Preparation method and application of o-chlorocyclohexanone synthesis catalyst

Abstract

The invention provides a preparation method and application of an o-chlorocyclohexanone synthesis catalyst. The preparation method comprises the following steps: treating a catalyst carrier in an acid solution, adding a first active component in mass fraction, performing ultrasonic dispersion treatment under a water bath condition, preserving heat, aging, washing to be neutral, and drying at low temperature to obtain a catalyst precursor; dissolving a second active component in an ethanol solution, adding into the catalyst precursor, stirring, standing, treating in nitrogen, and roasting to obtain the catalyst. The catalyst can effectively catalyze cyclohexene oxide to synthesize o-chlorocyclohexanone by a one-step method, and the product yield is greater than 92%.

Description

Technical Field

[0001] The invention belongs to the technical field of catalyst preparation, and particularly relates to a method for preparing a catalyst for synthesizing o-chlorocyclohexanone and a method for synthesizing o-chlorocyclohexanone. Background Art

[0002] o-Chlorocyclohexanone is used as an intermediate in organic synthesis. This product is mainly used in organic synthesis, such as the synthesis of o-hydroxycyclohexanone, catechol, o-chlorocyclohexanone oxime, furanocoumarin compounds, etc. It can produce rubber adhesives and promoters, and also has significant uses in agriculture and medicine. The synthesis method is mostly acid catalysis, and there are also some base catalysis synthesis methods. However, it is rare to use a supported catalyst to catalyze the reaction. The supported catalyst catalyzes the reaction, and the catalyst is solid and easy to separate and recover, and can be repeatedly applied many times.

[0003] Early methods used chlorine as a chlorinating agent, but due to the high toxicity of chlorine, when studying o-chlorocyclohexanone, chlorine-containing products were tried as the source of chlorine, such as sulfuryl chloride, trichloroisocyanuric acid, p-toluenesulfonyl chloride, acetyl chloride, hydrochloric acid, etc. However, when using sulfuryl chloride for reaction, the byproduct dichlorocyclohexanone is not easy to separate, and the reaction yield is low; when using trichloroisocyanuric acid, the yield is generally 75%, and the subsequent treatment is complicated; when using p-toluenesulfonyl chloride for reaction, the solution needs to be cooled to -78°C during the reaction, and the process is complicated; when using acetyl chloride, the subsequent purification is too cumbersome and is not suitable for industrial production.

[0004] Patent CN 107540531, in the presence of an auxiliary agent, a light oil and a hydrogen chloride solution undergo a ring-opening reaction to generate 2-chlorocyclohexanol, and the oil phase is obtained by standing and stratifying. The obtained oil phase is distilled at normal pressure or reduced pressure to remove relatively low-boiling point components, and high-purity 2-chlorocyclohexanol is reacted with an oxidant. After the reaction is completed, the obtained oil phase is washed with a washing solution, and the obtained oil phase is distilled at normal pressure to collect the fraction to obtain o-chlorocyclohexanone. The yield is high and the reaction is mild, but the reaction is a two-step reaction and the processing process is long.

[0005] Patent CN 113398978, a method for preparing o-chlorocyclohexanone and its catalyst, uses a supported cerium catalyst to effectively catalyze the one-step synthesis of o-chlorocyclohexanone from cyclohexene oxide; the process is simple and the one-step synthesis of o-chlorocyclohexanone is carried out, but the selectivity is poor and the yield of o-chlorocyclohexanone is low. Summary of the invention

[0006] The invention provides a preparation method of a catalyst for synthesizing o-chlorocyclohexanone, synthesizes a supported cerium catalyst, has a simple preparation process, is environmentally friendly, has high o-chlorocyclohexanone selectivity and high yield; treats a catalyst carrier in an acid solution, adds a first active component, performs ultrasonic dispersion treatment under water bath conditions, heat preservation and aging, washes with water to neutrality, and dries at low temperature to prepare a catalyst precursor; dissolves a second active component in an ethanol solution, adds the solution to the catalyst precursor, stirs and then stands, treats in nitrogen, and calcines to obtain a catalyst. The catalyst can effectively catalyze the one-step synthesis of o-chlorocyclohexanone from cyclohexene oxide.

