CN114797896B - Preparation and application methods of catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by fixed bed - Google Patents

Preparation and application methods of catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by fixed bed Download PDF

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CN114797896B
CN114797896B CN202110093359.8A CN202110093359A CN114797896B CN 114797896 B CN114797896 B CN 114797896B CN 202110093359 A CN202110093359 A CN 202110093359A CN 114797896 B CN114797896 B CN 114797896B
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resin
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deionized water
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CN114797896A (en
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李伟
张晓婧
关庆鑫
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Nankai University
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract

The invention provides a preparation method and a use method of a catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by a fixed bed. The method adopts D072, D061 and NKC-9 resin as precursors, and firstly, the resin is subjected to water washing treatment. The NKC-9 is a dry hydrogen type resin, and is directly washed by deionized water, and the D072 resin and the D061 resin are firstly treated by NaOH solution and HCl solution and then are converted into hydrogen type ion resin, and then are washed by deionized water. Adding the resin into sulfuric acid solution for high-temperature sulfonation treatment after washing, washing with deionized water, drying, and flowing N of the dried resin 2 And (5) carbonizing treatment is carried out under the atmosphere. Soaking the carbonized resin in ammonia water solution, and then using SnCl 2 、ZnCl 2 、NiCl 2 、FeCl 3 、CrCl 2 、CoCl 2 、CuCl 2 、FeCl 2 The desired catalyst is finally obtained by impregnation with an aqueous solution of (a). The synthesis method is simple and convenient to operate, low in cost and environment-friendly. Has better catalytic activity and selectivity in the synthesis reaction of the fixed bed 2, 6-tetramethyl-4-piperidone.

Description

Preparation and application methods of catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by fixed bed
Technical Field
The invention provides a preparation method and a use method of a catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by a fixed bed, and belongs to the field of material synthesis. The method adopts D072, D061 and NKC-9 resin as precursors, and uses SnCl after water washing, sulfonation, carbonization and ammonia treatment 2 、ZnCl 2 、NiCl 2 、FeCl 3 、CrCl 2 、CoCl 2 、CuCl 2 、FeCl 2 Is impregnated with an aqueous solution to obtain the desired catalyst. The preparation method of the catalyst is simple and environment-friendly, and the 2, 6-tetramethyl-4-methylphenidate is prepared in a fixed bedThe reaction of the pyridone has better catalytic activity and selectivity.
Background
The aging of the polymer material brings great inconvenience and loss to the industrial and agricultural production and the life of people. The service life of the material is prolonged by adding a proper light stabilizer into the polymer material in industry, so that the aging of the polymer material is effectively inhibited. Because of excellent light stabilization effect, hindered Amine Light Stabilizers (HALS) are a popular subject for development and research in the field of polymer stabilization in recent years, and are the most promising types of light stabilizers, and the demand for hindered amine light stabilizers is increasing at home and abroad. According to statistics, in the light stabilizer products applied abroad, the proportion of the hindered amine light stabilizer is about 60 percent; the proportion of hindered amine light stabilizer is higher, about 80% in China. 2, 6-tetramethyl-4-piperidone (triacetonamine) is used as the only matrix for synthesizing the hindered piperidine derivative, and the development of the 2, 6-tetramethyl-4-piperidone (triacetonamine) determines the development of the whole hindered amine light stabilizer industry, and plays a significant role in the development and application of HALS. At present, two methods for synthesizing 2, 6-tetramethyl-4-piperidone are reported in the literature, namely an indirect method and a direct method.
The indirect method is to take acetone as a raw material, generate diacetone alcohol, acetonin, phorone and the like under the action of a catalyst, and then continuously react the obtained diacetone alcohol, dipropanolamine, acetonin, phorone and the like under the action of the catalyst to obtain 2, 6-tetramethyl-4-piperidone. US4252958 discloses a method for synthesizing 2, 6-tetramethyl-4-piperidone by taking diacetone alcohol as a raw material; US3953459 discloses a method for synthesizing 2, 6-tetramethyl-4-piperidone by using acetonin as a raw material; U.S. Pat. No. 3, 3943139 discloses a process for obtaining 2, 6-tetramethyl-4-piperidone by reacting isophorone with ammonia. Although the yields of these methods are still acceptable, the synthesis and separation of acetonin, phorone and diacetone alcohol are quite difficult, and the use of these methods greatly increases the production cost, thus making it difficult to realize industrial production.
