CN112517039A - Novel nitrogen modified composite metal oxide insertion type catalyst and application thereof - Google Patents
Novel nitrogen modified composite metal oxide insertion type catalyst and application thereof Download PDFInfo
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- CN112517039A CN112517039A CN202011448123.3A CN202011448123A CN112517039A CN 112517039 A CN112517039 A CN 112517039A CN 202011448123 A CN202011448123 A CN 202011448123A CN 112517039 A CN112517039 A CN 112517039A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
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Abstract
The invention discloses a synthesis method of a novel carboxylic ester ethoxylation insertion type catalyst, wherein the catalyst is a nitrogen modified composite metal oxide catalyst and is synthesized by adopting a hydrothermal impregnation method, the synthesis method is simple and easy to operate, and the catalyst has good selectivity and excellent catalytic performance; in the preferable scheme, a titanate auxiliary agent is added during the synthesis of the carboxylic ester ethoxylate, the catalyst selectivity is further improved, the content of the byproduct polyethylene glycol is lower than 0.5%, and the catalytic performance can reach more than 5 gEO/gCat/min.
Description
Technical Field
The invention relates to a synthesis method of a novel nitrogen modified composite metal oxide insertion catalyst and application thereof in carboxylic ester insertion ethoxylation.
Background
In the daily chemical industry, the development of green detergents by using plant raw materials to replace mineral raw materials and adopting green surfactants and auxiliaries becomes the development trend of the future washing industry. The grease-based ethoxylate is a novel green surfactant which is generally prepared by inserting ethoxylation on fatty acid methyl ester, and the product can be prepared into fatty acid methyl ester ethoxylate sulfonate through sulfonation, so that the grease-based ethoxylate sulfonate has strong oil stain solubilizing capability and emulsifying property; the skin care product has mild performance, no toxicity or irritation, and good skin compatibility, and can reduce the irritation of the formula product; low foam; is an environment-friendly green nonionic surfactant.
The core of the technology is a catalyst, metal carboxylate is mostly adopted as the catalyst in China, the preparation cost of the catalyst is high, the selectivity is poor, 1% of polyethylene glycol byproduct exists in CN201680050314.X, the byproduct is not reduced, and the selectivity is improved. There is a need to develop new catalysts for carboxylate insertion ethoxylation.
Disclosure of Invention
The invention aims to provide a catalyst with good selectivity for carboxylic ester plug-in ethoxylation.
The invention adopts the following technical scheme:
a nitrogen-modified composite metal oxide catalyst, the preparation method of which comprises:
(1) adding MgO and ammonium nitrate in M1 (NO)3)yDipping in water solution, and carrying out precipitation reaction by using alkali metal hydroxide;
(2) and (2) adding the reaction solution obtained in the step (1) into a hydrothermal reaction kettle for hydrothermal reaction, washing with deionized water after the reaction is finished, and finally drying and grinding to obtain the catalyst.
In the present invention, M1 (NO)3)yIs one or more nitrates of metal elements selected from aluminum, zinc, cobalt, iron, silver, calcium, nickel, copper and the like, wherein aluminum nitrate is preferred;
with the reactant (MgO + ammonium nitrate + M1 (NO)3)y) The total mass is 100%, the MgO dosage is 20-78%, wherein the MgO dosage is preferably 45-70%; m1 (NO)3)yThe amount is 20-78%, preferably 25%40%, from 10 to 50% by weight of aqueous solution may be used; the amount of ammonium nitrate is 0.1-20%, preferably 1-15%.
In the invention, the temperature of the dipping process is 40-90 ℃, preferably 40-50 ℃; the time is 20-60h, preferably 30-40 h.
In the invention, the alkali metal hydroxide used in the precipitation reaction is, for example, sodium hydroxide and potassium hydroxide, and the alkali metal hydroxide is 20-50% aqueous solution, and the amount of the alkali metal hydroxide is enough to ensure that metal ions are completely precipitated.
In the invention, the precipitation reaction process is carried out, and the reaction temperature is 70-100 ℃, wherein the reaction temperature is preferably 70-80 ℃; the reaction time is 0.5-5h, preferably 1-2 h.
