CN113304764B - Catalyst for preparing acetonitrile by ammonification and dehydration of methyl acetate and preparation method thereof - Google Patents
Catalyst for preparing acetonitrile by ammonification and dehydration of methyl acetate and preparation method thereof Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract
The invention discloses a catalyst for preparing acetonitrile by ammonifying and dehydrating methyl acetate and a preparation method thereof, belonging to the technical field of chemical industry. The catalyst is prepared by adopting a precipitation impregnation method. Phosphate, nitrate and boron compound are dissolved in water in certain proportion. Adding a carrier with a certain weight, heating to a certain temperature, dripping alkali liquor, and adjusting the pH value of the solution to be 8.5-9. Stirring, filtering and washing with deionized water to ph=7. And (5) drying. And then calcined at a certain temperature for a certain time. The catalyst was charged into a fixed bed reactor to evaluate the reaction. The catalyst is prepared by adopting a precipitation impregnation method, and has high efficiency in the process of synthesizing acetonitrile by catalyzing ammonification and dehydration of ethyl acetate.
Description
Technical Field
The invention relates to a catalyst for preparing acetonitrile by ammonifying and dehydrating methyl acetate and a preparation method thereof, belonging to the technical field of chemical industry.
Background
Acetonitrile is an organic chemical raw material with wide application, and can be used in the fields of pharmacy, synthetic fiber, petrochemical industry and the like. With the research and development of downstream industries, the demand for acetonitrile has grown greatly. At present, most of acetonitrile in the world is derived from purification of byproducts of propylene ammoxidation, and the yield is only 1% -2%. In recent years, more mature routes for acetonitrile synthesis include: an ethanol ammoxidation route and an ethanol ammonization route. The two routes both use ethanol and ammonia with low price as raw materials, and the process has higher atom effectiveness and certain industrialization prospect. However, both of these synthetic processes produce unsafe byproducts, which makes the purification process of acetonitrile extremely complex: in the process of preparing acetonitrile by ammoxidation of ethanol, the byproduct is highly toxic hydrocyanic acid; in the process of preparing acetonitrile by ammonification of ethanol, the byproduct is explosive hydrogen. The existence of hydrocyanic acid or hydrogen severely restricts the industrial process of acetonitrile. At present, the trouble of poisoning and separating hydrocyanic acid in industry still exists. The existence of hydrogen is mentioned in the documents CN109999903 and Ind. Eng. Chem. Res.2020,59,5047-5055, which increases the difficulty of separating and purifying acetonitrile.
In 2017, with the success of a 10-ten thousand ton demonstration of a Chinese department synthesis gas ethanol (DMTE) process, the large-scale production of coal ethanol is accepted in the industry and rapidly promoted, the accumulated popularization capacity of the process is over 200 ten thousand tons at present, and the process can form a tens of millions of ton grade emerging industry in the future, so that the process has huge market prospect and potential. The core breakthrough in the process route is that dimethyl ether is carbonylated to prepare Methyl Acetate (MAC), compared with the traditional preparation route of the MAC by esterification synthesis, the process cost is reduced by 1/2, and the capacity scale of the single set of device in the megaton scale can be supported, so that the MAC has great potential of further extending and expanding as a platform compound in the aspects of economy and process scale. This provides a solid basis and economic guarantee for the process of preparing acetonitrile from MAC. The development of the process for preparing acetonitrile by using the MAC expands the application range of the MAC on one hand and enriches the industrial chain for preparing ethanol by using the synthesis gas. On the other hand, the process for preparing acetonitrile by using the MAC greatly strengthens the competition of acetonitrile in China in the international market due to the relatively low price of the MAC.