The direct method is to directly synthesize 2, 6-tetramethyl-4-methylphenidate by using acetone and ammonia gas as raw materials under the action of a catalystA method for preparing pyridone. Compared with an indirect method, the method avoids separation and purification of intermediate products and greatly reduces production cost. In the direct process production, a homogeneous reaction system and a heterogeneous reaction system are adopted. At present, in industrial production, a method which is generally adopted at home and abroad uses acetone and ammonia gas as raw materials, ammonium nitrate as a catalyst and an autoclave to directly produce 2, 6-tetramethyl-4-piperidone, and a large amount of sodium hydroxide is needed to be added to neutralize the ammonium nitrate as the catalyst in the post-treatment process, so that the environment is polluted, and meanwhile, hidden explosion hazards exist. US3960875 discloses a method for preparing a target product by catalyzing the reaction of acetone and ammonia gas by using an L acid, a B acid and their corresponding ammonium salts as catalysts; U.S. 2002/0128182A 1 reports a method for directly synthesizing 2, 6-tetramethyl-4-piperidone by using CaY molecular sieve as a catalyst. The above reaction is homogeneous phase reaction, the catalyst is difficult to recycle, the production cost is increased, and serious environmental pollution can be generated in the treatment process of the catalyst. CN109746004a discloses a load with SO 4 2- The zirconium-aluminum composite oxide catalyst is used for producing 2, 6-tetramethyl-4-piperidone by a fixed bed to obtain good effect, but the preparation process is complex; CN103224465a discloses a method for 2, 6-tetramethyl-4-piperidone production using sulfonic acid type resin or phosphoric acid type resin, which is simple in process but has activity to be improved. Therefore, the synthesis of triacetonamine by efficiently and selectively catalyzing the reaction of acetone and ammonia in a heterogeneous system is a difficult problem facing the prior art and is also a subject worthy of intensive research.
Disclosure of Invention
The invention aims to provide a preparation method and a use method of a catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by a fixed bed. The method adopts D072, D061 and NKC-9 resin as precursors, and uses SnCl after water washing, sulfonation, carbonization and ammonia treatment 2 、ZnCl 2 、NiCl 2 、FeCl 3 、CrCl 2 、CoCl 2 、CuCl 2 、FeCl 2 The required catalyst is obtained after the impregnation of the aqueous solution of the catalyst.
The specific technical scheme of the invention is as follows:
scheme 1: a method for preparing a catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by a fixed bed, which is characterized by comprising the following steps:
(1) Washing NKC-9 sulfonic acid resin with deionized water until the eluate is clear;
(2) Filling the washed resin into a reaction kettle, adding twice volume of sulfuric acid aqueous solution with the mass fraction of 5% -15%, sealing, and then putting into an oven for sulfonation at 180-200 ℃ for at least 6 hours;
(3) The resulting sample was then washed at least 7 times with 10 volumes of deionized water;
(4) Drying the washed sample at 100-120deg.C, and flowing N at 300-400deg.C 2 Carbonizing in the atmosphere for at least 1 hour;
(5) After cooling to room temperature, soaking the carbonized sample in twice volume of an aqueous solution of ammonia with the mass fraction of 5% -25% for at least 1 hour, and then filtering and drying to obtain an aminated sample; wherein the aqueous solution of ammonia is one or more of aqueous ammonia, ethylamine, propylamine and ethylenediamine;
(6) Dissolving metal chloride in deionized water, and then dipping the metal chloride on an aminated sample; wherein the metal chloride is SnCl 2 、ZnCl 2 、NiCl 2 、FeCl 3 、CrCl 2 、CoCl 2 、CuCl 2 、FeCl 2 One or more of the following; the metal chloride accounts for 5-20% of the total mass of the catalyst;
(7) Drying the impregnated sample at 80-120 ℃ to obtain the required catalyst.
Scheme 2: a method for preparing a catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by a fixed bed, which is characterized by comprising the following steps:
(1) Washing D072 sulfonic acid resin with deionized water until the eluate is clear;
(2) Soaking the resin washed by deionized water in 2-4% of HCl solution in the volume of 2 beds for at least 2 hours, and passing through the resin layer at the speed of 2-4 m/hour;
(3) Soaking the resin after acid washing in 2-4% NaOH solution in the volume of 2-bed for at least 2 hr, and passing through the resin layer at 2-4 m/hr;
(4) Soaking the resin subjected to alkali washing in 2-4% HCl solution in mass fraction of 2-bed volume for at least 2 hours, and passing through the resin layer at a speed of 2-4 m/hour;
(5) Washing the resin with deionized water at a rate of 10-12 meters/hour for at least half an hour;
(6) Filling the washed resin into a reaction kettle, adding twice volume of sulfuric acid aqueous solution with the mass fraction of 5% -15%, sealing, and then putting into an oven for sulfonation at 180-200 ℃ for at least 6 hours;
(7) The resulting sample was then washed at least 7 times with 10 volumes of deionized water;
(8) Drying the washed sample at 100-120deg.C, and flowing N at 300-400deg.C 2 Carbonizing in the atmosphere for at least 1 hour;
(9) After cooling to room temperature, soaking the carbonized sample in twice volume of an aqueous solution of ammonia with the mass fraction of 5% -25% for at least 1 hour, and then filtering and drying to obtain an aminated sample; wherein the aqueous solution of ammonia is one or more of aqueous ammonia, ethylamine, propylamine and ethylenediamine;
(10) Dissolving metal chloride in deionized water, and then dipping the metal chloride on an aminated sample; wherein the metal chloride is SnCl 2 、ZnCl 2 、NiCl 2 、FeCl 3 、CrCl 2 、CoCl 2 、CuCl 2 、FeCl 2 One or more of the following; the metal chloride accounts for 5-20% of the total mass of the catalyst;
(11) Drying the impregnated sample at 80-120 ℃ to obtain the required catalyst.
