A special catalyst for macromolecular special amines and its preparation method and application

Abstract

The present invention discloses a special catalyst for macromolecular special amines and its preparation method and application, belonging to the technical field of catalysts. The catalyst is Ni / M / Al2O3, in which the Ni content is 20-40%, the auxiliary agent M content is 0-10%, the auxiliary agent M is selected from one or more of Cu, Cr, La, Ce, and the Al2O3 content is 50-70%; the Al2O3 pore volume is 1.5-3.5mL.g ‑1 , pores with pore radius greater than 100nm account for 40-60%. The catalyst preparation steps include: preparation of macroporous carrier Al2O3, primary impregnation, drying and calcination of metal salt, catalyst molding, secondary impregnation, drying and calcination of metal salt to obtain Ni / M / Al2O3 catalyst. The catalyst is used for the hydroamination reaction of alkylphenol polyoxyethylene ether, and the alkylphenol polyoxyethylene ether has high conversion rate and high product yield.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and in particular relates to a special catalyst for macromolecular special amines and a preparation method and application thereof. Background Art

[0002] Alkylphenol polyoxyethylene ether monoamine belongs to the category of aromatic hydrocarbon specialty amines, which are a class of aromatic hydrocarbon compounds terminated by primary or secondary amino groups. Because its main molecular chain is a soft polyether chain and alkylphenol, and the hydrogen at the end is more active, it can replace alkylphenol polyoxyethylene ether in some fields and can improve the application performance of new materials. Alkylphenol polyoxyethylene ether monoamine is mainly used in polyurea spraying, gasoline detergent, polyurethane reaction injection molding materials and other fields. Affected by the development of terminal industries, the global market demand for aromatic hydrocarbon specialty amines has increased year by year in recent years, especially in Asia, which is in a stage of rapid economic development and has an increasing demand for aromatic hydrocarbon specialty amines.

[0003] C6-C 13 Alkylphenol polyoxyethylene ether is an important fuel additive, and its consumption is related to the amount of gasoline and diesel used. 13 The global market demand for alkylphenol polyoxyethylene ether is about 40,000 tons / year, and the domestic market demand is about 10,000 tons / year. Currently, the supply is in short supply. If all domestic fuels use fuel additives in the future, it is estimated that more than 8 million tons of carbon emissions can be reduced.

[0004] C6-C 13 Alkylphenol polyoxyethylene ether has a large molecular diameter. When using traditional small-pore supported catalysts for hydroamination reactions, there is a possibility of large molecules blocking the pores and depositing on the external surface, resulting in low hydroamination conversion rate of alkylphenol polyoxyethylene ether and low product yield. Summary of the invention

[0005] Purpose of the invention: The purpose of the present invention is to provide a special catalyst for macromolecular special amines and its preparation method and application in view of the deficiencies in the prior art. The catalyst of the present invention has high reaction activity, mild reaction conditions and high product yield in the hydroamination reaction in which it participates, and overcomes the shortcomings of low conversion rate and low product yield of the traditional small-pore supported catalyst in the hydroamination reaction.

[0006] Technical solution: The purpose of the present invention is achieved through the following technical solution:

[0007] The present invention provides a special catalyst for macromolecular special amines, wherein the catalyst is Ni / M / Al2O3, wherein the Ni content is 20-40%, the auxiliary agent M content is 0-10%, and the Al2O3 content is 50-70% by mass percentage;

[0008] The additive M is selected from one or more of Cu, Cr, La, and Ce;

[0009] The Al2O3 pore volume is 1.5 to 3.5 mL.g -1 , pores with a pore radius greater than 100nm account for 40-60%. For macromolecular specialty amines, the corresponding polyether has a large molecular weight and a large molecular radius. The internal diffusion during the reaction is the key control step of the reaction. Selecting the appropriate catalyst carrier pore size is crucial to the reaction and can significantly improve the reaction conversion rate.

[0010] The present invention also provides a method for preparing the above-mentioned macromolecular special amine catalyst, comprising the following steps:

[0011] (1) Using ammonium bicarbonate and pseudo-boehmite as raw materials to prepare a macroporous Al2O3 carrier;

[0012] (2) According to the composition of the catalyst, respectively prepare aqueous solutions of active component nickel salt and auxiliary agent M metal salt, add them to the macroporous Al2O3 carrier and immerse them at room temperature for 10 to 20 hours; dry the obtained catalyst precursor at 100 to 150° C. for 3 to 8 hours; calcine at 300 to 700° C. for 4 to 8 hours to obtain catalyst powder;

[0013] (3) adding 1 to 5% by weight of a weak acid aqueous solution and 1 to 3% by weight of graphite to the catalyst powder obtained in step (2), and pressing the mixture into tablets;

[0014] (4) The molded catalyst is subjected to secondary impregnation. A metal salt aqueous solution is prepared and added to the molded catalyst for impregnation at room temperature for 5 to 10 hours; the obtained secondary impregnated catalyst is dried at 100 to 120° C. for 3 to 8 hours; and the catalyst is calcined at 300 to 500° C. for 2 to 6 hours.

[0015] In the present invention, weak acid is added during the molding process to further expand the pores and increase the pore diameter of the catalyst; the metal content of the components is increased by secondary impregnation, thereby increasing the reaction conversion rate and product yield.

[0016] In the present invention, the concentration of the metal salt aqueous solution is not required for the first and second impregnations, as long as it can cover the solid catalyst. The concentrations of the aqueous solutions prepared for the two impregnations can be the same or different, and the density is generally controlled at 1.4-1.6 g / cm 3 .