[0007] The present invention also provides a method for synthesizing o-chlorocyclohexanone, wherein the o-chlorocyclohexanone is prepared by utilizing the light oil produced as a byproduct of cyclohexanone, the light oil and a chlorinating agent undergo a ring-opening oxidation reaction at a certain temperature to generate a crude o-chlorocyclohexanone product, and after the reaction is completed, the product is washed with sodium sulfate solution, separated and the oil phase is distilled to obtain pure o-chlorocyclohexanone.

[0008] The invention provides a method for preparing a catalyst for synthesizing o-chlorocyclohexanone. The catalyst consists of a carrier, a first active component and a second active component. The active components are loaded in batches to prepare the catalyst, which is used for synthesizing o-chlorocyclohexanone using light cyclohexanone as a raw material.

[0009] Generally, the catalyst preparation steps are: (1) treating the catalyst carrier in an acid solution, adding a first active component with a mass fraction of 5% to 30%, ultrasonically dispersing the catalyst carrier in a water bath at 60°C to 90°C for 1 to 4 h, aging the catalyst carrier at the same temperature, washing the catalyst carrier with water until the catalyst carrier is neutral, and drying the catalyst carrier at a low temperature to obtain the catalyst precursor; (2) After the second active component is dissolved in an ethanol solution, it is added to the catalyst precursor, stirred and then allowed to stand, and then calcined in nitrogen for 2 h to 6 h to obtain a catalyst.

[0010] Furthermore, the first active component is at least one of sodium chloride, magnesium chloride, calcium chloride and potassium chloride.

[0011] The acid is one of nitric acid, sulfuric acid and hydrochloric acid.

[0012] The second active component is cerium ammonium nitrate and cerium nitrate; the mass content of cerium in the catalyst is 0.01-5%; the ratio of cerium ammonium nitrate to cerium nitrate is 5:1-1:5.

[0013] The low-temperature drying temperature is 60°C-90°C, and the treatment temperature in nitrogen is 200-250°C.

[0014] The carrier is activated carbon or molecular sieve; the molecular sieve is MCM-41, ZSM-5, SAPO-34, MOR, preferably MCM-41.

[0015] The invention provides a method for synthesizing o-chlorocyclohexanone: cyclohexanone light oil and a catalyst are subjected to a reaction by dropwise adding a chlorinating agent under stirring to obtain o-chlorocyclohexanone.

[0016] The specific reaction steps are: cyclohexanone light oil and catalyst are reacted under stirring by dropping a chlorinating agent; after the reaction is completed, the reaction is allowed to stand and the layers are separated, the lower aqueous phase is filtered, the catalyst is recycled, the upper oil phase is washed with a Na2CO3 aqueous solution, the oil phase is distilled at atmospheric pressure, and the fraction between 203 and 204° C. is collected. After the crude o-chlorocyclohexanone is obtained by reaction, it is washed with a sodium carbonate solution, the layers are separated, and the oil phase is distilled to obtain pure o-chlorocyclohexanone.

[0017] Generally, the cyclohexanone light oil contains cyclohexane oxide, n-pentanol, cyclohexanol and cyclohexanone; the chlorinating agent is a mixture of one or two of chloric acid, chlorous acid and hypochlorous acid and hydrochloric acid; the mass content of hydrochloric acid in the chlorinating agent is 30%-80%.

[0018] The ring-opening reaction temperature is 20°C-50°C, the molar ratio of cyclohexene oxide in the light oil to the chlorinating agent is 1:1-1.5, and the added amount of the catalyst is 0.5%-5% of the cyclohexene oxide in the light oil.

