A method for preparing alkylphenol polyoxyethylene ether monoamine

Abstract

This invention discloses a method for preparing alkylphenol polyoxyethylene ether monoamines, belonging to the field of catalytic amination technology. In the presence of a supported nickel-based catalyst, the alkylphenol polyoxyethylene ether, liquid ammonia, and hydrogen are subjected to a hydroammoniation reaction in a polar solvent; the alkylphenol polyoxyethylene ether is C6-C. 13 Alkylphenol polyoxyethylene ether; the supported nickel catalyst, by weight, has a Ni content of 15-45%, a Cu content of 0-10%, a Cr content of 0-10%, and an Al₂O₃ support content of 45-80%; the conditions for the hydroammoniation reaction include: a reaction temperature of 180-290°C and a liquid hourly space velocity of 0.5-2.0 h⁻¹. ‑1 The reaction pressure is 2–8 MPa. The alkylphenol polyoxyethylene ether monoamine primary amine obtained by this invention has high purity and high reaction yield, and the reaction process can carry out the hydroammoniation reaction under relatively mild conditions.

Description

Technical Field

[0001] This invention belongs to the field of catalytic amination technology, specifically relating to a method for preparing alkylphenol polyoxyethylene ether monoamine. Background Technology

[0002] Alkylphenol polyoxyethylene ether monoamines belong to the aromatic hydrocarbon specialty amines, a class of aromatic hydrocarbon compounds capped with primary or secondary amino groups. Due to their flexible polyether chains and alkylphenol backbones, coupled with the more reactive terminal hydrogen, they can replace alkylphenol polyoxyethylene ethers in certain applications, enhancing the performance of new materials. Alkylphenol polyoxyethylene ether monoamines are mainly used in polyurea spraying, gasoline detergents, and polyurethane reaction injection molding materials. Driven by the development of end-use industries, the global market demand for aromatic hydrocarbon specialty amines has been increasing year by year in recent years, especially in Asia, which is experiencing rapid economic development and has a growing demand for aromatic hydrocarbon specialty amines. C6-C 13 Alkylphenol polyoxyethylene ethers are important fuel additives, and their consumption is related to the amount of gasoline and diesel used.

[0003] The traditional process for synthesizing alkylphenol polyoxyethylene ether monoamines uses alkylphenol polyoxyethylene ether and ammonia as raw materials. In the presence of nickel in the skeleton, the reaction is carried out in a batch reactor at 270–300°C and 10–25 MPa to obtain alkylphenol polyoxyethylene ether monoamines.

[0004] The above traditional reaction processes have high reaction pressures, and the primary amines produced have low purity and low reaction yields. Summary of the Invention

[0005] Objective of this invention: To address the shortcomings of existing technologies, this invention provides a method for preparing alkylphenol polyoxyethylene ether monoamines. This method features low reaction pressure, high purity of the primary amine, and high reaction yield.

[0006] Technical solution: The objective of this invention is achieved through the following technical solution:

[0007] This invention provides a method for preparing alkylphenol polyoxyethylene ether monoamine, comprising the following steps: in the presence of a supported nickel-based catalyst, alkylphenol polyoxyethylene ether, liquid ammonia, and hydrogen undergo a hydroammoniation reaction in a polar solvent; wherein the alkylphenol polyoxyethylene ether is C6-C. 13 Alkylphenol polyoxyethylene ether;

[0008] The supported nickel-based catalyst, by weight, has a Ni content of 15-45%, a Cu content of 0-10%, a Cr content of 0-10%, and a support Al2O3 content of 45-80%.

[0009] The conditions for the hydroammoniation reaction include: a reaction temperature of 180–290°C and a liquid hourly space velocity of 0.5–2.0 h⁻¹. -1 The reaction pressure is 2–8 MPa.

[0010] The alkylphenol polyoxyethylene ether monoamine primary amine prepared by this invention has high purity and high reaction yield, and the reaction process can carry out hydroammoniation reaction under relatively mild conditions.

[0011] In this invention, the polar solvent can be a conventional choice in the art. To further improve catalyst activity, reduce side reactions, and increase the purity of the primary amine product, preferably, the polar solvent is selected from one or more of water, tert-butanol, dioxane, or tetrahydrofuran.