[0017] In the present invention, there is no special requirement for the preparation process of the macroporous Al2O3 carrier. In order to further increase the pores of the catalyst carrier and increase the proportion of macropores, thereby reducing the phenomenon of pore blocking and external surface deposition of macromolecular raw materials, a preferred embodiment of the present invention is that the preparation of the macroporous Al2O3 carrier includes the following steps:

[0018] (1) mixing pseudo-boehmite and an aqueous solution of ammonium bicarbonate having a pH value of 10 to 11; wherein the molar ratio of the ammonium bicarbonate to the pseudo-boehmite is (0.5 to 0.8):1;

[0019] (2) Aging at 90-180°C for 10-24h;

[0020] (3) The aged solution is taken out, dried at 100-150°C for 5-9 hours, and calcined at 400-650°C for 2-6 hours to obtain a macroporous Al2O3 carrier.

[0021] In the process of preparing the macroporous Al2O3 carrier of the present invention, there is no special requirement for the molar ratio of the ammonium bicarbonate to the pseudo-boehmite. In order to further improve the conversion rate and product yield of the alkylphenol polyoxyethylene ether, preferably, the molar ratio of the ammonium bicarbonate to the pseudo-boehmite is (0.5-0.8):1.

[0022] In order to further increase the size of the catalyst pores and the proportion of large pores, a preferred embodiment of the present invention is to use a roller heating furnace to prepare a large-pore Al2O3 carrier. The roller heating furnace does not have stirring, and it uses external transmission to make the materials mix evenly, and minimizes the damage to the carrier pores during the aging process.

[0023] The auxiliary agent in the present invention can be a conventional auxiliary agent in the art. In order to further improve the catalyst activity and improve the product yield, preferably, in step (2), the active component nickel salt is nickel nitrate, and the auxiliary agent M metal salt is one or more of copper nitrate, chromium nitrate, lanthanum nitrate, and cerium nitrate.

[0024] In order to improve the catalyst activity, it is further preferred that the purity of the nitrate is greater than 99%, and the sulfide ion content in the nitrate is less than 20 ppm.

[0025] In order to further increase the size of the catalyst pores and the proportion of large pores, preferably, in step (3), the weak acid is acetic acid or carbonic acid; and the concentration of the weak acid aqueous solution is 1 to 15 wt%.

[0026] The present invention also provides the use of the above macromolecular special amine dedicated catalyst in the hydroamination reaction of alkylphenol polyoxyethylene ether.

[0027] In the present invention, the conditions for the hydroamination reaction of alkylphenol polyoxyethylene ether can be conventionally selected in the art. In order to further improve the catalyst activity, reaction conversion rate and product yield, preferably, the conditions for the hydroamination reaction of the catalyst for alkylphenol polyoxyethylene ether include: reaction temperature of 180-295°C; liquid volume space velocity of 0.5-2.0h -1; Reaction pressure 2 ~ 8MPa; The alkylphenol polyoxyethylene ether is C6-C13 alkylphenol polyoxyethylene ether.

[0028] Further preferably, the catalyst is one or more of Ni / Cu / Cr / Al2O3, Ni / Cu / La / Al2O3, Ni / Cu / Ce / Al2O3, Ni / Cu / Al2O3, Ni / Cr / Al2O3, and Ni / Al2O3 catalysts.

[0029] In the present invention, the catalyst exists in an oxidized state after calcination. Before the hydroamination reaction, the catalyst needs to be reduced with a hydrogen-nitrogen mixed gas, and the catalyst reduction conditions can be conventionally selected in the art. A preferred embodiment of the present invention is that the reduction treatment conditions include: a reduction temperature of 280 to 360°C; a concentration of the reducing gas hydrogen-nitrogen mixed gas gradually increased from 1% to 20%; and a reduction pressure of 0.25 to 0.8 MPa.

[0030] Beneficial effects:

[0031] (1) The catalyst of the present invention is used for the hydroamination reaction of alkylphenol polyoxyethylene ether, has high reaction activity, mild reaction conditions, high conversion rate of alkylphenol polyoxyethylene ether (conversion rate is greater than 94%), and high product yield (the yield of alkylphenol polyoxyethylene ether monoamine is greater than 93%).

[0032] (2) The catalyst preparation process of the present invention is simple and easy to industrialize, and can prepare a macroporous catalyst suitable for the synthesis of macromolecular special amines. DETAILED DESCRIPTION

[0033] The technical solution of the present invention is described in detail below through specific embodiments, but the protection scope of the present invention is not limited to the embodiments.

[0034] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0035] In the present invention, unless otherwise specified, the reagents used can be obtained commercially:

[0036] C6-C13 alkylphenol polyoxyethylene ether (Jiangsu Zhongshan New Materials Co., Ltd., model is industrial grade)

[0037] Nickel nitrate (Nanjing Chemical Reagent Co., Ltd., analytical grade)

[0038] Copper nitrate (Nanjing Chemical Reagent Co., Ltd., analytical grade)

[0039] Chromium nitrate (Nanjing Chemical Reagent Co., Ltd., analytical grade)

[0040] Lanthanum nitrate (Nanjing Chemical Reagent Co., Ltd., analytical grade)

[0041] Strontium nitrate (Nanjing Chemical Reagent Co., Ltd., analytical grade)

[0042] The purity of the above nitrates is greater than 99%;

[0043] Pseudo-boehmite (Shandong Jinqi Aluminum and Magnesium Technology Co., Ltd., industrial grade)

[0044] Ammonium bicarbonate (Sinopharm Chemical Reagent Co., Ltd., analytical grade)

[0045] Acetic acid (Sinopharm Chemical Reagent Co., Ltd., analytical grade)

[0046] Carbonic acid (Sinopharm Chemical Reagent Co., Ltd., analytical grade)

[0047] Fixed bed reactor (Beijing Tuochuan Instrument Equipment Co., Ltd., catalyst loading 100 mL)

[0048] Roller Heating Furnace (Qingdao Haitongda Special Instrument Co., Ltd.)