[0019] Furthermore, in the synthesis method, the catalyst adopts the catalyst prepared by the present invention, preferably Ce-MCM-41.

[0020] Compared with the prior art, the method of the present invention has the following advantages: 1) a batch-loaded cerium catalyst is synthesized, the preparation process is simple, and it can effectively catalyze the one-step synthesis of o-chlorocyclohexanone from cyclohexene oxide; 2) the resource advantage of cyclohexane oxide in light oil is utilized, and the selectivity and conversion rate of the ring-opening reaction are effectively improved by adding catalysts and chlorinating agents; 3) the process is simple and o-chlorocyclohexanone is synthesized in one step, and the selectivity and yield of o-chlorocyclohexanone are high. Implementation

[0021] The present invention is described in detail below with reference to the embodiments. Example 1

[0022] Catalyst preparation: (1) 50 g of MCM-41 carrier was boiled and refluxed in 5% hydrochloric acid solution for 1 h, 30% sodium chloride was added, and ultrasonic dispersion was performed in a water bath at 60 °C for 2 h. The ultrasound was turned off and the temperature was kept for 6 h. The carrier was washed with water until neutral and dried at 80 °C to prepare a catalyst precursor. (2) After dissolving 3 g of cerium nitrate and 2 g of cerium ammonium nitrate in 100 mL of 20% ethanol solution, the mixture was directly added to the catalyst precursor. The mixture was stirred for 3 h and allowed to stand for 5 h. The mixture was treated in nitrogen at 250 °C for 2 h and then calcined at 250 °C to obtain a Ce-MCM-41 catalyst.

[0023] Synthesis of o-chlorocyclohexanone: Take 200g of light oil (containing 40.6% by weight of cyclohexene oxide) and 1g of catalyst Ce-MCM-41, add them into a 500ml four-necked flask, and react by dropping 24g of 36% hydrochloric acid and 31g of sodium hypochlorite mixed solution under stirring. Control the reaction temperature to about 30°C, the reaction time to 1.5 hours, stand for stratification after the reaction, filter the lower aqueous phase, reuse the catalyst, take the upper oil phase and wash it with 100mL 10% Na2CO3 aqueous solution for 3 times, then distill the oil phase under normal pressure, collect the fraction between 203 and 204°C, and obtain 103.6g of product. According to gas chromatography analysis, the content of o-chlorocyclohexanone is 98.7%, and the yield of o-chlorocyclohexanone is 92.9%. Example 2

[0024] Catalyst preparation: (1) 50 g of MCM-41 carrier was boiled and refluxed in 5% nitric acid solution for 1 h, and a 30% by mass magnesium chloride solution was added. Ultrasonic dispersion was performed in a water bath at 90 °C for 4 h, and then the ultrasound was turned off and the mixture was kept warm for 2 h. The mixture was washed with water until neutral and dried at 60 °C to prepare a catalyst precursor. (2) After dissolving 0.9 g of cerium nitrate and 4.5 g of cerium ammonium nitrate in 100 mL of 20% ethanol solution, the mixture was directly added to the catalyst precursor. The mixture was stirred for 5 h and then allowed to stand for 10 h. The mixture was treated in nitrogen at 200 °C for 6 h and then calcined at 200 °C to obtain a Ce-MCM-41 catalyst.