In the invention, the hydrothermal reaction process is carried out at the reaction temperature of 100-150 ℃, preferably at the reaction temperature of 120-140 ℃; the reaction time is 10-40h, preferably 20-30 h.
The invention also relates to a catalyst prepared according to the above process.
In a further aspect, the invention relates to the use of the above catalyst for the carboxylate insertion ethoxylation.
Carboxylate plug-in ethoxylation, comprising: the raw material carboxylic ester reacts with ethylene oxide under the action of a catalyst to obtain the carboxylic ester ethoxylate.
In the present invention, the carboxylic ester may be methyl dodecanoate or methyl tetradecanoate, and the molar ratio of the carboxylic ester to ethylene oxide is 1: 3-1: 6.
the catalyst is the nitrogen modified composite metal oxide catalyst, and the dosage of the catalyst is 1-5 wt% of the carboxylate, preferably 2-4 wt%.
In the invention, the reaction temperature in the preparation process of the carboxylate ethoxylate is 100-180 ℃, and preferably 130-170 ℃.
In the preparation process of the carboxylate ethoxylate, the reaction pressure is 0.1-1MPa, and preferably 0.2-0.7 MPa.
In a preferred embodiment, in the preparation process of the carboxylic ester ethoxylate, a titanate auxiliary agent is further added, and the titanate auxiliary agent can be at least one of methyl titanate, ethyl titanate, propyl titanate, butyl titanate and isopropyl titanate, wherein butyl titanate is preferred; the titanate auxiliary agent is used in an amount of 0 to 5% by weight, preferably 1.5 to 4% by weight, based on the total amount of the carboxylic ester and ethylene oxide.
According to the method, the content of polyethylene glycol in the carboxylate ethoxylate is below 2%, and in a preferable scheme of adding the titanate auxiliary agent, the content of polyethylene glycol can be below 0.5%.
The invention has the beneficial effects that:
the invention adopts a hydrothermal impregnation method to synthesize the catalyst, and the catalyst synthesis method is simple and easy to operate. The catalyst has good selectivity and excellent catalytic performance, the selectivity of the catalyst can be further improved after the titanate auxiliary agent is added in the process of synthesizing the carboxylic ester ethoxylate, the content of the byproduct polyethylene glycol is lower than 0.5%, and the catalytic performance can reach more than 5 gEO/gCat/min.
Detailed Description
The reactants involved in the examples, not specifically indicated, were all purchased from samples of the reagent aladine.
Example 1
MgO 80g was charged into a 2L autoclave, and 10 wt% Al (NO) was added3)3Soaking 500g of aqueous solution and 10g of ammonium nitrate at 40 ℃ for 30 h; adding 500g of sodium hydroxide with the mass fraction of 20% into a reaction kettle at one time, heating to 70 ℃ and reacting for 1 h; adding the reacted reactants into a hydrothermal reaction kettle, and reacting for 30 hours at 120 ℃; after the reaction is finished, the catalyst is obtained by washing, drying and grinding, and is marked as CAT-1.
Example 2
MgO 100g was charged into a 2L autoclave, and Co (NO) 10 wt% was added3)2Soaking 500g of the solution and 5g of ammonium nitrate at 50 ℃ for 25 h; adding 600g of sodium hydroxide with the mass fraction of 20% into a reaction kettle at one time, heating to 80 ℃ and reacting for 1 h; adding the reacted reactants into a hydrothermal reaction kettle, and reacting for 30 hours at 140 ℃; after the reaction is finished, the catalyst is obtained by washing, drying and grinding, and is marked as CAT-2.
Example 3
MgO 90g was charged into a 2L autoclave, and 10 wt% Al (NO) was added3)3Soaking 500g of aqueous solution and 15g of ammonium nitrate at 50 ℃ for 30 h; adding 500g of sodium hydroxide with the mass fraction of 20% into a reaction kettle at one time, heating to 70 ℃ and reacting for 1 h; adding the reacted reactants into a hydrothermal reaction kettle, and reacting for 30 hours at 130 ℃; after the reaction is finished, the catalyst is obtained by washing, drying and grinding, and is marked as CAT-3.