Scheme 3: a method for preparing a catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by a fixed bed, which is characterized by comprising the following steps:
(1) Washing D061 sulfonic acid resin with deionized water until the eluate is clear;
(2) Soaking the resin washed by deionized water in 2-4% of HCl solution in the volume of 2 beds for at least 2 hours, and passing through the resin layer at the speed of 2-4 m/hour;
(3) Soaking the resin after acid washing in 2-4% NaOH solution in the volume of 2-bed for at least 2 hr, and passing through the resin layer at 2-4 m/hr;
(4) Soaking the resin subjected to alkali washing in 2-4% HCl solution in mass fraction of 2-bed volume for at least 2 hours, and passing through the resin layer at a speed of 2-4 m/hour;
(5) Washing the resin with deionized water at a rate of 10-12 meters/hour for at least half an hour;
(6) Filling the washed resin into a reaction kettle, adding twice volume of sulfuric acid aqueous solution with the mass fraction of 5% -15%, sealing, and then putting into an oven for sulfonation at 180-200 ℃ for at least 6 hours;
(7) The resulting sample was then washed at least 7 times with 10 volumes of deionized water;
(8) Drying the washed sample at 100-120deg.C, and flowing N at 300-400deg.C 2 Carbonizing in the atmosphere for at least 1 hour;
(9) After cooling to room temperature, soaking the carbonized sample in twice volume of an aqueous solution of ammonia with the mass fraction of 5% -25% for at least 1 hour, and then filtering and drying to obtain an aminated sample; wherein the aqueous solution of ammonia is one or more of aqueous ammonia, ethylamine, propylamine and ethylenediamine;
(10) Dissolving metal chloride in deionized water, and then dipping the metal chloride on an aminated sample; wherein the metal chloride is SnCl 2 、ZnCl 2 、NiCl 2 、FeCl 3 、CrCl 2 、CoCl 2 、CuCl 2 、FeCl 2 One or more of the following; the metal chloride accounts for 5-20% of the total mass of the catalyst;
(11) Drying the impregnated sample at 80-120 ℃ to obtain the required catalyst.
Scheme 4: a catalyst for the fixed bed synthesis of 2, 6-tetramethyl-4-piperidone, characterized in that it is prepared using the preparation method of any one of schemes 1-3.
Scheme 5: a method of using the catalyst of scheme 4, comprising the steps of:
(1) The catalyst was charged into the constant temperature zone of an atmospheric fixed bed reactor equipped with a condenser tube, at N 2 Heating the fixed bed reactor to 40-70 ℃ under flowing atmosphere and maintaining for at least 1 hour;
(2) Shut down N 2 Then the acetone and the ammonia gas are introduced into a fixed bed reactor according to the mol ratio of 3-12:1, and the volume airspeed of the ammonia gas is 5.5-50.5h -1 ；
(3) The product is cooled to obtain a crude product of 2, 6-tetramethyl-4-piperidone, and then the crude product is subjected to qualitative and quantitative analysis by using gas chromatography.
Compared with the prior art, the invention has the following remarkable innovation:
(1) The invention takes the sulfonic acid resin as the raw material, and the resin is firstly subjected to water washing treatment to remove a small amount of oligomers, organic solvents and the like in the resin, so that the utilization efficiency of pore channels is improved, and the activity of the catalyst is improved.
(2) The resin is subjected to high-temperature sulfonation in sulfuric acid solution again, and more B acid centers are introduced so as to improve the activity of the catalyst.
(3) In carbonization treatment, flowing N is used 2 The atmosphere aims to remove some small molecules generated in the carbonization process, prevent the pore channels from being blocked and make the resin skeleton more stable.