[0025] Synthesis of o-chlorocyclohexanone: The same synthesis method as in Example 1 was used to obtain 104.4 g of the product. Gas chromatography analysis showed that the content of o-chlorocyclohexanone was 98.3%, and the yield of o-chlorocyclohexanone was 93.3%. Example 3

[0026] Catalyst preparation: (1) 100 g of MCM-41 carrier was boiled and refluxed in 5% nitric acid solution for 1 h, and a 5% sodium chloride solution was added. Ultrasonic dispersion was performed in a water bath at 70 °C for 1 h, and then the ultrasound was turned off and the temperature was kept for 2 h. The carrier was washed with water until neutral and dried at 70 °C to prepare a catalyst precursor. (2) After dissolving 4.5 g of cerium nitrate and 0.9 g of cerium ammonium nitrate in 100 mL of 20% ethanol solution, the mixture was directly added to the catalyst precursor. The mixture was stirred for 5 h and then allowed to stand for 5 h. The mixture was treated in nitrogen at 220 °C for 2 h and then calcined at 200 °C to obtain a Ce-MCM-41 catalyst.

[0027] Synthesis of o-chlorocyclohexanone: The same synthesis method as in Example 1 was used to obtain 102.6 g of the product. Gas chromatography analysis showed that the content of o-chlorocyclohexanone was 98.7% and the yield of o-chlorocyclohexanone was 92.0%. Example 4

[0028] Catalyst preparation: (1) 100 g of MCM-41 carrier was boiled and refluxed in 20% nitric acid solution for 2 h, 30% calcium chloride solution was added, and ultrasonic dispersion was performed in a water bath at 70 °C for 2 h. The ultrasonic wave was turned off, the mixture was kept warm for 2 h, washed with water until neutral, and dried at 70 °C to prepare a catalyst precursor. (2) After dissolving 4 g of cerium nitrate and 1 g of cerium ammonium nitrate in 100 mL of 20% ethanol solution, the mixture was directly added to the catalyst precursor. The mixture was stirred for 3 h and then allowed to stand for 3 h. The mixture was treated in nitrogen at 220 °C for 2 h and then calcined at 200 °C to obtain a Ce-MCM-41 catalyst.

[0029] Synthesis of o-chlorocyclohexanone: The same synthesis method as in Example 1 was used to obtain 103.1 g of the product. Gas chromatography analysis showed that the content of o-chlorocyclohexanone was 98.5%, and the yield of o-chlorocyclohexanone was 92.3%. Example 5

[0030] Catalyst preparation: (1) 100 g of ZSM-5 carrier was boiled and refluxed in 10% sulfuric acid solution for 2 h, and a 20% potassium chloride solution was added. Ultrasonic dispersion was performed in a water bath at 60 °C for 1 h, and then the ultrasound was turned off and the mixture was kept warm for 2 h. The mixture was washed with water until neutral and dried at 70 °C to prepare a catalyst precursor. (2) Dissolve 1 g of cerium nitrate and 4 g of cerium ammonium nitrate in 100 mL of 20% ethanol solution and add directly to the catalyst precursor. Stir for 3 h and let stand for 3 h. Treat in nitrogen at 220 °C for 2 h and then calcine at 200 °C to obtain a Ce-ZSM-5 catalyst.

[0031] Synthesis of o-chlorocyclohexanone: The same synthesis method as in Example 1 was used to obtain 103.5 g of the product. Gas chromatography analysis showed that the content of o-chlorocyclohexanone was 98.1% and the yield of o-chlorocyclohexanone was 92.3%. Example 6

[0032] Catalyst preparation: (1) 100 g of ZSM-5 carrier was boiled and refluxed in 20% sulfuric acid solution for 2 h, and a 20% sodium chloride solution was added. Ultrasonic dispersion was performed in a water bath at 60 °C for 1 h, and then the ultrasound was turned off and the mixture was kept warm for 2 h. The mixture was washed with water until neutral and dried at 70 °C to prepare a catalyst precursor. (2) Dissolve 2 g of cerium nitrate and 3 g of cerium ammonium nitrate in 100 mL of 20% ethanol solution and add directly to the catalyst precursor. Stir for 3 h and let stand for 3 h. Treat in nitrogen at 220 °C for 2 h and then calcine at 200 °C to obtain a Ce-ZSM-5 catalyst.