[0049] Alkylphenol polyoxyethylene ether monoamine product analysis method: Weigh 2 samples of a certain mass into a 250mL conical flask (1-4g, accurate to 0.1mg, if solid, dissolve first), mark as S and T, add 50mL CHCl3 and heat for 1 minute to prevent NH 4+ interference, and then cool to room temperature. Add 3mL of salicylaldehyde to the S sample, let it stand for 30 minutes, add 1mL of bromophenol blue indicator, and titrate with about 0.1mol / L HCl to the yellow end point under stirring. Calculate the sum of the secondary and tertiary amine values ​​based on the volume V2 of HCl consumed. Add 3mL of phenyl isothiocyanate to the T sample, let it stand for 30 minutes, add 1mL of bromophenol blue indicator, and titrate with about 0.1mol / L HCl to the yellow end point under stirring. Calculate the tertiary amine value based on the volume V3 of HCl consumed.

[0050] The sum of the secondary and tertiary amine values ​​(mmol / g) = C*V2 / M

[0051] Tertiary amine value (mmol / g) = C*V3 / M

[0052] Secondary amine value = sum of secondary amine and tertiary amine values ​​- tertiary amine value;

[0053] Primary amine value = total amine value - sum of secondary amine and tertiary amine values.

[0054] C: hydrochloric acid concentration, mol / L;

[0055] M: sample mass, g;

[0056] V2: volume of hydrochloric acid consumed, mL;

[0057] V3: Volume of hydrochloric acid consumed, mL.

[0058] Calculation method of alkylphenol polyoxyethylene ether monoamine yield and primary amine purity:

[0059]

[0060]

[0061]

[0062] Yield % = X × S

[0063] Example 1

[0064] Weigh 50g of pseudo-boehmite and add it to a polytetrafluoroethylene-lined autoclave, then add an aqueous solution of ammonium bicarbonate with a pH value of 10.5, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.65:1; put the autoclave into a roller heating furnace and age it at 170℃ for 20h; take out the aged solution and put it into an oven and dry it at 120℃ for 8h, and finally put it into a muffle furnace and calcine it at 600℃ for 5h to obtain a macroporous Al2O3 carrier. Al2O3 pore volume 3.27mL.g -1 , pores with a pore radius greater than 100 nm account for 54.80%.

[0065] Weigh 38.67g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 56.31wt% aqueous solution, stir at room temperature for 8h, add 30g macroporous Al2O3 carrier and impregnate at room temperature for 18h; put the obtained catalyst precursor into an oven at 120℃ for 4h; then put it into a muffle furnace and roast it at 500℃ for 5h. Add 3% acetic acid solution (concentration 12wt%) and 1.5% graphite to the obtained catalyst powder, and press it into a 3mm*3mm cylindrical catalyst.

[0066] 17.187 g of nickel nitrate hexahydrate (sulfide ion content less than 15 ppm) was weighed to prepare a 63.22 wt% aqueous solution, added to 40 g of the formed catalyst and immersed at room temperature for 8 hours; placed in an oven at 105°C for 5 hours; finally placed in a muffle furnace and calcined at 450°C for 4 hours to obtain the catalyst.

[0067] The catalyst was loaded into a fixed bed reactor and reduced at 0.3 MPa using a hydrogen-nitrogen mixture at 320°C for 5 h; the concentration of the hydrogen-nitrogen mixture was gradually increased from 1% to 20%.

[0068] Weigh 500g of decylphenol polyoxyethylene ether, the molar ratio of liquid ammonia to decylphenol polyoxyethylene ether is 8:1, and stir at a volume space velocity of 1.5h -1 , a reaction temperature of 265° C. and a reaction pressure of 5 MPa were used to carry out a hydroamination reaction to obtain decylphenol polyoxyethylene ether amine.

[0069] The yield of decylphenol polyoxyethylene ether amine was 98.28%, and the conversion rate of decylphenol polyoxyethylene ether was 94.29%.

[0070] Example 2

[0071] 9.72 g of copper nitrate hexahydrate (sulfide ion content less than 18 ppm) was weighed and prepared into a 50 wt% aqueous solution, added to 40 g of the cylindrical catalyst formed in Example 1, immersed at room temperature for 9 hours, placed in an oven at 110° C. for 6 hours; finally, placed in a muffle furnace and calcined at 480° C. for 4 hours to obtain the catalyst.

[0072] The catalyst was loaded into a fixed bed reactor and reduced at 350°C for 6 h at 0.25 MPa using a hydrogen-nitrogen mixer.

[0073] Weigh 500g of undecylphenol polyoxyethylene ether, the molar ratio of liquid ammonia to undecylphenol polyoxyethylene ether is 10:1, and stir at a volume space velocity of 1.2h -1 , reaction temperature 260°C, reaction pressure 5MPa conditions, a hydrogenation reaction was carried out to obtain undecylphenol polyoxyethylene ether amine.

[0074] The yield of undecylphenol polyoxyethylene ether amine was 97.38%, and the conversion rate of undecylphenol polyoxyethylene ether was 96.54%.

[0075] Example 3

[0076] Weigh 50g of pseudo-boehmite and add it to a polytetrafluoroethylene-lined autoclave, then add an aqueous solution of ammonium bicarbonate with a pH value of 11, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.55:1; put the autoclave into a roller heating furnace and age it at 160℃ for 15h; take out the aged solution and put it into an oven to dry at 120℃ for 9h, and finally put it into a muffle furnace and calcine it at 650℃ for 4h to obtain a macroporous Al2O3 carrier. Al2O3 pore volume 2.75mL.g -1 , pores with a pore radius greater than 100 nm account for 48.89%.

[0077] Weigh 38.67g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 56.31wt% aqueous solution, stir at room temperature for 8h, add 30g macroporous Al2O3 carrier and impregnate at room temperature for 15h; put the obtained catalyst precursor into an oven at 120℃ for 5h; then put it into a muffle furnace for calcination at 550℃ for 4h. Add acetic acid solution (concentration 10wt%) accounting for 5% of the system mass and 2% graphite to the obtained catalyst powder and press it into a 3mm*3mm cylindrical catalyst.