[0012] In this invention, there are no particular requirements for the mass ratio of the alkylphenol polyoxyethylene ether to the polar solvent. To further improve the conversion rate of the alkylphenol polyoxyethylene ether monoamine and the purity of the primary amine, preferably, the mass ratio of the alkylphenol polyoxyethylene ether to the polar solvent is (0.3–0.6):1.

[0013] In this invention, there are no particular requirements for the molar ratio of liquid ammonia to alkylphenol polyoxyethylene ether. However, to further improve the primary amine purity of the alkylphenol polyoxyethylene ether monoamine, preferably, the molar ratio of liquid ammonia to alkylphenol polyoxyethylene ether is (5-15):1.

[0014] To further improve the yield of alkylphenol polyoxyethylene ether monoamine, preferably, the water content of the alkylphenol polyoxyethylene ether is less than 1 wt%, and the potassium ion content of the alkylphenol polyoxyethylene ether is less than 20 ppm. Water in the alkylphenol polyoxyethylene ether inhibits the hydroammoniation reaction, and the lower the water content, the better; potassium ions in the alkylphenol polyoxyethylene ether affect catalyst performance, therefore, the potassium ion content is controlled to be less than 20 ppm in this invention.

[0015] Preferably, the supported nickel-based catalyst is one or more of Ni / Cu / Cr / Al2O3, Ni / Cu / Al2O3, and Ni / Al2O3 catalysts.

[0016] A preferred embodiment of the present invention includes the following steps:

[0017] (1) The supported nickel catalyst was loaded into the fixed bed reactor, and the fixed bed reactor was subjected to nitrogen purging and airtightness test;

[0018] (2) Activation of the supported nickel catalyst in the reactor;

[0019] (3) Mix alkylphenol polyoxyethylene ether, polar solvent and liquid ammonia evenly;

[0020] (4) Pressurize and heat the reactor, and introduce hydrogen and liquid mixture to carry out the amination reaction.

[0021] In order to further improve the primary amine purity and product yield of alkylphenol polyoxyethylene ether monoamine, more preferably, in step (2), the activation method of the supported nickel catalyst is: the catalyst is pre-adsorbed with an alkaline solution, the adsorption temperature is 5-30℃, and the adsorption time is 5-15h.

[0022] Furthermore, the concentration of the alkaline solution is 1–15 wt%; the alkaline solution is selected from one or more of ammonia water, sodium bicarbonate aqueous solution, sodium hydroxide aqueous solution, or potassium hydroxide aqueous solution. In this invention, the alkaline solution serves as an activator, and sodium hydroxide or sodium bicarbonate aqueous solution is more preferably used.

[0023] To further improve catalyst activity and increase the primary amine purity and product yield of alkylphenol polyoxyethylene ether monoamine, this invention performs a reduction treatment on the supported nickel catalyst with hydrogen before the hydroammoniation reaction. The conditions for the reduction treatment can be conventionally chosen in the art. Preferably, the conditions for the reduction treatment include: a reduction temperature of 280–360°C; a hydrogen-nitrogen mixture concentration gradually increased from 1% to 20%; and a reduction pressure of 0.05–0.8 MPa.

[0024] The present invention does not impose any special requirements on the preparation method of the supported nickel catalyst, and the method is a conventional technique in the field.

[0025] Beneficial effects:

[0026] The method for preparing alkylphenol polyoxyethylene ether monoamine of this invention features a simple reaction process, flexible quality switching, and easy scale-up, making it readily applicable for industrial production. During production, the reaction conditions are mild, the reaction pressure is low, the primary amine selectivity is high (greater than 92%), and the reaction yield is high (the yield of alkylphenol polyoxyethylene ether monoamine is greater than 91%). Detailed Implementation

[0027] The technical solution of the present invention will be described in detail below through specific embodiments, but the scope of protection of the present invention is not limited to the embodiments described.