(4) The carbonized resin is soaked in ammonia water solution again, and before the reaction, the amino and the sulfonic acid group react in the water solution to prevent the catalyst from being deactivated due to violent reaction when ammonia gas is directly introduced into the fixed bed.
(5) The sample after ammonia treatment is required to be reintroduced with SnCl 2 、ZnCl 2 、NiCl 2 、FeCl 3 、CrCl 2 、CoCl 2 、CuCl 2 、FeCl 2 And the auxiliary agent can obtain the required catalyst.
Drawings
Fig. 1: SEM of the catalyst CAT-1 prepared in example 1.
Fig. 2: SEM of catalyst CAT-8 prepared in example 8.
Fig. 3: SEM image of catalyst CAT-11 prepared in comparative example 1.
Detailed Description
For a better illustration of this patent, the following examples are presented. The following examples are presented to enable one of ordinary skill in the art to more fully understand the invention or to make various insubstantial modifications and adaptations in light of the disclosure herein. However, the scope of the present invention is not limited by these examples. The protection scope of the invention is set forth in the appended claims.
Example 1
(1) 40mL of NKC-9 sulfonic acid resin was washed with deionized water until the eluate was clear;
(2) Filling the washed resin into a reaction kettle, adding 80mL of sulfuric acid aqueous solution with the mass fraction of 10%, sealing, and then putting into a baking oven to sulfonate for 6 hours at 200 ℃;
(3) The resulting sample was then washed 7 times with 400mL of deionized water;
(4) Drying the washed sample at 110deg.C, and flowing the dried sample at 300deg.C to obtain N 2 Carbonizing for 1 hour in the atmosphere;
(5) After cooling to room temperature, soaking the carbonized sample in 80mL of aqueous solution of propylamine with mass fraction of 25% for 1 hour, and then filtering and drying to obtain an aminated sample;
(6) 1g of SnCl 2 Dissolving in 20g deionized water, and then dipping the solution into 19g of aminated sample;
(7) Drying the impregnated sample at 120 ℃ to obtain the required catalyst, wherein the number of the catalyst is CAT-1.
Example 2
(1) 40mL of D072 sulfonic acid resin was washed with deionized water until the eluate was clear;
(2) Soaking the resin washed by deionized water in 80mL of 2% HCl solution for 2 hours, and passing through the resin layer at a speed of 4 m/h;
(3) Soaking the resin after pickling in 80mL of 2% NaOH solution for 2 hours, and passing through the resin layer at a speed of 4 m/h after soaking;
(4) The resin after alkali washing is soaked in 80mL of HCl solution with the mass fraction of 2% for 2 hours, and the resin passes through the resin layer at the speed of 4 meters/hour after being soaked;
(5) Washing the resin with deionized water at a rate of 10 meters per hour for 1 hour;
(6) Filling the washed resin into a reaction kettle, adding 80mL of sulfuric acid aqueous solution with the mass fraction of 5%, sealing, and then putting into a baking oven to sulfonate for 6 hours at 200 ℃;
(7) The resulting sample was then washed 7 times with 400mL of deionized water;
(8) Drying the washed sample at 120deg.C, and flowing N at 300deg.C 2 Carbonizing for 1 hour in the atmosphere;
(9) After cooling to room temperature, soaking the carbonized sample in 80mL of aqueous solution of 5% ethylamine by mass fraction for 1 hour, and then filtering and drying to obtain an aminated sample;
(10) 1g FeCl 2 Dissolving in 20g deionized water, and then dipping the solution into 19g of aminated sample;
(11) Drying the impregnated sample at 120 ℃ to obtain the required catalyst, wherein the number of the catalyst is CAT-2.
Example 3
The procedure of example 3 was the same as in example 1, except that 1g of SnCl in step (6) was added 2 ZnCl replaced by 1g 2 The catalyst obtained was numbered CAT-3.
Example 4
The procedure of example 4 was the same as in example 1, except that the aqueous solution of propylamine in the mass fraction of 25% in step (5) was replaced with the aqueous solution of ethylamine in the mass fraction of 10%, and the catalyst was designated CAT-4.
Example 5
The procedure of example 5 was the same as in example 1, except that 1g of SnCl in step (6) was added 2 Change to 1g of CuCl 2 The catalyst obtained was numbered CAT-5.
Example 6
The procedure for the preparation of example 6 was the same as in example 2, except that the D072 sulfonic acid type resin in step (1) was replaced with a D061 sulfonic acid type resin, and the catalyst was designated CAT-6.
Example 7
The procedure of example 7 was the same as in example 2, except that the aqueous solution of 5% by mass of ethylamine in step (9) was replaced with an aqueous solution of 15% by mass of propylamine, and the resultant catalyst was designated CAT-7.
