press the obtained catalyst powder into 5-mm spherical tablets, load the catalyst into a tubular reactor, and activate the catalyst using hydrogen. The activation temperature is 400 °C, the hydrogen flow rate is 0.005 g H2 / (g catalyst·h), and activate for 8 h.

[0065] Use the catalyst for the amination reaction of ethanolamine and liquid ammonia. The space velocity of ethanolamine is 2 h -1 , and the mass flow ratio of liquid ammonia, hydrogen to ethanolamine is 6.4:0.131:1. The reaction temperature is 200 °C, and the absolute reaction pressure is 14 MPa. After the product is vacuum-deammoniated and dehydrated, it is analyzed by gas chromatography. The conversion rate of ethanolamine is 98.6%, and the selectivity of ethylenediamine is 96.1%.

[0066] Example 3

[0067] Weigh 242.0 g of Cu(NO3)2·3H2O, 8.8 g of (NH4)6Mo7O 24· 4H2O and 18.6 g of Ce(NO3)2·6H2O were added to 2 L of deionized water to obtain a metal salt solution. Another 139.9 g of Na2CO3 was weighed and added to 2 L of deionized water to prepare a precipitant solution. The precipitant solution was slowly added dropwise to the salt solution, controlling the reaction temperature at 60 °C, the stirring speed at 400 revolutions per minute, and maintaining the pH of the mixed solution at 7.3. After 7 h of dropping, the stirring was stopped. The precipitate solution was allowed to stand and age at 60 °C for 16 h,

[0068] After aging, the obtained suspension was filtered to separate the precipitate, and washed with water until the conductivity of the filtrate reached 70 μS / cm, and then suction filtered to obtain a filter cake.

[0069] An isopropanol solution of benzoylacetone with a mass concentration of 0.3 mol / L was prepared. An equal volume of ion exchange resin was placed in the solution and stirred at 65 °C at a speed of 500 revolutions per minute for 5 h. The solution was filtered to obtain the resin, and the resin was dried at 115 °C for 8 h to obtain benzoylacetone-modified ion exchange resin.

[0070] The filter cake was added to water with a volume 6 times that of the filter cake to form a solution. Benzoylacetone-modified ion exchange resin with the same mass as the filter cake was added to the solution. The diameter of the resin was 2 mm. The solution was stirred at 65 °C at a speed of 400 revolutions per minute for 5 h to adsorb Na + in it. The ion exchange resin was filtered out using a 50-mesh sieve to obtain a filtrate. The ion exchange resin was washed 4 times with deionized water to obtain a washing solution. The filtrate and the washing solution were mixed and then filtered to obtain a filter cake. The filter cake was dried at 120 °C for 8 h and calcined at 500 °C for 5 h. The Na + content in the powder was tested to be 25 ppm. The obtained catalyst powder was pressed into 4-mm cylindrical tablets, and the catalyst was loaded into a tubular reactor and activated with hydrogen. The activation temperature was 300 °C, the hydrogen flow rate was 0.03 g H2 / (g catalyst·h), and the activation time was 24 h.

[0071] The catalyst was used for the amination reaction of diethylene glycol and liquid ammonia. The space velocity of diethylene glycol was 1 h -1 . The mass flow ratio of liquid ammonia, hydrogen and ethanolamine was 3.8:0.094:1. The reaction temperature was 180 °C, and the absolute reaction pressure was 8 MPa. After the product was vacuum-deammoniated and dehydrated, it was analyzed by gas chromatography. The conversion rate of diethylene glycol was 96.5%, and the selectivity of diethylene glycol amine was 90.4%.

[0072] Example 4

[0073] Weigh 145.5 g of Ni(NO3)2·6H2O, 145.5 g of Co(NO3)2·6H2O, 6.5 g of La(NO3)3·6H2O, and 3.9 g of SnCl4 separately, and add them to 2 L of deionized water to obtain a metal salt solution. Weigh another 116.0 g of Na2CO3 and add it to 2 L of deionized water to prepare a precipitant solution. Slowly drip the precipitant solution into the salt solution, control the reaction temperature at 70 °C, the stirring speed at 300 revolutions per minute, and keep the pH of the mixed solution at 7.1. After dripping for 5 h, stop stirring. Let the precipitate solution stand and age at 70 °C for 10 h.

[0074] After aging, filter the obtained suspension to separate the precipitate, and wash it with water until the conductivity of the filtrate is 50 μS / cm, then perform suction filtration to obtain a filter cake.