[0028] The endpoints and any values ​​of the ranges disclosed herein 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0029] C6-C 13Alkylphenol polyoxyethylene ether (Jiangsu Zhongshan New Materials Co., Ltd., industrial grade)

[0030] Tetrahydrofuran (Nanjing Chemical Reagent Co., Ltd., analytical grade)

[0031] Dioxane (Nanjing Chemical Reagent Co., Ltd., analytical grade)

[0032] tert-Butanol (Nanjing Chemical Reagent Co., Ltd., analytical grade)

[0033] Sodium hydroxide (Nanjing Chemical Reagent Co., Ltd., analytical grade)

[0034] Potassium hydroxide (Nanjing Chemical Reagent Co., Ltd., analytical grade)

[0035] Sodium bicarbonate (Nanjing Chemical Reagent Co., Ltd., analytical grade)

[0036] Supported nickel-based catalyst (in-house developed by Jinpu Group Research Institute, model JP-1)

[0037] Fixed-bed reactor (Beijing Tuochuan Instrument Equipment Co., Ltd., catalyst loading 150mL)

[0038] The method involved in this invention is as follows:

[0039] Preparation method of supported nickel catalyst: Weigh appropriate amounts of nickel nitrate, copper nitrate, or chromium nitrate to prepare an aqueous solution. Add a pre-formed alumina support (3mm*3mm cylindrical support) to the aqueous solution and impregnate overnight. Place the impregnated support in an oven and dry at 120-150℃ for 10 hours. Finally, calcine it in a muffle furnace at 300-380℃ for 8-12 hours.

[0040] Analytical method for alkylphenol polyoxyethylene ether monoamine products: Weigh two portions of a certain mass into 250mL Erlenmeyer flasks (1–4g, accurate to 0.1mg; if solid, dissolve first), label them S and T, add 50mL of CHCl3 and heat for 1 minute to prevent NH4+ ions from forming. 4+ To eliminate interference, cool the sample to room temperature. Add 3 mL of salicylaldehyde to sample S, let it stand for 30 minutes, add 1 mL of bromophenol blue indicator, and titrate with approximately 0.1 mol / L HCl to a yellow endpoint while stirring. Calculate the sum of the secondary and tertiary amine values ​​based on the volume of HCl consumed, V2. Add 3 mL of phenyl isothiocyanate to sample T, let it stand for 30 minutes, add 1 mL of bromophenol blue indicator, and titrate with approximately 0.1 mol / L HCl to a yellow endpoint while stirring. Calculate the tertiary amine value based on the volume of HCl consumed, V3.

[0041] The sum of the values ​​of secondary and tertiary amines (mmol / g) = C*V² / M

[0042] Tertiary amine value (mmol / g) = C*V3 / M

[0043] Secondary amine value = Sum of secondary and tertiary amine values ​​- Tertiary amine value;

[0044] Primary amine value = Total amine value - Sum of secondary and tertiary amine values.

[0045] C: Hydrochloric acid concentration, mol / L;

[0046] M: Sample mass, g;

[0047] V2: Volume of hydrochloric acid consumed, mL;

[0048] V3: Volume of hydrochloric acid consumed, mL.

[0049] Methods for calculating the yield and primary amine purity of alkylphenol polyoxyethylene ether monoamines:

[0050]

[0051]

[0052]

[0053] Yield % = X × S

[0054] Example 1

[0055] A Ni / Cu / Al2O3 supported nickel catalyst (Ni content 28wt%, Cu content 8wt%, Al2O3 content 64wt%, 3mm*3mm cylindrical shape, based on total catalyst weight) was prepared by impregnation method. The catalyst was pre-adsorbed with 10wt% sodium hydroxide solution at 25℃ for 10h and then loaded into a fixed-bed reactor. The fixed-bed reactor underwent nitrogen purging and airtightness tests. Under hydrogen pressure of 0.1MPa, the hydrogen concentration of the reducing gas was gradually increased from 1% to 20%, increasing by 2% each time, and reduction was performed at 340℃ for 10h.

[0056] Weigh 500g of decylphenol polyoxyethylene ether (ethylene oxide repeating unit 10, water content 0.5wt%, potassium ion content 10ppm) and 1000g of tetrahydrofuran, mix thoroughly, and then mix liquid ammonia with decylphenol polyoxyethylene ether at a molar ratio of 10:1 at a volume hourly space velocity (VHSV) of 1.5h. -1 Decylphenol polyoxyethylene etheramine was obtained by hydroammoniation under reaction conditions of 255℃ and 4MPa.