Example 8
The procedure of example 8 was the same as in example 2, except that 1g of FeCl in step (10) was added 2 Replaced with 1g of CoCl 2 The catalyst obtained was numbered CAT-8.
Example 9
The procedure of example 9 is the same as in example 2, except that the N flowing at 300℃in step (8) is used 2 Atmosphere change to flowing N at 400 DEG C 2 The atmosphere and the catalyst obtained were numbered CAT-9.
Example 10
The procedure for the preparation of example 10 was the same as in example 2, except that sulfonation at 200℃for 6 hours and sulfonation at 180℃for 8 hours in step (6) were carried out, and the catalyst obtained was designated CAT-10.
Comparative example 1
The purpose was to illustrate the effect of the deionized water wash step on catalyst activity in comparison to example 1.
(1) 40mL of NKC-9 sulfonic acid type resin is filled into a reaction kettle, 80mL of sulfuric acid aqueous solution with the mass fraction of 10% is added, and the mixture is put into an oven for sulfonation for 6 hours at 200 ℃ after being sealed;
(2) Drying the sulfonated sample at 110 ℃;
(3) The dried sample was flowed N at 300℃ 2 Carbonizing for 1 hour in the atmosphere;
(4) After cooling to room temperature, soaking the carbonized sample in 80mL of aqueous solution of propylamine with mass fraction of 25% for 1 hour, and then filtering and drying to obtain an aminated sample;
(5) 1g of SnCl 2 Dissolving in 20g deionized water, and then dipping the solution into 19g of aminated sample;
(6) Drying the impregnated sample at 120 ℃ to obtain the required catalyst, wherein the number of the catalyst is CAT-11.
Comparative example 2
The purpose was to illustrate the effect of the sulfonation treatment step on the catalyst activity in comparison with example 1.
(1) 40mL of NKC-9 sulfonic acid resin was washed with deionized water until the eluate was clear;
(2) Drying the washed sample at 110deg.C, and flowing the dried sample at 300deg.C to obtain N 2 Carbonizing for 1 hour in the atmosphere;
(3) After cooling to room temperature, soaking the carbonized sample in 80mL of aqueous solution of propylamine with mass fraction of 25% for 1 hour, and then filtering and drying to obtain an aminated sample;
(4) 1g of SnCl 2 Dissolving in 20g deionized water, and then dipping the solution into 19g of aminated sample;
(5) Drying the impregnated sample at 120 ℃ to obtain the required catalyst, wherein the number of the catalyst is CAT-12.
Comparative example 3
The purpose was to illustrate the effect of the carbonization treatment step on the catalyst activity in comparison with example 1.
(1) 40mL of NKC-9 sulfonic acid resin was washed with deionized water until the eluate was clear;
(2) Filling the washed resin into a reaction kettle, adding 80mL of sulfuric acid aqueous solution with the mass fraction of 10%, sealing, and then putting into a baking oven to sulfonate for 6 hours at 200 ℃;
(3) The resulting sample was then washed 7 times with 400mL of deionized water;
(4) Drying the washed sample at 110 ℃, soaking the dried sample in 80mL of aqueous solution of propylamine with the mass fraction of 25% for 1 hour, and then filtering and drying to obtain an aminated sample;
(5) 1g of SnCl 2 Dissolving in 20g deionized water, and then dipping the solution into 19g of aminated sample;
(6) Drying the impregnated sample at 120 ℃ to obtain the required catalyst, wherein the number of the catalyst is CAT-13.
Comparative example 4
The purpose was to illustrate the effect of the ammoniation treatment step on the catalyst activity in comparison with example 1.
(1) 40mL of NKC-9 sulfonic acid resin was washed with deionized water until the eluate was clear;
(2) Filling the washed resin into a reaction kettle, adding 80mL of sulfuric acid aqueous solution with the mass fraction of 10%, sealing, and then putting into a baking oven to sulfonate for 6 hours at 200 ℃;
(3) The resulting sample was then washed 7 times with 400mL of deionized water;
(4) Drying the washed sample at 110deg.C, and flowing the dried sample at 300deg.C to obtain N 2 Carbonizing for 1 hour in the atmosphere;
(5) After cooling to room temperature, 1g of SnCl 2 Dissolving in 20g deionized water, and then dipping the solution into 19g carbonized sample;
(6) Drying the impregnated sample at 120 ℃ to obtain the required catalyst, wherein the number of the catalyst is CAT-14.
Comparative example 5
The purpose was to illustrate the effect of the aqueous chloride impregnation treatment step on the catalyst activity in comparison to example 1.