[0033] Synthesis of o-chlorocyclohexanone: The same synthesis method as in Example 1 was used to obtain 103.8 g of the product. Gas chromatography analysis showed that the content of o-chlorocyclohexanone was 98.2% and the yield of o-chlorocyclohexanone was 92.7%. Example 7

[0034] Catalyst preparation: (1) 100 g of MCM-41 carrier was boiled and refluxed in 10% nitric acid solution for 2 h, and a 20% sodium chloride solution was added. Ultrasonic dispersion was performed in a water bath at 60 °C for 1 h, and then the ultrasound was turned off and the mixture was kept warm for 2 h. The mixture was washed with water until neutral and dried at 70 °C to prepare a catalyst precursor. (2) After dissolving 2.5 g of cerium nitrate and 2.5 g of cerium ammonium nitrate in 100 mL of 20% ethanol solution, the mixture was directly added to the catalyst precursor. After stirring for 1 h, the mixture was allowed to stand for 4 h. The mixture was treated in nitrogen at 200 °C for 3 h and then calcined at 200 °C to obtain a Ce-MCM-41 catalyst.

[0035] Synthesis of o-chlorocyclohexanone: The same synthesis method as in Example 1 was used to obtain 103.3 g of the product. The content of o-chlorocyclohexanone was 98.2% and the yield of o-chlorocyclohexanone was 93.2% after gas chromatography analysis.

[0036] Comparative Example 1: Catalyst preparation: (1) 50 g of MCM-41 carrier was boiled and refluxed in 5% hydrochloric acid solution for 1 h, 30% sodium chloride was added, and the mixture was kept in a water bath at 60 °C for 6 h, washed with water until neutral, and dried at 80 °C to prepare a catalyst precursor; (2) After dissolving 3 g of cerium nitrate and 2 g of cerium ammonium nitrate in 100 mL of 20% ethanol solution, the mixture was directly added to the catalyst precursor. The mixture was stirred for 3 h and allowed to stand for 5 h. The mixture was treated in nitrogen at 250 °C for 2 h and then calcined at 250 °C to obtain a Ce-MCM-41 catalyst.

[0037] Synthesis of o-chlorocyclohexanone: The same synthesis method as in Example 1 was used to obtain 100.9 g of the product. The content of o-chlorocyclohexanone was 97.5% and the yield of o-chlorocyclohexanone was 89.4% after gas chromatography analysis.

[0038] Comparative Example 2: Catalyst preparation: (1) 50 g of MCM-41 carrier was boiled and refluxed in 5% hydrochloric acid solution for 1 h, 30% sodium chloride was added, and ultrasonic dispersion was performed in a water bath at 60 °C for 2 h. The ultrasound was turned off and the temperature was kept for 6 h. The carrier was washed with water until neutral and dried at 80 °C to prepare a catalyst precursor. (2) After dissolving 5 g of cerium nitrate in 100 mL of 20% ethanol solution, add it directly to the catalyst precursor, stir it for 3 h, let it stand for 5 h, treat it in nitrogen at 250 °C for 2 h, and then calcine it at 250 °C to obtain Ce-MCM-41 catalyst.

[0039] Synthesis of o-chlorocyclohexanone: The same synthesis method as in Example 1 was used to obtain 102.2 g of the product. The content of o-chlorocyclohexanone was 98.1% by gas chromatography analysis, and the yield of o-chlorocyclohexanone was 91.1%.

[0040] Comparative Example 3: Catalyst preparation: (1) 50 g of MCM-41 carrier was boiled and refluxed in 5% hydrochloric acid solution for 1 h as a catalyst precursor; (2) After dissolving 3 g of cerium nitrate and 2 g of cerium ammonium nitrate in 100 mL of 20% ethanol solution, the mixture was directly added to the catalyst precursor. The mixture was stirred for 3 h and allowed to stand for 5 h. The mixture was treated in nitrogen at 250 °C for 2 h and then calcined at 250 °C to obtain a Ce-MCM-41 catalyst.