[0078] Weigh 21.105 g of chromium nitrate nonahydrate (sulfide ion content less than 10 ppm) and 46.397 g of copper nitrate trihydrate (sulfide ion content less than 13 ppm) to prepare a 50 wt% aqueous solution, add it to 50 g of the formed catalyst and soak it at room temperature for 8 hours; put it in an oven at 105°C and dry it for 5 hours; finally, put it in a muffle furnace and calcine it at 480°C for 5 hours to obtain the catalyst.

[0079] The catalyst was loaded into a fixed bed reactor and reduced at 350°C for 5 h at 0.25 MPa using a hydrogen-nitrogen mixer.

[0080] Weigh 500g of nonylphenol polyoxyethylene ether, the molar ratio of liquid ammonia to nonylphenol polyoxyethylene ether is 12:1, and stir at a volume space velocity of 0.95h -1 , reaction temperature 250°C, reaction pressure 5MPa conditions, a hydrogenation reaction was carried out to obtain nonylphenol polyoxyethylene ether amine.

[0081] The yield of nonylphenol polyoxyethylene ether amine was 96.99%, and the conversion rate of nonylphenol polyoxyethylene ether was 98.96%.

[0082] Example 4

[0083] Weigh 50g of pseudo-boehmite and add it to a polytetrafluoroethylene-lined autoclave, then add an aqueous solution of ammonium bicarbonate with a pH value of 10.5, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.7:1; put the autoclave into a roller heating furnace and age it at 170℃ for 20h; take out the aged solution and put it into an oven and dry it at 120℃ for 8h, and finally put it into a muffle furnace and calcine it at 600℃ for 5h to obtain a macroporous Al2O3 carrier. Al2O3 pore volume 2.57mL.g -1 , pores with a pore radius greater than 100 nm account for 59.80%.

[0084] Weigh 38.67g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 56.31wt% aqueous solution, stir at room temperature for 8h, add 30g macroporous Al2O3 carrier and impregnate at room temperature for 18h; put the obtained catalyst precursor into an oven at 120℃ for 4h; then put it into a muffle furnace and roast it at 500℃ for 5h. Add 4.5% acetic acid solution (concentration 12wt%) and 1.5% graphite to the obtained catalyst powder to press it into a 3mm*3mm cylindrical catalyst.

[0085] Weigh 17.187g of nickel nitrate hexahydrate (sulfide ion content less than 15ppm) and 14.671g of copper nitrate trihydrate (sulfide ion content less than 13ppm), prepare a 65wt% aqueous solution, add it to 40g of the formed catalyst and soak it at room temperature for 8h; put it in an oven at 105℃ and dry it for 5h; finally, put it in a muffle furnace and calcine it at 450℃ for 4h to obtain the catalyst.

[0086] The catalyst was loaded into a fixed bed reactor and reduced at 320°C for 5 h at 0.3 MPa using a hydrogen-nitrogen mixer.

[0087] 500 g of undecylphenol polyoxyethylene ether was weighed and the reaction conditions of Example 1 were repeated to carry out a hydroamination reaction to obtain undecylphenol polyoxyethylene ether amine. The yield of undecylphenol polyoxyethylene ether amine was 98.59% and the conversion rate of undecylphenol polyoxyethylene ether was 98.88%.

[0088] Example 5

[0089] The preparation method of Example 4 was repeated, except that dodecylphenol polyoxyethylene ether was used to replace the undecylphenol polyoxyethylene ether in Example 4. Other treatment conditions were the same as those in Example 4 to obtain dodecylphenol polyoxyethylene ether amine.

[0090] The yield of dodecylphenol polyoxyethylene ether amine was 98.89%, and the conversion rate of dodecylphenol polyoxyethylene ether was 97.86%.

[0091] Example 6

[0092] Weigh 50g of pseudo-boehmite and add it to a polytetrafluoroethylene-lined autoclave, then add an aqueous solution of ammonium bicarbonate with a pH value of 10, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.5:1; put the autoclave into a roller heating furnace and age it at 160℃ for 15h; take out the aged solution and put it into an oven to dry at 120℃ for 9h, and finally put it into a muffle furnace and calcine it at 650℃ for 4h to obtain a macroporous Al2O3 carrier. Al2O3 pore volume 2.57mL.g -1 , pores with a pore radius greater than 100 nm account for 46.88%.

[0093] Weigh 35.74g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 60wt% aqueous solution, stir at room temperature for 8h, add 30g macroporous Al2O3 carrier and impregnate at room temperature for 15h; put the obtained catalyst precursor into an oven at 120℃ for 5h; then put it into a muffle furnace for calcination at 520℃ for 4h. The obtained catalyst powder is added with 4.5% of the system mass of carbonic acid solution (concentration 10wt%) and 2% graphite to form a 3mm*3mm cylindrical catalyst.

[0094] Weigh 21.105 g of chromium nitrate nonahydrate (sulfide ion content less than 10 ppm) to prepare a 50 wt% aqueous solution and add it to 50 g of the formed catalyst and soak it at room temperature for 8 hours; put it in an oven and dry it at 105°C for 5 hours; finally, put it in a muffle furnace and calcine it at 450°C for 5 hours to obtain the catalyst.

[0095] The catalyst was loaded into a fixed bed reactor and reduced at 330°C for 5 h at 0.25 MPa using a hydrogen-nitrogen mixer.

[0096] Weigh 500g of nonylphenol polyoxyethylene ether, the molar ratio of liquid ammonia to nonylphenol polyoxyethylene ether is 10:1, and stir at a volume space velocity of 1h -1 , reaction temperature 270°C, reaction pressure 6MPa conditions, a hydrogenation reaction was carried out to obtain nonylphenol polyoxyethylene ether amine.

[0097] The yield of nonylphenol polyoxyethylene ether amine was 97.81%, and the conversion rate of nonylphenol polyoxyethylene ether was 97.89%.