[0057] The yield of decylphenol polyoxyethylene ether amine was 96.28%, and the primary amine selectivity was 96.84%.

[0058] Example 2

[0059] A Ni / Cr / Al2O3 supported nickel catalyst (Ni content 35wt%, Cr content 8wt%, Al2O3 content 57wt%, honeycomb briquette form) was prepared by impregnation method. It was pre-adsorbed with 13wt% sodium bicarbonate aqueous solution at 30℃ for 14h and then loaded into a fixed-bed reactor. The fixed-bed reactor was subjected to nitrogen purging and airtightness tests. Under hydrogen pressure of 0.2MPa, the hydrogen concentration of the reducing gas was gradually increased from 1% to 20%, with each increase of 2%, and the reduction was carried out at 350℃ for 12h.

[0060] Weigh 500g of undecylphenol polyoxyethylene ether (ethylene oxide repeating unit 12, water content 0.6wt%, potassium ion content 12ppm) and 1200g of tert-butanol, mix thoroughly, and then mix liquid ammonia with undecylphenol polyoxyethylene ether at a molar ratio of 12:1 at a volume hourly space velocity (VHSV) of 1.0 h⁻¹. -1 Undecylphenol polyoxyethylene etheramine was obtained by hydroammoniation under reaction conditions of 265℃ and 6MPa.

[0061] The yield of undecylphenol polyoxyethylene ether amine was 97.29%, and the primary amine selectivity was 97.94%.

[0062] Example 3

[0063] A Ni / Al2O3 supported nickel catalyst (Ni content 35wt%, Al2O3 content 65wt%, clover-shaped) was prepared by impregnation. It was pre-adsorbed with 15wt% ammonia solution at 15℃ for 10h and then loaded into a fixed-bed reactor. The fixed-bed reactor was subjected to nitrogen purging and airtightness tests. The hydrogen concentration of the reducing gas was gradually increased from 1% to 20%, increasing by 2% each time. The reduction was carried out at 360℃ for 10h under hydrogen pressure of 0.5MPa.

[0064] Weigh 500g of nonylphenol polyoxyethylene ether (ethylene oxide repeating unit 14, water content 0.4wt%, potassium ion content 10ppm) and 1000g of dioxane, mix thoroughly, and then mix liquid ammonia with nonylphenol polyoxyethylene ether at a molar ratio of 15:1 at a volume hourly space velocity of 0.9h. -1 Nonylphenol polyoxyethylene etheramine was obtained by hydroammoniation under reaction conditions of 260℃ and 3MPa.

[0065] The yield of nonylphenol polyoxyethylene ether amine was 94.89%, and the primary amine selectivity was 98.94%.

[0066] Example 4

[0067] The preparation method of Example 1 was repeated, except that the 10 wt% sodium hydroxide solution in Example 1 was replaced with a mixed solution of 10 wt% sodium hydroxide and sodium bicarbonate, and the molar ratio of sodium hydroxide to sodium bicarbonate was 2:1. All other treatment conditions were the same as in Example 1.

[0068] The yield of decylphenol polyoxyethylene ether amine was 97.95%, and the primary amine selectivity was 95.14%.

[0069] Example 5

[0070] The preparation method of Example 1 was repeated, except that dodecylphenol polyoxyethylene ether (ethylene oxide repeating unit 10, water content 0.4wt%, potassium ion content 12ppm) was used instead of decylphenol polyoxyethylene ether in Example 1, and all other treatment conditions were the same as in Example 1.

[0071] The yield of dodecylphenol polyoxyethylene ether amine was 95.46%, and the primary amine selectivity was 97.64%.

[0072] Example 6

[0073] The preparation method of Example 1 was repeated, except that nonylphenol polyoxyethylene ether (ethylene oxide repeating unit 18, water content 0.4wt%, potassium ion content 10ppm) was used instead of decylphenol polyoxyethylene ether in Example 1, and all other treatment conditions were the same as in Example 1.

[0074] The yield of nonylphenol polyoxyethylene ether amine was 96.82%, and the primary amine selectivity was 96.68%.

[0075] Example 7

[0076] The preparation method of Example 3 was repeated, but the molar ratio of liquid ammonia to nonylphenol polyoxyethylene ether was 5:1 instead of 15:1 in Example 3. All other treatment conditions were the same as in Example 3.