(1) 40mL of NKC-9 sulfonic acid resin was washed with deionized water until the eluate was clear;
(2) Filling the washed resin into a reaction kettle, adding 80mL of sulfuric acid aqueous solution with the mass fraction of 10%, sealing, and then putting into a baking oven to sulfonate for 6 hours at 200 ℃;
(3) The resulting sample was then washed 7 times with 400mL of deionized water;
(4) Drying the washed sample at 110deg.C, and flowing the dried sample at 300deg.C to obtain N 2 Carbonizing for 1 hour in the atmosphere;
(5) After cooling to room temperature, soaking the carbonized sample in 80mL of aqueous solution of propylamine with mass fraction of 25% for 1 hour, and then filtering and drying to obtain an aminated sample;
(6) 20g of the sample after ammoniation is taken as the required catalyst, and the number of the catalyst is CAT-15.
Comparative example 6
The purpose was to illustrate the effect of the time of carbonization treatment on the catalyst activity in comparison with example 2.
(1) 40mL of D072 sulfonic acid resin was washed with deionized water until the eluate was clear;
(2) Soaking the resin washed by deionized water in 80mL of 2% HCl solution for 2 hours, and passing through the resin layer at a speed of 4 m/h;
(3) Soaking the resin after pickling in 80mL of 2% NaOH solution for 2 hours, and passing through the resin layer at a speed of 4 m/h after soaking;
(4) The resin after alkali washing is soaked in 80mL of HCl solution with the mass fraction of 2% for 2 hours, and the resin passes through the resin layer at the speed of 4 meters/hour after being soaked;
(5) Washing the resin with deionized water at a rate of 10 meters per hour for 1 hour;
(6) Filling the washed resin into a reaction kettle, adding 80mL of sulfuric acid aqueous solution with the mass fraction of 5%, sealing, and then putting into a baking oven to sulfonate for 6 hours at 200 ℃;
(7) The resulting sample was then washed 7 times with 400mL of deionized water;
(8) Drying the washed sample at 120deg.C, and flowing N at 300deg.C 2 Carbonizing for 2 hours in the atmosphere;
(9) After cooling to room temperature, soaking the carbonized sample in 80mL of aqueous solution of 5% ethylamine by mass fraction for 1 hour, and then filtering and drying to obtain an aminated sample;
(10) 1g of FeCl 2 Dissolving in 20g deionized water, and then dipping the solution into 19g of aminated sample;
(11) Drying the impregnated sample at 120 ℃ to obtain the required catalyst, wherein the number of the catalyst is CAT-16.
Comparative example 7
The purpose is to compare with example 2, N, which is used to illustrate the flow 2 Influence of atmosphere treatment on catalyst activity.
(1) 40mL of D072 sulfonic acid resin was washed with deionized water until the eluate was clear;
(2) Soaking the resin washed by deionized water in 80mL of 2% HCl solution for 2 hours, and passing through the resin layer at a speed of 4 m/h;
(3) Soaking the resin after pickling in 80mL of 2% NaOH solution for 2 hours, and passing through the resin layer at a speed of 4 m/h after soaking;
(4) The resin after alkali washing is soaked in 80mL of HCl solution with the mass fraction of 2% for 2 hours, and the resin passes through the resin layer at the speed of 4 meters/hour after being soaked;
(5) Washing the resin with deionized water at a rate of 10 meters per hour for 1 hour;
(6) Filling the washed resin into a reaction kettle, adding 80mL of sulfuric acid aqueous solution with the mass fraction of 5%, sealing, and then putting into a baking oven to sulfonate for 6 hours at 200 ℃;
(7) The resulting sample was then washed 7 times with 400mL of deionized water;
(8) Drying the washed sample at 120deg.C, and standing the dried sample at 300deg.C for N 2 Carbonizing for 1 hour in the atmosphere;
(9) After cooling to room temperature, soaking the carbonized sample in 80mL of aqueous solution of 5% ethylamine by mass fraction for 1 hour, and then filtering and drying to obtain an aminated sample;
(10) 1g of FeCl 2 Dissolving in 20g deionized water, and then dipping the solution into 19g of aminated sample;
(11) Drying the impregnated sample at 120 ℃ to obtain the required catalyst, wherein the number of the catalyst is CAT-17.
The evaluation process and conditions of the catalyst are as follows:
(1) 40mL of the catalyst was charged into the constant temperature zone of an atmospheric fixed bed reactor equipped with a condenser, at N 2 Heating the fixed bed reactor to 50 ℃ under flowing atmosphere, and maintaining for 1 hour;
(2) Shut down N 2 Then the acetone and the ammonia gas are introduced into a fixed bed reactor according to the mol ratio of 6:1, and the volume space velocity of the ammonia gas is 20.7h -1 ；
(3) The product was cooled to give crude 2, 6-tetramethyl-4-piperidone, which was then analyzed qualitatively and quantitatively by chromatography.