The three synthetic routes are shown below:
2CH 3 CH 2 OH+3NH 3 +3O 2 →CH 3 CN+2HCN+8H 2 O (1)
CH 3 CH 2 OH+NH 3 →CH 3 CN+2H 2 +H 2 O (2)
CH 3 COOCH 3 +NH 3 →CH 3 CN+CH 3 OH+H 2 O (3)
CO+2CH 3 OH→CH 3 COOCH 3 +H 2 O (4)
the process for preparing the acetonitrile by the MAC ammoniation dehydration is based on the factors of large-scale raw material sources, controllable price and the like, meanwhile, the byproducts are methanol and water, the unsafe factors of the acetonitrile synthesis process are perfectly solved, and the methanol can be used for synthesizing the MAC in a repeated and circulating way, so that the process accords with the current development trend of safety and environmental protection.
The synthesis of acetonitrile by MAC ammoniation dehydration has been relatively few, and extremely toxic mercury compounds or radioactive compounds were used as catalysts in the beginning of the 20 th century. In 2012, RUS 2440331C1 reported the use of H 3 PO 4 /r-Al 2 O 3 As a catalyst, the process for synthesizing acetonitrile by heterogeneous catalysis of ammonification and dehydration of ethyl acetate is required, but the raw materials need to contain a considerable proportion of acetic anhydride or ammonium salt of acetic acid, and the service life of the catalyst for synthesizing supported phosphoric acid is also worth considering. In summary, the process for synthesizing acetonitrile by MAC ammonification and dehydration is still immature.
Disclosure of Invention
In order to solve the problems, the invention provides a catalyst for preparing acetonitrile by ammonifying and dehydrating methyl acetate and a preparation method thereof.
The preparation method of the catalyst for preparing acetonitrile by ammonifying and dehydrating methyl acetate comprises the following steps: phosphate, nitrate, boron compounds are dissolved in water. Adding carrier, dropping alkali solution at a certain temperature, and adjusting pH=8.5-9. Stirring for a period of time, filtering, and washing with deionized water until the solution is neutral. Drying and calcining to obtain the catalyst for preparing acetonitrile by ammonifying and dehydrating methyl acetate.
The prepared catalyst was charged into a fixed bed reactor to evaluate the reaction. The catalyst has high efficiency in the process of synthesizing acetonitrile by catalyzing MAC ammonification and dehydration.
Further, the phosphate comprises one of sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate and potassium phosphate. Sodium dihydrogen phosphate is preferred. The weight of the phosphate is 1% -20% of the weight of the carrier.
Further, the nitrate comprises one, two or more of magnesium nitrate, cobalt nitrate, nickel nitrate, chromium nitrate, zinc nitrate, zirconium nitrate and bismuth nitrate. The weight of nitrate is 1% -15% of the weight of the carrier.
Further, the boron compound comprises one of boric acid, sodium borate, trimethyl borate and triethyl borate. Sodium borate is preferred. The weight of boride is 1-10% of the weight of carrier.
Further, the carrier comprises r-Al 2 O 3 One of silica gel, HZSM-5 molecular sieve, MCM-41 molecular sieve and all-silicon molecular Sieve (SI). Preferably silica gel. The specific surface area of the carrier is 200-600M 2 And/g. Preferably 380-400M 2 /g。
Further, the alkali liquor comprises sodium bicarbonate, sodium carbonate or sodium hydroxide carbonate aqueous solution. Aqueous sodium carbonate solutions are preferred.
Further, the certain temperature is 25 ℃ to 100 ℃, preferably 60 ℃ for 4 hours to 12 hours, preferably 8 hours. The concentration of the alkaline solution is 2wt% to 15wt%, preferably 10wt%.
Further, the drying temperature is 80-150 ℃, preferably 120 ℃, and the drying time is 6-18 hours, preferably 8 hours; the calcination temperature is 400-800 ℃, preferably 550 ℃, and the calcination time is 3-12 hours, preferably 5 hours.
Further, cooling to room temperature after calcining, tabletting, crushing, and sieving with 20-40 mesh sieve.