[0098] Example 7

[0099] Example 1 was repeated, except that nickel nitrate hexahydrate (sulfide ion content: 20 ppm) was used instead of nickel nitrate hexahydrate (sulfide ion content: 15 ppm). Other treatment conditions were the same as those in Example 1.

[0100] The yield of decylphenol polyoxyethylene ether amine was 93.45%, and the conversion rate of decylphenol polyoxyethylene ether was 95.52%.

[0101] Example 8

[0102] Weigh 50g of pseudo-boehmite and add it to a polytetrafluoroethylene-lined autoclave, then add an aqueous solution of ammonium bicarbonate with a pH value of 10, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.8:1; put the autoclave into a roller heating furnace and age it at 160℃ for 15h; take out the aged solution and put it into an oven and dry it at 120℃ for 9h, and finally put it into a muffle furnace and calcine it at 600℃ for 4h to obtain a macroporous Al2O3 carrier. Al2O3 pore volume 2.97mL.g -1 , pores with a pore radius greater than 100 nm account for 57.86%.

[0103] Weigh 35.74g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 60wt% aqueous solution, stir at room temperature for 8h, add 30g macroporous Al2O3 carrier and impregnate at room temperature for 15h; put the obtained catalyst precursor into an oven at 120℃ for 5h; then put it into a muffle furnace for calcination at 520℃ for 4h. Add 5% of the system mass of carbonic acid solution (concentration 10wt%) and 2% graphite to the obtained catalyst powder and press it into a 3mm*3mm cylindrical catalyst.

[0104] Weigh 19.689 g of lanthanum nitrate hexahydrate (sulfide ion content less than 10 ppm), prepare a 50 wt% aqueous solution, add it to 50 g of the formed catalyst and soak it at room temperature for 8 hours; put it in an oven at 105°C and dry it for 5 hours; finally, put it in a muffle furnace and calcine it at 500°C for 5 hours to obtain the catalyst.

[0105] The catalyst was loaded into a fixed bed reactor and reduced at 350°C for 5 h at 0.3 MPa using a hydrogen-nitrogen mixer.

[0106] Weigh 500g of nonylphenol polyoxyethylene ether, the molar ratio of liquid ammonia to nonylphenol polyoxyethylene ether is 10:1, and stir at a volume space velocity of 0.8h -1 , reaction temperature 260°C, reaction pressure 5MPa conditions, a hydrogenation reaction was carried out to obtain nonylphenol polyoxyethylene ether amine.

[0107] The yield of nonylphenol polyoxyethylene ether amine was 98.83%, and the conversion rate of nonylphenol polyoxyethylene ether was 98.11%.

[0108] Example 9

[0109] Weigh 50g of pseudo-boehmite and add it to a polytetrafluoroethylene-lined autoclave, then add an aqueous solution of ammonium bicarbonate with a pH value of 10, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.6:1; put the autoclave into a roller heating furnace and age it at 170℃ for 20h; take out the aged solution and put it into an oven to dry at 120℃ for 8h, and finally put it into a muffle furnace and calcine it at 650℃ for 5h to obtain a macroporous Al2O3 carrier. Al2O3 pore volume 2.66mL.g -1 , pores with a pore radius greater than 100 nm account for 44.68%.

[0110] Weigh 40.123g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 60wt% aqueous solution, stir at room temperature for 8h, add 30g macroporous Al2O3 carrier and impregnate at room temperature for 18h; put the obtained catalyst precursor into an oven at 120℃ for 4h; then put it into a muffle furnace and roast it at 550℃ for 5h. Add 3% acetic acid solution (concentration 12wt%) and 1.5% graphite to the obtained catalyst powder to press it into a 3mm*3mm cylindrical catalyst.

[0111] Weigh 17.187g of nickel nitrate hexahydrate (sulfide ion content less than 15ppm) and 15.678g of lanthanum nitrate hexahydrate (sulfide ion content less than 13ppm), prepare a 65wt% aqueous solution, add it to 40g of the formed catalyst and soak it at room temperature for 8h; put it in an oven at 105°C and dry it for 5h; finally, put it in a muffle furnace and calcine it at 450°C for 4h to obtain the catalyst.

[0112] The catalyst was loaded into a fixed bed reactor and reduced at 350°C for 6 h at 0.25 MPa using a hydrogen-nitrogen mixer.

[0113] Weigh 500g of decylphenol polyoxyethylene ether, the molar ratio of liquid ammonia to decylphenol polyoxyethylene ether is 13:1, and stir at a volume space velocity of 1.0h -1 , reaction temperature 250°C, reaction pressure 6MPa conditions, a hydrogenation reaction was carried out to obtain decylphenol polyoxyethylene ether amine.

[0114] The yield of decylphenol polyoxyethylene ether amine was 97.88%, and the conversion rate of decylphenol polyoxyethylene ether was 97.56%.

[0115] Example 10

[0116] Weigh 50g of pseudo-boehmite and add it to a polytetrafluoroethylene-lined autoclave, then add an aqueous solution of ammonium bicarbonate with a pH value of 10, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.75:1; put the autoclave into a roller heating furnace and age it at 160℃ for 15h; take out the aged solution and put it into an oven to dry at 120℃ for 9h, and finally put it into a muffle furnace and calcine it at 650℃ for 6h to obtain a macroporous Al2O3 carrier. Al2O3 pore volume 2.37mL.g -1 , pores with a pore radius greater than 100 nm account for 42.37%.

[0117] Weigh 35.74g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 60wt% aqueous solution, stir at room temperature for 8h, add 30g macroporous Al2O3 carrier and impregnate at room temperature for 15h; put the obtained catalyst precursor into an oven at 120℃ for 5h; then put it into a muffle furnace for calcination at 520℃ for 4h. Add 2.5% of the system mass of carbonic acid solution (concentration 10wt%) and 2% graphite to the obtained catalyst powder and press it into a 3mm*3mm cylindrical catalyst.