[0075] Prepare a methanol solution of dibenzoylacetone with a mass concentration of 0.4 mol / L, place an equal volume of ion exchange resin in the solution, stir at 55 °C at a speed of 400 revolutions per minute for 4 h, filter the solution to obtain the resin, and dry the resin at 110 °C for 6 h to obtain the ion exchange resin modified with dibenzoylacetone.

[0076] Add the filter cake to water with a volume 5 times that of the filter cake to form a solution, add the ion exchange resin modified with dibenzoylacetone with the same mass as the filter cake to the solution, the diameter of the resin is 2 mm, stir the solution at 75 °C at a speed of 200 revolutions per minute for 3 h to adsorb Na + , use a 50-mesh sieve to filter out the ion exchange resin to obtain a filtrate. Wash the ion exchange resin 4 times with deionized water to obtain a washing solution. Mix the filtrate and the washing solution, filter to obtain a filter cake, dry the filter cake at 130 °C for 6 h, and calcine it at 550 °C for 4 h. Test that the Na + content in the powder is 15 ppm. Press the obtained catalyst powder into 3-mm spherical tablets, load the catalyst into a tubular reactor, and activate the catalyst with hydrogen. The activation temperature is 250 °C, the hydrogen flow rate is 0.04 g H2 / (g catalyst·h), and activate for 36 h.

[0077] Use the catalyst for the amination reaction of isopropylamine and liquid ammonia. The space velocity of isopropylamine is 0.6 h -1 , and the mass flow ratio of liquid ammonia, hydrogen to isopropylamine is 4.7:0.08:1. The reaction temperature is 190 °C, and the absolute reaction pressure is 11 MPa. After the product is vacuum-deammoniated and dehydrated, it is analyzed by gas chromatography. The conversion rate of isopropylamine is 98.8%, and the selectivity of 1,2-propanediamine is 95.7%.

[0078] Example 5

[0079] Weigh 145.5 g of Ni(NO3)2·6H2O, 121.0 g of Cu(NO3)2·3H2O, 16.0 g of Cr(NO3)3·9H2O, and 10.2 g of Mg(NO3)2·6H2O separately, and add them to 2 L of deionized water to obtain a metal salt solution. Weigh another 125.9 g of Na2CO3 and add it to 2 L of deionized water to prepare a precipitant solution. Slowly add the precipitant solution to the salt solution, control the reaction temperature at 65 °C, the stirring speed at 500 revolutions per minute, and keep the pH of the mixed solution at 7.2. After adding for 6 h, stop stirring. Let the precipitate stand and age at 65 °C for 12 h.

[0080] After the aging is completed, filter the obtained suspension, separate the precipitate, and wash it with water until the conductivity of the filtrate is 60 μS / cm, and then perform suction filtration to obtain a filter cake.

[0081] Prepare an ethanol solution of thenoyltrifluoroacetone with a mass concentration of 1 mol / L. Place an equal volume of ion exchange resin in the solution, stir at 40 °C at a speed of 100 revolutions per minute for 1 h, filter the solution to obtain the resin, and dry the resin at 80 °C for 1 h to obtain the thenoyltrifluoroacetone-modified ion exchange resin.

[0082] Add the filter cake to water with a volume 7 times that of the filter cake to form a solution. Add the thenoyltrifluoroacetone-modified ion exchange resin with the same mass as the filter cake to the solution. The diameter of the resin is 2 mm. Stir the solution at 60 °C at a speed of 600 revolutions per minute for 6 h to adsorb Na + , use a 50-mesh sieve to filter out the ion exchange resin to obtain a filtrate. Wash the ion exchange resin with deionized water 3 times to obtain a washing solution. Mix the filtrate and the washing solution, filter to obtain a filter cake, dry the filter cake at 110 °C for 10 h, and calcine it at 450 °C for 6 h. Test the Na + content in the powder to be 25 ppm. Press the obtained catalyst powder into 5-mm cylindrical tablets, load the catalyst into a tubular reactor, and activate the catalyst with hydrogen. The activation temperature is 350 °C, the hydrogen flow rate is 0.015 g H2 / (g catalyst·h), and activate for 14 h.

[0083] Use the catalyst for the amination reaction of polyether polyol with an average molecular weight of 230 and liquid ammonia. The space velocity of the polyether polyol is 1.2 h -1 , and the mass flow ratio of liquid ammonia, hydrogen to polyether polyol is 2.2:0.017:1. The reaction temperature is 210 °C, and the absolute reaction pressure is 12 MPa. After the product is vacuum-deammoniated and dehydrated, it is analyzed by gas chromatography. The conversion rate of polyether polyol is 98.6%, and the selectivity of polyetheramine is 99.1%.