Example 4
MgO 80g is added into a 2L pressure kettle, and Zn (NO) with 10wt percent is added3)2Soaking 600g of aqueous solution and 15g of ammonium nitrate at 50 ℃ for 35 hours; adding 500g of sodium hydroxide with the mass fraction of 20% into a reaction kettle at one time, heating to 70 ℃ and reacting for 1 h; adding the reacted reactants into a hydrothermal reaction kettle, and reacting for 30 hours at 140 ℃; after the reaction is finished, the catalyst is obtained by washing, drying and grinding, and is marked as CAT-4.
Example 5
MgO 90g was charged into a 2L autoclave, and 10 wt% Al (NO) was added3)3Soaking 600g of aqueous solution and 10g of ammonium nitrate at 50 ℃ for 30 h; adding 600g of sodium hydroxide with the mass fraction of 20% into a reaction kettle at one time, heating to 70 ℃ and reacting for 1 h; adding the reacted reactants into a hydrothermal reaction kettle, and reacting for 30 hours at 120 ℃; after the reaction is finished, the catalyst is obtained by washing, drying and grinding, and is marked as CAT-5.
Example 6
Adding 100g of MgO into a 2L pressure kettle, and adding 10% of Fe (NO)3)3Soaking 500g of aqueous solution and 5g of ammonium nitrate at 50 ℃ for 30 h; adding 500g of sodium hydroxide with the mass fraction of 20% into a reaction kettle at one time, heating to 80 ℃ and reacting for 1 h; adding the reacted reactants into a hydrothermal reaction kettle, and reacting for 10 hours at 130 ℃; after the reaction is finished, the catalyst is obtained by washing, drying and grinding, and is marked as CAT-6.
Catalyst evaluation experiment
Example 7
Sequentially adding 200g of dehydrated methyl laurate, 4g of nitrogen modified composite metal oxide catalyst CAT-1 and 4g of tetrabutyl titanate into a pressure reaction kettle; controlling the reaction temperature to be 160 ℃ and the pressure to be 0.4MPa, and continuously and stably dripping 200g of ethylene oxide; and (5) after aging for 2h, introducing cooling water for cooling, releasing pressure, and removing the product.
Example 8
Sequentially adding 200g of dehydrated methyl laurate and 4g of nitrogen modified composite metal oxide catalyst CAT-1 into a pressure reaction kettle; controlling the reaction temperature to be 160 ℃ and the pressure to be 0.4MPa, and continuously and stably dripping 200g of ethylene oxide; and (5) after aging for 2h, introducing cooling water for cooling, releasing pressure, and removing the product.
Example 9
200g of dehydrated methyl laurate, 4g of nitrogen modified composite metal oxide catalyst CAT-2 and 6g of isopropyl titanate are sequentially added into a pressure reaction kettle; controlling the reaction temperature to be 160 ℃ and the pressure to be 0.4MPa, and continuously and stably dripping 200g of ethylene oxide; and (5) after aging for 2h, introducing cooling water for cooling, releasing pressure, and removing the product.
Example 10
Sequentially adding 200g of dehydrated methyl myristate and 4g of nitrogen modified composite metal oxide catalyst CAT-2 into a pressure reaction kettle; controlling the reaction temperature to be 150 ℃ and the pressure to be 0.4MPa, and continuously and stably dripping 200g of ethylene oxide; and (5) after aging for 2h, introducing cooling water for cooling, releasing pressure, and removing the product.
Example 11
Sequentially adding 200g of dehydrated methyl myristate, 6g of nitrogen modified composite metal oxide catalyst CAT-3 and 5g of tetrabutyl titanate into a pressure reaction kettle; controlling the reaction temperature to be 170 ℃ and the pressure to be 0.7MPa, and continuously and stably dripping 200g of ethylene oxide; and (5) after aging for 2h, introducing cooling water for cooling, releasing pressure, and removing the product.