The invention also provides a catalyst for preparing acetonitrile by ammonifying and dehydrating methyl acetate, which is prepared by the preparation method.
Detailed Description
The following detailed description of the embodiments of the technical solution of the present invention is provided, but the present invention is not limited to the following description.
The catalyst is prepared by adopting a precipitation impregnation method. The invention uses alkali solution as precipitant, and then stirs and impregnates at a certain temperature. The carriers used are all commercially available (except for all-silicon molecular sieves). The synthesis of all-silicon molecular sieves is prepared as described in US 4061724. The weight of phosphate relative to the carrier is the weight after subtraction of the water of crystallization.
Example 1
11.5g of potassium dihydrogen phosphate (KH) 2 PO 4 ) 14.7g of zirconium nitrate (Zr (NO) 3 ) 4 .H 2 O), 3.04g boric acid was added to 160g deionized water. Heating to 40deg.C, stirring and dissolving. 100g of silica gel (20-40 mesh) was added thereto. After stirring for 30 minutes, 8wt% sodium hydroxide solution was added dropwise, and the pH of the solution was adjusted=8.5 to 9. Stirred for 8 hours, filtered and washed with deionized water to ph=7. Drying in an oven at 120deg.C for 12 hr. Then put into a muffle furnace at 550 ℃ for calcination for 8 hours. Cooling to room temperature, taking 5g and loading into a fixed bed reactor for evaluation.
When the temperature of the reaction bed reaches 520 ℃, MAC (media access control) enters from the upper end of the catalyst bed at a rate of 18g/h, ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactant is obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reactants were analyzed by gas phase and consisted of 12.9% mac, 83.5% acetonitrile, 1.58% acetamide intermediate. The conversion rate is more than 87.1 percent. After rectification and purification, the purity of acetonitrile is more than 99 percent, and the yield is more than 84 percent.
Example 2
13.2g of sodium dihydrogen phosphate (NaH) 2 PO 4 .2H 2 O), 12.2g zinc nitrate (Zn (NO) 3 ) 2 .6H 2 O), 3.04g boronSodium acid was added to 160g deionized water. Heating to 60 ℃, stirring and dissolving. To this was added 100g of MCM-41 molecular sieve (20-40 mesh). After stirring for 30 minutes, a 10wt% sodium carbonate solution was added dropwise, and the pH of the solution was adjusted=8.5 to 9. Stirred for 12 hours, filtered, washed with deionized water to ph=7. Drying in an oven at 120deg.C for 12 hr. Then put into a muffle furnace at 450 ℃ for calcination for 8 hours. Cooling to room temperature, taking 5g and loading into a fixed bed reactor for evaluation.
When the temperature of the reaction bed reaches 520 ℃, MAC (media access control) enters from the upper end of the catalyst bed at a rate of 18g/h, ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactant is obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reactants were analyzed by gas phase and consisted of 15.02% mac, 82.3% acetonitrile, 1.38% acetamide intermediate. The conversion rate is more than 85%. The purity of acetonitrile is more than 99 percent and the yield is more than 81 percent after rectification and purification.
Example 3
13.2g of sodium dihydrogen phosphate (NaH) 2 PO 4 .2H 2 O), 9.99g nickel nitrate (Ni (NO) 3 ) 2 .6H 2 O), 5.04g of sodium borate was added to 160g of deionized water. Heating to 60 ℃, stirring and dissolving. To this was added 100g of HZSM-5 molecular sieve (20-40 mesh). After stirring for 30 minutes, a 10wt% sodium carbonate solution was added dropwise, and the pH of the solution was adjusted=8.5 to 9. Stirred for 8 hours, filtered and washed with deionized water to ph=7. Drying in an oven at 120deg.C for 12 hr. Then put into a muffle furnace at 500 ℃ for calcination for 8 hours. Cooling to room temperature, taking 5g and loading into a fixed bed reactor for evaluation.