Sample analysis was performed at the point of 9 hours of reaction, and the acetone conversion and triacetonamine selectivity of the CAT-1 to CAT-17 catalysts are shown in the table
Catalyst numbering Acetone conversion (%) Triacetonamine selectivity (%)
CAT-1 45.8 46.7
CAT-2 36.7 40.6
CAT-3 46.7 47.5
CAT-4 42.5 43.5
CAT-5 37.8 25.7
CAT-6 39.6 30.5
CAT-7 35.9 29.5
CAT-8 37.5 39.6
CAT-9 29.6 30.5
CAT-10 30.5 40.6
CAT-11 20.5 16.8
CAT-12 26.3 20.5
CAT-13 27.7 17.8
CAT-14 20.8 18.9
CAT-15 21.5 17.6
CAT-16 16.5 10.5
CAT-17 5.6 8.9

Claims (5)

1. A method for preparing a catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by a fixed bed, which is characterized by comprising the following steps:
(1) Washing NKC-9 sulfonic acid resin with deionized water until the eluate is clear;
(2) Filling the washed resin into a reaction kettle, adding twice volume of sulfuric acid aqueous solution with the mass fraction of 5% -15%, sealing, and then putting into an oven for sulfonation at 180-200 ℃ for at least 6 hours;
(3) The resulting sample was then washed at least 7 times with 10 volumes of deionized water;
(4) Drying the washed sample at 100-120deg.C, and flowing N at 300-400deg.C 2 Carbonizing in the atmosphere for at least 1 hour;
(5) After cooling to room temperature, soaking the carbonized sample in twice volume of an aqueous solution of ammonia with the mass fraction of 5% -25% for at least 1 hour, and then filtering and drying to obtain an aminated sample; wherein the aqueous solution of ammonia is one or more of aqueous ammonia, ethylamine, propylamine and ethylenediamine;
(6) Dissolving metal chloride in deionized water, and then dipping the metal chloride on an aminated sample; wherein the metal chloride is SnCl 2 、ZnCl 2 、NiCl 2 、FeCl 3 、CrCl 2 、CoCl 2 、CuCl 2 、FeCl 2 One or more of the following; the metal chloride accounts for 5-20% of the total mass of the catalyst;
(7) Drying the impregnated sample at 80-120 ℃ to obtain the required catalyst.
2. A method for preparing a catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by a fixed bed, which is characterized by comprising the following steps:
(1) Washing D072 sulfonic acid resin with deionized water until the eluate is clear;
(2) Soaking the resin washed by deionized water in 2-4% of HCl solution in the volume of 2 beds for at least 2 hours, and passing through the resin layer at the speed of 2-4 m/hour;
(3) Soaking the resin after acid washing in 2-4% NaOH solution in the volume of 2-bed for at least 2 hr, and passing through the resin layer at 2-4 m/hr;
(4) Soaking the resin subjected to alkali washing in 2-4% HCl solution in mass fraction of 2-bed volume for at least 2 hours, and passing through the resin layer at a speed of 2-4 m/hour;
(5) Washing the resin with deionized water at a rate of 10-12 meters/hour for at least half an hour;
(6) Filling the washed resin into a reaction kettle, adding twice volume of sulfuric acid aqueous solution with the mass fraction of 5% -15%, sealing, and then putting into an oven for sulfonation at 180-200 ℃ for at least 6 hours;
(7) The resulting sample was then washed at least 7 times with 10 volumes of deionized water;
(8) Drying the washed sample at 100-120deg.C, and drying at 300-400deg.CDown-flowing N 2 Carbonizing in the atmosphere for at least 1 hour;
(9) After cooling to room temperature, soaking the carbonized sample in twice volume of an aqueous solution of ammonia with the mass fraction of 5% -25% for at least 1 hour, and then filtering and drying to obtain an aminated sample; wherein the aqueous solution of ammonia is one or more of aqueous ammonia, ethylamine, propylamine and ethylenediamine;
(10) Dissolving metal chloride in deionized water, and then dipping the metal chloride on an aminated sample; wherein the metal chloride is SnCl 2 、ZnCl 2 、NiCl 2 、FeCl 3 、CrCl 2 、CoCl 2 、CuCl 2 、FeCl 2 One or more of the following; the metal chloride accounts for 5-20% of the total mass of the catalyst;
(11) Drying the impregnated sample at 80-120 ℃ to obtain the required catalyst.