Example 12
Sequentially adding 200g of dehydrated methyl myristate, 6g of nitrogen modified composite metal oxide catalyst CAT-4 and 4g of tetrabutyl titanate into a pressure reaction kettle; controlling the reaction temperature to be 130 ℃ and the pressure to be 0.4MPa, and continuously and stably dripping 200g of ethylene oxide; and (5) after aging for 2h, introducing cooling water for cooling, releasing pressure, and removing the product.
Example 13
Sequentially adding 200g of dehydrated methyl laurate, 8g of nitrogen modified composite metal oxide catalyst CAT-5 and 6g of tetrabutyl titanate into a pressure reaction kettle; controlling the reaction temperature to be 170 ℃ and the pressure to be 0.7MPa, and continuously and stably dripping 200g of ethylene oxide; and (5) after aging for 2h, introducing cooling water for cooling, releasing pressure, and removing the product.
Example 14
Sequentially adding 200g of dehydrated methyl myristate, 6g of nitrogen modified composite metal oxide catalyst CAT-6 and 5g of isopropyl titanate into a pressure reaction kettle; controlling the reaction temperature to be 150 ℃ and the pressure to be 0.2MPa, and continuously and stably dripping 200g of ethylene oxide; and (5) after aging for 2h, introducing cooling water for cooling, releasing pressure, and removing the product.
Comparative example 1
Sequentially adding 200g of dehydrated methyl laurate and 8g of calcined hydrotalcite catalyst into a pressure reaction kettle; controlling the reaction temperature to be 150 ℃ and the pressure to be 0.4MPa, and continuously and stably dripping 200g of ethylene oxide; and (5) after aging for 2h, introducing cooling water for cooling, releasing pressure, and removing the product.
The test results of examples 7-14 and comparative example 1 are shown in Table 1.
TABLE 1
Claims (10)
1. A nitrogen-modified composite metal oxide catalyst, the preparation method of which comprises:
(1) adding MgO and ammonium nitrate in M1 (NO)3)yDipping in water solution, and carrying out precipitation reaction by using alkali metal hydroxide;
(2) carrying out hydrothermal reaction on the reaction solution obtained in the step (1), washing after the reaction is finished, and drying to obtain a catalyst;
wherein M1 (NO)3)yIs nitrate of any one or more selected from aluminum, zinc, cobalt, iron, silver, calcium, nickel and copper.
2. The process according to claim 1, characterized in that MgO is used in amounts of 20 to 78%, preferably 45 to 70%, based on 100% of the total mass of the reactants; m1 (NO)3)yThe amount is 20-78%, preferably 25-40%; the ammonium nitrate is used in an amount of 0.1-20%, preferably 1-15%.
3. A method according to claim 1 or 2, characterized in that the temperature of the impregnation process is 40-90 ℃, preferably 40-50 ℃; the time is 20-60h, preferably 30-40 h.
4. A process according to any one of claims 1 to 3, characterized in that the precipitation reaction temperature is 70-100 ℃, preferably 70-80 ℃; the reaction time is 0.5-5h, preferably 1-2 h.
5. The process according to any one of claims 1 to 4, characterized in that the hydrothermal reaction temperature is 100-; the reaction time is 10-40h, preferably 20-30 h.
6. A catalyst prepared according to the process of any one of claims 1 to 5.
7. Carboxylate plug-in ethoxylation, comprising: reacting raw materials of carboxylic ester with ethylene oxide under the action of a catalyst to obtain carboxylic ester ethoxylate; the catalyst is the catalyst of claim 6.
8. The process according to claim 7, characterized in that the carboxylic acid ester is methyl dodecanoate or methyl tetradecanoate, the molar ratio of carboxylic acid ester to ethylene oxide being 1: 3-1:6.
9. A process according to claim 7 or 8, characterized in that the catalyst is used in an amount of 1% to 5% by weight of the carboxylic ester.
10. A method according to any one of claims 7 to 9, characterised in that a titanate-based adjuvant selected from the group consisting of methyl titanate, ethyl titanate, propyl titanate, butyl titanate, isopropyl titanate is added during the preparation of the carboxylic ester ethoxylate, the titanate-based adjuvant being used in an amount of 0-5%, preferably 1.5-4% of the total amount of carboxylic ester and ethylene oxide.
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