[0041] Synthesis of o-chlorocyclohexanone: The same synthesis method as in Example 1 was used to obtain 99.5 g of the product. The content of o-chlorocyclohexanone was 98.2% and the yield of o-chlorocyclohexanone was 88.8% after gas chromatography analysis.

Claims

1. A method for preparing an o-chlorocyclohexanone synthesis catalyst, characterized in that The catalyst consists of a carrier, a first active component and a second active component. The active components are loaded in batches to obtain the catalyst, which is used to synthesize o-chlorocyclohexanone using light cyclohexanone as a raw material.

2. The preparation method according to claim 1, characterized in that The steps for preparing the catalyst are: (1) treating the catalyst carrier in an acid solution, adding a first active component with a mass fraction of 5% to 30%, ultrasonically dispersing the catalyst carrier in a water bath at 60°C to 90°C for 1 to 4 h, aging the catalyst carrier at the same temperature, washing the catalyst carrier with water until the catalyst carrier is neutral, and drying the catalyst carrier at a low temperature to obtain the catalyst precursor; (2) After the second active component is dissolved in an ethanol solution, it is added to the catalyst precursor, stirred and then allowed to stand, treated in nitrogen for 2h-6h and then calcined to obtain a catalyst.

3. The preparation method according to claim 2, characterized in that The first active component is at least one of sodium chloride, magnesium chloride, calcium chloride and potassium chloride.

4. The preparation method according to claim 2, characterized in that The acid is one of nitric acid, sulfuric acid and hydrochloric acid.

5. The preparation method according to claim 2, characterized in that The second active component is cerium ammonium nitrate and cerium nitrate; the mass content of cerium in the catalyst is 0.01-5%; the ratio of cerium ammonium nitrate to cerium nitrate is 5:1-1:

5.

6. The method according to claim 2, characterized in that The low-temperature drying temperature is 60°C-90°C, and the treatment temperature in nitrogen is 200-250°C.

7. The preparation method according to claim 2, characterized in that The carrier is activated carbon or molecular sieve; the molecular sieve is MCM-41, ZSM-5, SAPO-34, MOR, preferably MCM-41.

8. A method for synthesizing o-chlorocyclohexanone, characterized in that The cyclohexanone light oil and the catalyst are reacted under stirring by adding a chlorinating agent dropwise to obtain o-chlorocyclohexanone.

9. The synthesis method according to claim 8, characterized in that The specific reaction steps are: cyclohexanone light oil and catalyst are subjected to ring-opening reaction by dropping a chlorinating agent under stirring; after the reaction is completed, the reaction is allowed to stand and the layers are separated, the lower aqueous phase is filtered, the catalyst is recycled, the upper oil phase is washed with a Na2CO3 aqueous solution, the oil phase is distilled at atmospheric pressure, and the fraction between 203 and 204° C. is collected to obtain a crude o-chlorocyclohexanone product, which is then washed with a sodium carbonate solution, separated, and the oil phase is distilled to obtain pure o-chlorocyclohexanone.

10. The synthesis method according to claim 9, characterized in that The cyclohexanone light oil contains cyclohexane oxide, n-pentanol, cyclohexanol and cyclohexanone; the chlorinating agent is a mixture of one or two of chloric acid, chlorous acid and hypochlorous acid and hydrochloric acid; the mass content of hydrochloric acid in the chlorinating agent is 30%-80%.

11. The synthesis method according to claim 1, characterized in that The ring-opening reaction temperature is 20°C-50°C, the molar ratio of cyclohexene oxide in the light oil to the chlorinating agent is 1:1-1.5, and the amount of catalyst added is 0.5%-5% of the cyclohexene oxide in the cyclohexanone light oil.

12. The synthesis method according to claim 1, characterized in that The catalyst is a catalyst prepared according to any one of claims 1 to 7, preferably Ce-MCM-41.