[0084] Example 6

[0085] Weigh 145.5 g of Ni(NO3)2·6H2O, 121.0 g of Cu(NO3)2·3H2O, 8.9 g of Zn(NO3)2·6H2O and 7.8 g of SnCl4 respectively, and add them to 2 L of deionized water to obtain a metal salt solution. Weigh another 122.5 g of Na2CO3 and add it to 2 L of deionized water to prepare a precipitant solution. Slowly add the precipitant solution to the salt solution, control the reaction temperature at 75 °C, the stirring speed at 200 revolutions per minute, keep the pH of the mixed solution at 7.4, and stop stirring after 4 h of dropping. Let the precipitate solution stand and age at 75 °C for 6 h.

[0086] After the aging is completed, filter the obtained suspension, separate the precipitate, and wash it with water until the conductivity of the filtrate is 70 μS / cm, and then perform suction filtration to obtain a filter cake.

[0087] Prepare an isopropanol solution of benzoyltrifluoroacetone with a mass concentration of 0.8 mol / L, place an equal volume of ion exchange resin in the solution, stir at 50 °C at a speed of 200 revolutions per minute for 2 h, filter the solution to obtain the resin, and dry the resin at 90 °C for 3 h to obtain the ion exchange resin modified with benzoyltrifluoroacetone.

[0088] Add the filter cake to water with a volume 4 times that of the filter cake to form a solution, add the ion exchange resin modified with benzoyltrifluoroacetone with the same mass as the filter cake to the solution, the diameter of the resin is 2 mm, stir the solution at 70 °C at a speed of 300 revolutions per minute for 4 h to adsorb the Na + , use a 50-mesh sieve to filter out the ion exchange resin to obtain a filtrate. Wash the ion exchange resin 4 times with deionized water to obtain a washing solution. Mix the filtrate and the washing solution, filter to obtain a filter cake, dry the filter cake at 140 °C for 4 h, and calcine it at 550 °C for 3 h. Test that the Na + content in the powder is 30 ppm. Press the obtained catalyst powder into 4-mm spherical tablets, load the catalyst into a tubular reactor, and activate the catalyst with hydrogen. The activation temperature is 280 °C, the hydrogen flow rate is 0.035 g H2 / (g catalyst·h), and activate for 30 h.

[0089] Use the catalyst for the amination reaction of polyether polyol with an average molecular weight of 2000 and liquid ammonia. The space velocity of the polyether polyol is 0.8 h -1 , and the mass flow ratio of liquid ammonia, hydrogen to polyether polyol is 1.2:0.01:1. The reaction temperature is 220 °C, and the reaction absolute pressure is 12 MPa. After the product is vacuum-deammoniated and dehydrated, it is analyzed by gas chromatography. The conversion rate of polyether polyol is 98.2%, and the selectivity of polyetheramine is 99.2%.

[0090] Comparative Example 2

[0091] The difference from Example 5 lies in that amyl alcohol is used to modify the ion exchange resin, and the modification conditions are the same as those in Example 5. After analysis, the Na + content in the catalyst powder is 500 ppm. Under the same reaction conditions as in Example 5, the product was analyzed by gas chromatography. The conversion rate of polyether polyol was 83.2%, and the selectivity of 1,2-propanediamine was 88.5%.

Claims

1. A preparation method of an amination reaction catalyst, characterized in that It includes the following steps: (1) Drop the metal salt solution containing the active component and the precipitant solution into a container, keep the pH of the solution stable, and continuously stir during the dropping process to cause the co-precipitation of the metal salt solution and the precipitant solution; (2) After the dropping of the metal salt solution is completed, use the precipitant solution to adjust the pH of the mixed solution to a specified value, let it stand for aging, then filter and wash until the conductivity of the filtrate is less than 100 μS / m; (3) Add water to the filter cake obtained by filtration to form a solution, add an ion exchange resin modified with a β-diketone organic compound to the solution, stir and heat up for adsorption. After filtering the ion exchange resin, obtain a filtrate. Filter the filtrate to obtain a filter cake, and dry and calcine the filter cake to obtain a catalyst.

2. The preparation method according to claim 1, characterized in that, In step (1), the metals of the active components include the metals of the main active components and the metals of the promoter active components; among them, the metals of the main active components are selected from one or more of Ni, Co, and Cu, and the metals of the promoter active components are selected from one or more of Zn, Zr, Sn, Cr, Mo, Ce, La, and Mg; preferably, the metal salt is a water-soluble metal salt, preferably any one of nitrates, acetates, and oxalates, and more preferably a nitrate; and / or The precipitant solution is an alkaline solution, preferably an aqueous solution of sodium carbonate, sodium bicarbonate, or ammonium carbonate, and more preferably an aqueous solution of sodium carbonate.