When the temperature of the reaction bed reaches 520 ℃, MAC (media access control) enters from the upper end of the catalyst bed at a rate of 18g/h, ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactant is obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reactants were analyzed by gas phase and consisted of 43.4% mac, 51.1% acetonitrile, 2.81% acetamide intermediate. The conversion rate is more than 56.6%. The purity of acetonitrile is more than 99 percent and the yield is more than 53 percent after rectification and purification.
Example 4
13.87g of sodium phosphate (Na 3 PO 4 ) 2g of magnesium nitrate, 10g of cobalt nitrate (Co (NO) 3 ) 3 .6H 2 O), 4.04g of sodium borate was added to 160g of deionized water. Heating to 60 ℃, stirring and dissolving. To this was added 100g of all-silicon molecular Sieve (SI) (20-40 mesh). After stirring for 30 minutes, a 10wt% sodium carbonate solution was added dropwise, and the pH of the solution was adjusted=8.5 to 9. Stirred for 8 hours, filtered and washed with deionized water to ph=7. Drying in an oven at 120deg.C for 8 hr. Then put into a muffle furnace at 600 ℃ for calcination for 8 hours. Cooling to room temperature, taking 5g and loading into a fixed bed reactor for evaluation.
When the temperature of the reaction bed reaches 520 ℃, MAC (media access control) enters from the upper end of the catalyst bed at a rate of 18g/h, ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactant is obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reactants were analyzed by gas phase and consisted of 12.9% mac, 83.6% acetonitrile, 1.58% acetamide intermediate. The conversion rate is more than 87.1 percent. The purity of acetonitrile is more than 99 percent and the yield is more than 82 percent after rectification and purification.
Example 5
17.2g of disodium hydrogen phosphate, 5g of magnesium nitrate, 18g of cobalt nitrate (Co (NO) 3 ) 3 .6H 2 O), 3.04g of sodium borate was added to 160g of deionized water. Heating to 100deg.C, stirring and dissolving. 100g of silica gel (20-40 mesh) was added thereto. After stirring for 30 minutes, a 10wt% sodium carbonate solution was added dropwise, and the pH of the solution was adjusted=8.5 to 9. Stirred for 8 hours, filtered and washed with deionized water to ph=7. Drying in an oven at 120deg.C for 12 hr. Then put into a muffle furnace at 500 ℃ for calcination for 6 hours. Cooling to room temperature, taking 5g and loading into a fixed bed reactor for evaluation.
When the temperature of the reaction bed reaches 520 ℃, MAC (media access control) enters from the upper end of the catalyst bed at a rate of 18g/h, ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactant is obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reactants were analyzed by gas phase and consisted of 2.4% mac, 94.3% acetonitrile, 1.0% acetamide intermediate. The conversion rate is more than 97.6%. The purity of acetonitrile is more than 99 percent and the yield is more than 90 percent after rectification and purification.
Example 6
6.6g of sodium dihydrogen phosphate (NaH) 2 PO 4 .2H 2 O), 5g of magnesium nitrate, 18g of cobalt nitrate (Co (NO) 3 ) 3 .6H 2 O), 3.04g of sodium borate was added to 160g of deionized water. Heating to 100deg.C, stirring and dissolving. 100g of silica gel (20-40 mesh) was added thereto. After stirring for 30 minutes, a 10wt% sodium carbonate solution was added dropwise, and the pH of the solution was adjusted=8.5 to 9. Stirred for 8 hours, filtered and washed with deionized water to ph=7. Drying in a 100 ℃ oven for 12 hours. Then put into a muffle furnace at 500 ℃ for calcination for 8 hours. Cooling to room temperature, taking 5g and loading into a fixed bed reactor for evaluation.