[0077] The yield of nonylphenol polyoxyethylene ether amine was 94.13%, and the primary amine selectivity was 93.01%.

[0078] Example 8

[0079] The preparation method of Example 3 was repeated, but a 1 wt% ammonia solution was used instead of the 15 wt% ammonia solution in Example 3 for catalyst activation, and all other treatment conditions were the same as in Example 3.

[0080] The yield of nonylphenol polyoxyethylene ether amine was 91.69%, and the primary amine selectivity was 92.94%.

[0081] Comparative Example 1

[0082] The preparation method of Example 1 was repeated, except that decylphenol polyoxyethylene ether (ethylene oxide repeating unit 10, water content 2.5 wt%, potassium ion content 30 ppm) was used instead of decylphenol polyoxyethylene ether (ethylene oxide repeating unit 10, water content 0.5 wt%, potassium ion content 10 ppm) in Example 1, and all other treatment conditions were the same as in Example 1.

[0083] The yield of decylphenol polyoxyethylene ether amine was 80.48%, and the primary amine selectivity was 95.74%.

[0084] Comparative Example 2

[0085] The preparation method of Example 1 was repeated, with the quality of the added decylphenol polyoxyethylene ether remaining unchanged, the molar ratio of liquid ammonia to alkylphenol polyoxyethylene ether being introduced being 4:1, and all other treatment conditions being the same as in Example 1.

[0086] The yield of decylphenol polyoxyethylene ether amine was 76.25%, and the primary amine selectivity was 65.14%.

[0087] Comparative Example 3

[0088] The preparation method of Example 1 was repeated, with the addition of decylphenol polyoxyethylene ether maintaining the same quality, the hydroammoniation reaction temperature being 150°C, and all other treatment conditions being the same as in Example 1.

[0089] The yield of decylphenol polyoxyethylene ether amine was 86.74%, and the primary amine selectivity was 90.24%.

[0090] Comparative Example 4

[0091] The preparation method of Example 1 was repeated, with the addition of decylphenol polyoxyethylene ether maintaining the same quality, the hydroammoniation reaction pressure being 1.5 MPa, and all other treatment conditions being the same as in Example 1.

[0092] The yield of decylphenol polyoxyethylene ether amine was 86.14%, and the primary amine selectivity was 54.32%.

[0093] Comparative Example 5

[0094] The preparation method of Example 1 was repeated, except that the supported nickel catalyst was not pre-adsorbed with an alkaline solution, and all other treatment conditions were the same as in Example 1.

[0095] The yield of decylphenol polyoxyethylene ether amine was 90.04%, and the primary amine selectivity was 73.54%.

[0096] Comparative Example 6

[0097] The preparation method of Example 1 was repeated, with the addition of decylphenol polyoxyethylene ether maintaining the same quality, and the liquid hourly space velocity (LHSV) was 0.2 h⁻¹. -1 All other processing conditions are the same as in Example 1.

[0098] The yield of decylphenol polyoxyethylene ether amine was 96.25%, and the primary amine selectivity was 65.43%.

[0099] Comparative Example 7

[0100] 30g of decylphenol polyoxyethylene ether (ethylene oxide repeating unit 10, water content 0.5wt%, potassium ion content 10ppm) and 4.5g of skeletal nickel catalyst were weighed and placed in a high-pressure reactor. The reactor was purged twice with nitrogen, and then 60L of ammonia and 1.5MPa of hydrogen were introduced respectively. The temperature was raised to 280℃ and the reaction pressure was 15MPa. The reaction was carried out for 6h, and the yield of decylphenol polyoxyethylene ether amine was 80.15%, with a primary amine selectivity of 65.84%.

[0101] Comparative Example 8

[0102] The preparation method of Example 1 was repeated, and the Cu / Zn / Al2O3 catalyst was prepared by impregnation instead of the Ni / Cu / Al2O3 supported nickel catalyst in Example 1. All other processing conditions were the same as in Example 1.

[0103] The yield of decylphenol polyoxyethylene ether amine was 40.25%, and the primary amine selectivity was 85.96%.