[0118] Weigh 21.378g of cerium nitrate hexahydrate (sulfide ion content less than 10ppm) to prepare a 50wt% aqueous solution and add it to 50g of the formed catalyst and soak it at room temperature for 8h; put it in an oven at 105℃ and dry it for 5h; finally put it in a muffle furnace and calcine it at 550℃ for 6h to obtain the catalyst.

[0119] The catalyst was loaded into a fixed bed reactor and reduced at 340°C for 6 h at 0.3 MPa using a hydrogen-nitrogen mixer.

[0120] Weigh 500g of nonylphenol polyoxyethylene ether, the molar ratio of liquid ammonia to nonylphenol polyoxyethylene ether is 12:1, and stir at a volume space velocity of 0.8h -1 , reaction temperature 260°C, reaction pressure 5MPa conditions, a hydrogenation reaction was carried out to obtain nonylphenol polyoxyethylene ether amine.

[0121] The yield of nonylphenol polyoxyethylene ether amine was 96.23%, and the conversion rate of nonylphenol polyoxyethylene ether was 97.81%.

[0122] Embodiment 11

[0123] Weigh 50g of pseudo-boehmite and add it to a polytetrafluoroethylene-lined autoclave, then add an aqueous solution of ammonium bicarbonate with a pH value of 10.5, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.8:1; put the autoclave into a roller heating furnace and age it at 150℃ for 15h; take out the aged solution and put it into an oven and dry it at 120℃ for 8h, and finally put it into a muffle furnace and calcine it at 600℃ for 5h to obtain a macroporous Al2O3 carrier. Al2O3 pore volume 2.99mL.g -1 , pores with a pore radius greater than 100 nm account for 59.86%.

[0124] Weigh 38.67g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 56.31wt% aqueous solution, stir at room temperature for 8h, add 30g macroporous Al2O3 carrier and impregnate at room temperature for 18h; put the obtained catalyst precursor into an oven at 120℃ for 4h; then put it into a muffle furnace and roast it at 500℃ for 5h. Add 3% acetic acid solution (concentration 12wt%) and 1.5% graphite to the obtained catalyst powder to press it into a 3mm*3mm cylindrical catalyst.

[0125] Weigh 16.573 g of lanthanum nitrate hexahydrate (sulfide ion content less than 10 ppm) and 14.671 g of copper nitrate trihydrate (sulfide ion content less than 13 ppm), prepare a 65 wt% aqueous solution, add it to 40 g of the formed catalyst and soak it at room temperature for 8 hours; put it in an oven at 105°C and dry it for 5 hours; finally, put it in a muffle furnace and calcine it at 450°C for 4 hours to obtain the catalyst.

[0126] The catalyst was loaded into a fixed bed reactor and reduced at 320°C for 5 h at 0.3 MPa using a hydrogen-nitrogen mixer.

[0127] Weigh 500g of dodecylphenol polyoxyethylene ether, the molar ratio of liquid ammonia to dodecylphenol polyoxyethylene ether is 12:1, and at a volume space velocity of 0.95h -1, reaction temperature 250°C, reaction pressure 5MPa conditions, a hydrogenation reaction was carried out to obtain dodecylphenol polyoxyethylene ether amine.

[0128] The yield of dodecylphenol polyoxyethylene ether amine was 98.21%, and the conversion rate of dodecylphenol polyoxyethylene ether was 98.16%.

[0129] Example 12

[0130] Weigh 50g of pseudo-boehmite and add it to a polytetrafluoroethylene-lined autoclave, then add an aqueous solution of ammonium bicarbonate with a pH value of 10, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.5:1; put the autoclave into a roller heating furnace and age it at 180℃ for 24h; take out the aged solution and put it into an oven to dry at 120℃ for 8h, and finally put it into a muffle furnace and calcine it at 650℃ for 8h to obtain a macroporous Al2O3 carrier. Al2O3 pore volume 2.17mL.g -1 , pores with a pore radius greater than 100 nm account for 41.18%.

[0131] Weigh 38.67g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 56.31wt% aqueous solution, stir at room temperature for 8h, add 30g macroporous Al2O3 carrier and impregnate at room temperature for 18h; put the obtained catalyst precursor into an oven at 120℃ for 4h; then put it into a muffle furnace for calcination at 500℃ for 5h. Add 4.5% acetic acid solution (concentration 12wt%) and 2% graphite to the obtained catalyst powder to press it into a 3mm*3mm cylindrical catalyst.

[0132] Weigh 15.234 g of cerium nitrate hexahydrate (sulfide ion content less than 10 ppm) and 14.671 g of copper nitrate trihydrate (sulfide ion content less than 13 ppm), prepare a 65 wt% aqueous solution, add it to 40 g of the molded catalyst and soak it at room temperature for 8 hours; put it in an oven at 105°C and dry it for 5 hours; finally, put it in a muffle furnace and calcine it at 450°C for 4 hours to obtain the catalyst.

[0133] The catalyst was loaded into a fixed bed reactor and reduced at 320°C for 5 h at 0.3 MPa using a hydrogen-nitrogen mixer.

[0134] Weigh 500g of dodecylphenol polyoxyethylene ether, the molar ratio of liquid ammonia to dodecylphenol polyoxyethylene ether is 12:1, and at a volume space velocity of 0.95h -1 , reaction temperature 250°C, reaction pressure 5MPa conditions, a hydrogenation reaction was carried out to obtain dodecylphenol polyoxyethylene ether amine.

[0135] The yield of dodecylphenol polyoxyethylene ether amine was 95.27%, and the conversion rate of dodecylphenol polyoxyethylene ether was 96.46%.