When the temperature of the reaction bed reaches 520 ℃, MAC (media access control) enters from the upper end of the catalyst bed at a rate of 18g/h, ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactant is obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reactants were analyzed by gas phase and consisted of 6.4% mac, 91.3% acetonitrile, 1.6% acetamide intermediate. The conversion rate is more than 93.6%. The purity of acetonitrile is more than 99 percent and the yield is more than 86 percent after rectification and purification.
Example 7
30.3g of disodium hydrogen phosphate (Na 2 HPO 4 .12H 2 O), 5g of magnesium nitrate, 18g of bismuth nitrate (Bi (NO) 3 ) 3 .5H 2 O), 3.04g of sodium borate was added to 150g of deionized water. Heating to 100deg.C, stirring and dissolving. 100g of silica gel (20-40 mesh) was added thereto. After stirring for 30 minutes, a 10wt% sodium carbonate solution was added dropwise, and the pH of the solution was adjusted=8.5 to 9. Stirred for 8 hours, filtered and washed with deionized water to ph=7. Drying in an oven at 120deg.C for 12 hr. Then put into a muffle furnace at 500 ℃ for calcination for 8 hours. Cooling to room temperature, taking 5g and loading into a fixed bed reactor for evaluation.
When the temperature of the reaction bed reaches 520 ℃, MAC (media access control) enters from the upper end of the catalyst bed at a rate of 18g/h, ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactant is obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reactants were analyzed by gas phase and consisted of 5% mac, 92.5% acetonitrile, 1.2% acetamide intermediate. The conversion rate is more than 95%. The purity of acetonitrile is more than 99 percent and the yield is more than 88 percent after rectification and purification.
Claims (10)
1. A preparation method of a catalyst for preparing acetonitrile by ammonifying and dehydrating methyl acetate is characterized by comprising the following steps of: the method comprises the following steps: dissolving phosphate, nitrate and boron compound into water, adding carrier, dropping alkali solution at certain temperature, and regulating pH value of the solution to 8.5-9; stirring for a period of time, filtering, and washing with deionized water until the solution is neutral; drying and calcining to obtain the catalyst for preparing acetonitrile by ammonifying and dehydrating methyl acetate;
the phosphate is selected from one of sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate and potassium phosphate;
the nitrate is one, two or more than two selected from magnesium nitrate, cobalt nitrate, nickel nitrate, chromium nitrate, zinc nitrate, zirconium nitrate and bismuth nitrate;
the boron compound is selected from one of boric acid, sodium borate, trimethyl borate and triethyl borate.
2. The method of manufacturing according to claim 1, characterized in that: the weight of the phosphate is 1% -20% of the weight of the carrier.
3. The method of manufacturing according to claim 1, characterized in that: the weight of nitrate is 1% -15% of the weight of the carrier.
4. The method of manufacturing according to claim 1, characterized in that: the weight of boride is 1-10% of the weight of carrier.
5. The method of manufacturing according to claim 1, characterized in that: the carrier comprises r-Al 2 O 3 One of silica gel, HZSM-5 molecular sieve, MCM-41 molecular sieve and all-silicon molecular Sieve (SI); the specific surface area of the carrier is 200-600M 2/g.
6. The method of manufacturing according to claim 1, characterized in that: the certain temperature is 25-100 ℃, the period of time is 4-12 hours, and the concentration of the alkali solution is 2-15 wt%.
7. The method of manufacturing according to claim 1, characterized in that: the alkali liquor comprises sodium bicarbonate, sodium carbonate or sodium hydroxide aqueous solution.
8. The method of manufacturing according to claim 1, characterized in that: the drying temperature is 80-150 ℃ and the drying time is 6-18 hours; the calcination temperature is 400-800 ℃ and the calcination time is 3-12 hours.
9. The method of manufacturing according to claim 1, characterized in that: cooling to room temperature after calcining, tabletting, crushing, and sieving with 20-40 mesh sieve.
10. The catalyst for preparing acetonitrile by ammonification and dehydration of methyl acetate, which is prepared by the preparation method of any one of claims 1-9.
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