[0104] Comparative Example 9

[0105] A Ni / Cr / Al2O3 supported nickel catalyst (Ni content 35wt%, Cr content 8wt%, Al2O3 content 57wt%, honeycomb briquette form) was prepared by impregnation method. It was pre-adsorbed with 13wt% sodium bicarbonate aqueous solution at 30℃ for 14h, then loaded into a fixed bed reactor and reduced at 350℃ for 12h under hydrogen gas at 0.2MPa.

[0106] Weigh 500g of undecylphenol polyoxyethylene ether (ethylene oxide repeating unit 12, water content 0.6wt%, potassium ion content 12ppm), mix it thoroughly with liquid ammonia at a molar ratio of 12:1, and then mix at a volume hourly space velocity (VHSV) of 1.0 h⁻¹. -1 Undecylphenol polyoxyethylene etheramine was obtained by hydroammoniation under reaction conditions of 265℃ and 6MPa.

[0107] The yield of undecylphenol polyoxyethylene ether amine was 91.29%, and the primary amine selectivity was 77.24%.

[0108] As can be seen from Examples 1-8 and Comparative Examples 1-9, the alkylphenol polyoxyethylene ether monoamine prepared by the method of the present invention has a high yield, high primary amine purity, relatively mild reaction conditions, and does not involve high-pressure reaction.

[0109] As described above, although the invention has been shown and described with reference to specific preferred embodiments, it should not be construed as limiting the invention itself. Various changes in form and detail may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims

1. A method for preparing an alkylphenol polyoxyethylene ether monoamine, characterized in that, Includes the following steps: In the presence of a supported nickel-based catalyst, alkylphenol polyoxyethylene ether, liquid ammonia, and hydrogen undergo a hydroammoniation reaction in a polar solvent; the alkylphenol polyoxyethylene ether is C6-C. 13 Alkylphenol polyoxyethylene ether; The supported nickel-based catalyst, by weight, has a Ni content of 15-45%, a Cu content of 0-10%, a Cr content of 0-10%, and a support Al2O3 content of 45-80%. The conditions for the hydroammoniation reaction include: a reaction temperature of 255~260℃ and a liquid hourly space velocity of 0.9~1.5 h⁻¹. -1 The reaction pressure is 3~6 MPa; The polar solvent is selected from one or more of tert-butanol, dioxane, or tetrahydrofuran; The molar ratio of liquid ammonia to alkylphenol polyoxyethylene ether is (5-15):1; The alkylphenol polyoxyethylene ether has a water content of less than 1 wt% and a potassium ion content of less than 20 ppm. The activation method of the supported nickel catalyst is as follows: the catalyst is pre-adsorbed with an alkaline solution at an adsorption temperature of 5~30℃ for 5~15h.

2. The preparation method according to claim 1, characterized in that, The mass ratio of the alkylphenol polyoxyethylene ether to the polar solvent is (0.3~0.6):

1.

3. The preparation method according to claim 1, characterized in that, The supported nickel-based catalyst is one or more of Ni / Cu / Cr / Al2O3, Ni / Cu / Al2O3, and Ni / Al2O3 catalysts.

4. The preparation method according to any one of claims 1 to 3, characterized in that, Includes the following steps: (1) The supported nickel catalyst was loaded into the fixed bed reactor, and the fixed bed reactor was subjected to nitrogen purging and airtightness test; (2) Activate the supported nickel catalyst in the reactor; (3) Mix alkylphenol polyoxyethylene ether, polar solvent and liquid ammonia evenly; (4) Pressurize and heat the reactor, and introduce hydrogen and liquid mixture to carry out amination reaction.

5. The preparation method according to claim 1, characterized in that, The concentration of the alkaline solution is 1~15wt%; the alkaline solution is selected from one or more of ammonia water, sodium bicarbonate aqueous solution, sodium hydroxide aqueous solution or potassium hydroxide aqueous solution.

6. The preparation method according to claim 1, characterized in that, Before the hydroammoniation reaction, the supported nickel catalyst is reduced with hydrogen. The conditions for the reduction treatment include: a reduction temperature of 280~360℃; a hydrogen-nitrogen mixture concentration of reducing gas gradually increasing from 1% to 20%; and a reduction pressure of 0.05~0.8MPa.

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