3. The preparation method according to claim 1 or 2, characterized in that, During the dropping process of step (1), control the reaction temperature to be 50-80 °C, preferably 60-70 °C; and / or During the dropping process of step (1), keep the pH of the solution between 7 and 7.5, preferably 7.1-7.4; and / or In step (1), for the stirring, the stirring speed is 100-600 revolutions per minute, the dropping time is 3-8 h, and after the dropping of the metal salt solution is completed, stop stirring.

4. The preparation method according to claim 1, characterized in that, In step (2), use the precipitant solution to adjust the pH of the mixed solution to 7-7.1; Preferably, the standing aging time is 1-24 h, preferably 6-12 h; More preferably, in step (2), the deionized water used to wash the filter cake is 3 times the volume of the filtrate, and wash until the conductivity of the filtrate is less than 100 μS / m.

5. The preparation method according to claim 1, wherein The filter cake obtained by filtering the solution in step (2) is added to water with a volume 2 - 10 times that of the filter cake to form a solution, and an ion exchange resin modified with a β-diketone organic compound is added to the solution to adsorb the remaining Na + ; Preferably, the ion exchange resin is an acrylic weak acidic cation exchange resin, and the resin diameter is 1-3 mm.

6. The preparation method according to claim 1 or 5, characterized in that, The modification steps of the ion exchange resin modified with the β-diketone organic compound are as follows: a. Prepare an alcohol solution of the β-diketone organic compound, place an equal volume of the ion exchange resin in the solution, stir, and graft the β-diketone organic compound onto the ion exchange resin; b. Filter the solution to obtain the resin, and dry the resin to obtain the ion exchange resin modified with the β-diketone organic compound.

7. The preparation method according to claim 6, characterized in that, In step a, the β-diketone organic compound is selected from at least one of acetylacetone, propionyl butanone, benzoyl acetone, dibenzoyl acetone, thenoyltrifluoroacetone, and benzoyltrifluoroacetone; and / or The alcohol is any one of methanol, ethanol, and isopropanol; and / or The mass concentration of the alcohol solution of the β-diketone organic compound is 0.1-1 mol / L; and / or For the stirring, stir at 40-70 °C and at a speed of 100-600 revolutions per minute for 1-6 h; and / or The drying is carried out at 80 - 120°C for 1 - 10 h.

8. The preparation method according to claim 1, characterized in that, The stirring and temperature rising are carried out at a temperature of 50 - 80°C and a rotation speed of 100 - 800 rpm for 1 - 8 h. Preferably, after the adsorption is completed, the ion exchange resin is filtered out using a 50 - mesh sieve to obtain a filtrate; the ion exchange resin is washed 3 - 5 times with deionized water to obtain a washing solution. More preferably, the filtrate and the washing solution are mixed and then filtered to obtain a filter cake, which is dried at a temperature of 100 - 150°C for 2 - 12 h; the dried filter cake is calcined at 400 - 600°C for 2 - 8 h.

9. The amination reaction catalyst prepared by the preparation method according to any one of claims 1 to 8. Preferably, the content of Na in the calcined powder of the catalyst + is less than 50 ppm.

10. Use of the amination reaction catalyst prepared by the preparation method according to any one of claims 1 to 8 or the amination reaction catalyst according to claim 9 in the amination reaction of alcohols or alkanolamines with liquid ammonia; Preferably, the alcohols or alkanolamines, liquid ammonia and hydrogen are fed together and react in the presence of the amination reaction catalyst; and / or Before use, the amination reaction catalyst is tableted to obtain a cylindrical or spherical catalyst with a size of 3 - 5 mm, and then the shaped catalyst is loaded into a tubular reactor and subjected to hydrogen reduction activation treatment. More preferably, the alcohols or alkanolamines are selected from at least one of propylene glycol, dipropylene glycol, diethylene glycol, mono - isopropanolamine, ethanolamine, and polyether polyol; and / or The space velocity of the alcohol or alkanolamine is 0.2 - 2 h -1 , and the mass flow ratio of liquid ammonia, hydrogen, and the alcohol or alkanolamine is (1.2 - 6.4):(0.01 - 0.131):1; and / or The reaction temperature is 160 - 220°C and the absolute reaction pressure is 5 - 14 MPa.