[0136] Comparative Example 1

[0137] Weigh 38.67g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 56.31wt% aqueous solution, stir at room temperature for 8h, add 30g commercial Al2O3 (Al2O3 pore volume 2.17mL.g -1 , pores with pore radius greater than 100nm account for 31.80%) in a carrier at room temperature for 18 hours; the obtained catalyst precursor is placed in an oven at 120°C for 4 hours; and then placed in a muffle furnace for calcination at 500°C for 5 hours. The obtained catalyst powder is added with acetic acid solution (concentration 12wt%) accounting for 3% of the system mass and 1.5% graphite to form a 3mm*3mm cylindrical catalyst.

[0138] Weigh 17.187g of nickel nitrate hexahydrate (sulfide ion content less than 15ppm), prepare a 63.22% aqueous solution, add it to 40g of the formed catalyst and soak it at room temperature for 8h; put it in an oven at 105℃ and dry it for 5h; finally, put it in a muffle furnace and calcine it at 450℃ for 4h to obtain the catalyst.

[0139] The catalyst was loaded into a fixed bed reactor and reduced at 320°C for 5 h at 0.3 MPa using a hydrogen-nitrogen mixer.

[0140] Weigh 500g of decylphenol polyoxyethylene ether, the molar ratio of liquid ammonia to decylphenol polyoxyethylene ether is 8:1, and stir at a volume space velocity of 1.5h -1 , reaction temperature 265°C, reaction pressure 5MPa conditions, a hydrogenation reaction was carried out to obtain decylphenol polyoxyethylene ether amine.

[0141] The yield of decylphenol polyoxyethylene ether amine was 88.24%, and the conversion rate of decylphenol polyoxyethylene ether was 90.41%.

[0142] Comparative Example 2

[0143] Weigh 38.67g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 56.31wt% aqueous solution, stir at room temperature for 8h, add 30g commercial Al2O3 (Al2O3 pore volume 2.87mL.g -1 , pores with pore radius greater than 100nm account for 24.81%) in a carrier at room temperature for 18 hours; the obtained catalyst precursor is placed in an oven at 120°C for 4 hours; and then placed in a muffle furnace for calcination at 500°C for 5 hours. The obtained catalyst powder is added with graphite accounting for 1.5% of the system mass and pressed into a 3mm*3mm cylindrical catalyst.

[0144] Weigh 17.187g of nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 63.22wt% aqueous solution and add it to 40g of the formed catalyst and soak it at room temperature for 8h; put it in an oven and dry it at 105℃ for 5h; finally, put it in a muffle furnace and calcine it at 450℃ for 4h to obtain the catalyst.

[0145] The catalyst was loaded into a fixed bed reactor and reduced at 320°C for 5 h at 0.3 MPa using a hydrogen-nitrogen mixer.

[0146] Weigh 500g of decylphenol polyoxyethylene ether, liquid ammonia and alkylphenol polyoxyethylene ether in a molar ratio of 8:1, at a volume space velocity of 1.5h -1 , reaction temperature 265°C, reaction pressure 5MPa conditions, a hydrogenation reaction was carried out to obtain decylphenol polyoxyethylene ether amine.

[0147] The yield of decylphenol polyoxyethylene ether amine was 75.25%, and the conversion rate of decylphenol polyoxyethylene ether was 80.40%.

[0148] Comparative Example 3

[0149] Weigh 50g of pseudo-boehmite and add it to a polytetrafluoroethylene-lined autoclave, then add an aqueous solution of ammonium bicarbonate with a pH value of 10.5, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.75:1; start stirring and age in the autoclave at 170°C for 20h; take out the aged solution and put it in an oven at 120°C to dry for 8h, and finally put it in a muffle furnace at 600°C for 5h to obtain the carrier Al2O3. The pore volume of Al2O3 is 2.98mL.g -1 , pores with a pore radius greater than 100 nm account for 35.18%.

[0150] Weigh 38.67g nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 56.31wt% aqueous solution, stir at room temperature for 8h, add 30g macroporous Al2O3 carrier and impregnate at room temperature for 18h; put the obtained catalyst precursor into an oven at 120℃ for 4h; then put it into a muffle furnace and roast it at 500℃ for 5h. Add 3% acetic acid solution (concentration 12wt%) and 1.5% graphite to the obtained catalyst powder to press it into a 3mm*3mm cylindrical catalyst.

[0151] Weigh 17.187g of nickel nitrate hexahydrate (sulfide ion content less than 15ppm) to prepare a 63.22wt% aqueous solution and add it to 40g of the formed catalyst and soak it at room temperature for 8h; put it in an oven and dry it at 105℃ for 5h; finally, put it in a muffle furnace and calcine it at 450℃ for 4h to obtain the catalyst.

[0152] The catalyst was loaded into a fixed bed reactor and reduced at 320°C for 5 h at 0.3 MPa using a hydrogen-nitrogen mixer.

[0153] Weigh 500g of decylphenol polyoxyethylene ether, liquid ammonia and alkylphenol polyoxyethylene ether in a molar ratio of 8:1, at a volume space velocity of 1.5h -1 , reaction temperature 265°C, reaction pressure 5MPa conditions, a hydrogenation reaction was carried out to obtain decylphenol polyoxyethylene ether amine.

[0154] The yield of decylphenol polyoxyethylene ether amine was 81.45%, and the conversion rate of decylphenol polyoxyethylene ether was 83.67%.

[0155] It can be seen from Examples 1-12 and Comparative Examples 1-3 that the alkylphenol polyoxyethylene ethers prepared by the method of Examples 1 to 12 of the present invention have high conversion rates and high reaction yields.

[0156] As described above, although the present invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the present invention itself. Various changes in form and details may be made without departing from the spirit and scope of the present invention as defined in the appended claims.