3. A method for preparing a catalyst for synthesizing 2, 6-tetramethyl-4-piperidone by a fixed bed, which is characterized by comprising the following steps:
(1) Washing D061 sulfonic acid resin with deionized water until the eluate is clear;
(2) Soaking the resin washed by deionized water in 2-4% of HCl solution in the volume of 2 beds for at least 2 hours, and passing through the resin layer at the speed of 2-4 m/hour;
(3) Soaking the resin after acid washing in 2-4% NaOH solution in the volume of 2-bed for at least 2 hr, and passing through the resin layer at 2-4 m/hr;
(4) Soaking the resin subjected to alkali washing in 2-4% HCl solution in mass fraction of 2-bed volume for at least 2 hours, and passing through the resin layer at a speed of 2-4 m/hour;
(5) Washing the resin with deionized water at a rate of 10-12 meters/hour for at least half an hour;
(6) Filling the washed resin into a reaction kettle, adding twice volume of sulfuric acid aqueous solution with the mass fraction of 5% -15%, sealing, and then putting into an oven for sulfonation at 180-200 ℃ for at least 6 hours;
(7) The resulting sample was then washed at least 7 times with 10 volumes of deionized water;
(8) Drying the washed sample at 100-120deg.C, and flowing N at 300-400deg.C 2 Carbonizing in the atmosphere for at least 1 hour;
(9) After cooling to room temperature, soaking the carbonized sample in twice volume of an aqueous solution of ammonia with the mass fraction of 5% -25% for at least 1 hour, and then filtering and drying to obtain an aminated sample; wherein the aqueous solution of ammonia is one or more of aqueous ammonia, ethylamine, propylamine and ethylenediamine;
(10) Dissolving metal chloride in deionized water, and then dipping the metal chloride on an aminated sample; wherein the metal chloride is SnCl 2 、ZnCl 2 、NiCl 2 、FeCl 3 、CrCl 2 、CoCl 2 、CuCl 2 、FeCl 2 One or more of the following; the metal chloride accounts for 5-20% of the total mass of the catalyst;
(11) Drying the impregnated sample at 80-120 ℃ to obtain the required catalyst.
4. A catalyst for the fixed bed synthesis of 2, 6-tetramethyl-4-piperidone, characterized in that it is prepared using the preparation method of any of claims 1-3.
5. A method of using the catalyst of claim 4, comprising the steps of:
(1) The catalyst was charged into the constant temperature zone of an atmospheric fixed bed reactor equipped with a condenser tube, at N 2 Heating the fixed bed reactor to 40-70 ℃ under flowing atmosphere and maintaining for at least 1 hour;
(2) Shut down N 2 Then the acetone and the ammonia gas are introduced into a fixed bed reactor according to the mol ratio of 3-12:1, and the volume airspeed of the ammonia gas is 5.5-50.5h -1 ；
(3) The product is cooled to obtain a crude product of 2, 6-tetramethyl-4-piperidone, and then the crude product is subjected to qualitative and quantitative analysis by using gas chromatography.
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JPH09316054A (en) * 1996-05-24 1997-12-09 Mitsubishi Chem Corp Production of 2,2,6,6-tetramethyl-4-hydroxypiperidine
CN102516158A (en) * 2011-12-12 2012-06-27 宿迁市振兴化工有限公司 Method for synthesizing triacetonamine in fixed bed
CN103224465A (en) * 2013-01-31 2013-07-31 天津大学 2,2,6,6,-tetramethyl-4-piperidone continuous synthesis method
CN106866503A (en) * 2017-02-23 2017-06-20 武汉理工大学 A kind of method that low temperature liquid phase reaction fixed bed continuously synthesizes triacetonamine
CN108097251A (en) * 2018-01-10 2018-06-01 南开大学 A kind of catalyst and application method for the reaction of fixed bed acetylene hydrochlorination
CN109746004A (en) * 2017-11-07 2019-05-14 万华化学集团股份有限公司 A kind of catalyst and its preparing the application in 2,2,6,6- tetramethyl -4- piperidones

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09316054A (en) * 1996-05-24 1997-12-09 Mitsubishi Chem Corp Production of 2,2,6,6-tetramethyl-4-hydroxypiperidine
CN102516158A (en) * 2011-12-12 2012-06-27 宿迁市振兴化工有限公司 Method for synthesizing triacetonamine in fixed bed
CN103224465A (en) * 2013-01-31 2013-07-31 天津大学 2,2,6,6,-tetramethyl-4-piperidone continuous synthesis method
CN106866503A (en) * 2017-02-23 2017-06-20 武汉理工大学 A kind of method that low temperature liquid phase reaction fixed bed continuously synthesizes triacetonamine
CN109746004A (en) * 2017-11-07 2019-05-14 万华化学集团股份有限公司 A kind of catalyst and its preparing the application in 2,2,6,6- tetramethyl -4- piperidones
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