Claims

1. Application of a macromolecular special amine catalyst in the hydroamination reaction of alkylphenol polyoxyethylene ether, characterized in that: The catalyst is prepared by the following method: 50 g of pseudo-boehmite is weighed and added into a high-pressure reactor lined with polytetrafluoroethylene, and then an aqueous solution of ammonium bicarbonate with a pH value of 10.5 is added, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.7:1; the high-pressure reactor is placed in a roller heating furnace for aging at 170° C. for 20 h; the aged solution is taken out and placed in an oven for drying at 120° C. for 8 h, and finally placed in a muffle furnace for calcination at 600° C. for 5 h to obtain a macroporous Al2O3 carrier; the pore volume of Al2O3 is 2.57 mL·g -1 , the pores with pore radius greater than 100 nm account for 59.80%; Weigh 38.67g of nickel nitrate hexahydrate with a sulfide ion content of less than 15ppm, prepare a 56.31wt% aqueous solution, stir at room temperature for 8h, add 30g of macroporous Al2O3 carrier, and impregnate at room temperature for 18h; put the obtained catalyst precursor into an oven at 120℃ and dry it for 4h; then put it into a muffle furnace and roast it at 500℃ for 5h, add 4.5% of the system mass of acetic acid solution and 1.5% of graphite to obtain the catalyst powder and press it into a 3mm*3mm cylindrical catalyst; the concentration of the acetic acid solution is 12wt%; Weigh 17.187g of nickel nitrate hexahydrate with a sulfide ion content less than 15ppm and 14.671g of copper nitrate trihydrate with a sulfide ion content less than 13ppm, prepare a 65wt% aqueous solution, add it to 40g of the formed catalyst and soak it at room temperature for 8h; put it in an oven and dry it at 105℃ for 5h; finally, put it in a muffle furnace and calcine it at 450℃ for 4h to obtain the catalyst.

2. Application of a macromolecular special amine catalyst in the hydroamination reaction of alkylphenol polyoxyethylene ether, characterized in that: The catalyst is prepared by the following method: 50 g of pseudo-boehmite is weighed and added into a high-pressure reactor lined with polytetrafluoroethylene, and then an aqueous solution of ammonium bicarbonate with a pH value of 10 is added, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.8:1; the high-pressure reactor is placed in a roller heating furnace for aging at 160° C. for 15 hours; the aged solution is taken out and placed in an oven for drying at 120° C. for 9 hours, and finally placed in a muffle furnace for calcination at 600° C. for 4 hours to obtain a macroporous Al2O3 carrier; the pore volume of Al2O3 is 2.97 mL·g -1 , the pores with pore radius greater than 100 nm account for 57.86%; Weigh 35.74g of nickel nitrate hexahydrate with a sulfide ion content of less than 15ppm, prepare a 60wt% aqueous solution, stir at room temperature for 8h, add 30g of macroporous Al2O3 carrier, and impregnate at room temperature for 15h; put the obtained catalyst precursor into an oven at 120℃ and dry it for 5h; then put it into a muffle furnace and roast it at 520℃ for 4h, add 5% of the system mass of carbonic acid solution and 2% of graphite to obtain the catalyst powder and press it into a 3mm*3mm cylindrical catalyst; the concentration of the carbonic acid solution is 10wt%; Weigh 19.689 g of lanthanum nitrate hexahydrate with a sulfide ion content of less than 10 ppm, prepare a 50 wt% aqueous solution, add it to 50 g of the formed catalyst and soak it at room temperature for 8 hours; put it in an oven at 105°C and dry it for 5 hours; finally, put it in a muffle furnace and calcine it at 500°C for 5 hours to obtain the catalyst.

3. Application of a macromolecular special amine catalyst in the hydroamination reaction of alkylphenol polyoxyethylene ether, characterized in that: The catalyst is prepared by the following method: 50g of pseudo-boehmite is weighed and added into a high-pressure reactor lined with polytetrafluoroethylene, and then an ammonium bicarbonate aqueous solution with a pH value of 10.5 is added, and the molar ratio of ammonium bicarbonate to pseudo-boehmite is 0.8:1; the high-pressure reactor is placed in a roller heating furnace for aging at 150°C for 15h; the aged solution is taken out and placed in an oven for drying at 120°C for 8h, and finally placed in a muffle furnace for calcination at 600°C for 5h to obtain a macroporous Al2O3 carrier; the pore volume of Al2O3 is 2.99mL·g -1 , the pores with pore radius greater than 100 nm account for 59.86%; Weigh 38.67g of nickel nitrate hexahydrate with a sulfur ion content of less than 15ppm, prepare a 56.31wt% aqueous solution, stir at room temperature for 8h, add 30g of macroporous Al2O3 carrier, and impregnate at room temperature for 18h; put the obtained catalyst precursor into an oven and dry it at 120℃ for 4h; then put it into a muffle furnace and roast it at 500℃ for 5h, add 3% of the system mass of acetic acid solution and 1.5% of graphite to obtain the catalyst powder and press it into a 3mm*3mm cylindrical catalyst; the concentration of the acetic acid solution is 12wt%; Weigh 16.573 g of lanthanum nitrate hexahydrate with a sulfide ion content less than 10 ppm and 14.671 g of copper nitrate trihydrate with a sulfide ion content less than 13 ppm, prepare a 65 wt% aqueous solution, add it to 40 g of the formed catalyst and soak it at room temperature for 8 hours; put it in an oven and dry it at 105°C for 5 hours; finally, put it in a muffle furnace and calcine it at 450°C for 4 hours to obtain the catalyst.

4. The use according to any one of claims 1 to 3, characterized in that: The conditions for using the catalyst for the hydroamination of alkylphenol polyoxyethylene ether include: reaction temperature of 180-295°C; liquid volume space velocity of 0.5-2.0h -1 ; Reaction pressure 2~8MPa; The alkylphenol polyoxyethylene ether is C6-C13 alkylphenol polyoxyethylene ether.

5. The use according to any one of claims 1 to 3, characterized in that: Before the hydroamination reaction, the catalyst is reduced with a hydrogen-nitrogen mixed gas, and the reduction treatment conditions include: a reduction temperature of 280-360° C.; a concentration of the reducing gas hydrogen-nitrogen mixed gas gradually increased from 1% to 20%; and a reduction pressure of 0.25-0.8 MPa.

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