CN113304764A - Catalyst for preparing acetonitrile by ammoniation and dehydration of methyl acetate and preparation method thereof - Google Patents
Catalyst for preparing acetonitrile by ammoniation and dehydration of methyl acetate and preparation method thereof Download PDFInfo
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- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
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- B01J27/14—Phosphorus; Compounds thereof
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- B01J29/0352—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites containing iron group metals, noble metals or copper
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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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- B01J29/00—Catalysts comprising molecular sieves
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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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- C07C253/00—Preparation of carboxylic acid nitriles
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Abstract
The invention discloses a catalyst for preparing acetonitrile by ammoniation and dehydration of methyl acetate and a preparation method thereof, belonging to the technical field of chemical industry. The catalyst is prepared by a precipitation impregnation method. Phosphate, nitrate and boron compound are dissolved in water according to a certain proportion. Adding a certain weight of carrier, heating to a certain temperature, dropwise adding alkali liquor, and adjusting the pH value of the solution to 8.5-9. Stirred, filtered and washed with deionized water to pH 7. And (5) drying. Then calcining at a certain temperature for a certain time. The catalyst was charged into a fixed bed reactor to conduct the evaluation reaction. The catalyst is prepared by a precipitation impregnation method, and has high efficiency in a process of catalyzing ethyl acetate to ammoniate and dehydrate to synthesize acetonitrile.
Description
Technical Field
The invention relates to a catalyst for preparing acetonitrile by ammoniation and dehydration of 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 fibers, petrochemical industry and the like. With the research and development of downstream industries, the demand of acetonitrile is greatly increased. At present, most of acetonitrile in the world comes from the purification of byproducts of propylene ammoxidation, and the yield is only 1-2%. In recent years, the more mature research routes for acetonitrile synthesis include: an ethanol ammoxidation route and an ethanol amination route. The two routes both use ethanol and ammonia with low price as raw materials, and meanwhile, the process has high atomic effectiveness and certain industrial prospect. However, both of these synthetic processes produce unsafe by-products, which makes the purification process of acetonitrile extremely complicated: in the process of preparing acetonitrile by ammoxidation of ethanol, a byproduct is virulent hydrocyanic acid; in the process of preparing acetonitrile by ethanol ammoniation, the byproduct is explosive hydrogen. The existence of hydrocyanic acid or hydrogen severely restricts the industrial process of the acetonitrile. The trouble of poisoning and separating hydrocyanic acid in the industry still exists at present. The existence of hydrogen is mentioned in 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 10-ten-thousand-ton demonstration of a process for preparing ethanol (DMTE) from synthesis gas in Chinese academy of sciences, the large-scale production of the ethanol prepared from coal is accepted by the industry and rapidly popularized, the accumulated popularization productivity of the process is over 200-ten-thousand-ton at present, ten-thousand-ton-level emerging industries can be formed in the future, and the market prospect and the potential are huge. The core breakthrough in the process route is the preparation of Methyl Acetate (MAC) by carbonylation of dimethyl ether, compared with the traditional preparation of MAC by esterification synthesis, the process cost is reduced by 1/2, and megaton-level capacity scale of a single set of device can be supported, so that the MAC has great potential for further extension and development as a platform compound in the aspects of economy and process scale. And the method provides a solid foundation and economic guarantee for the process for preparing the acetonitrile from the MAC. The development of the process for preparing the acetonitrile by the MAC expands the application range of the MAC on one hand, and enriches the industrial chain for preparing the ethanol by the synthesis gas. On the other hand, in the process for preparing acetonitrile by MAC, the MAC price is relatively low, so that the competitive strength of acetonitrile in international markets in China is greatly enhanced.
The three synthetic routes are given below:
2CH3CH2OH+3NH3+3O2→CH3CN+2HCN+8H2O (1)
CH3CH2OH+NH3→CH3CN+2H2+H2O (2)
CH3COOCH3+NH3→CH3CN+CH3OH+H2O (3)
CO+2CH3OH→CH3COOCH3+H2O (4)
the process for preparing the acetonitrile by MAC ammoniation and dehydration is based on the factors of large-scale raw material sources, controllable price and the like, meanwhile, the by-products are the methanol and the water, the unsafe factors of the acetonitrile synthesis process are perfectly solved, the methanol can be repeatedly and circularly synthesized into the MAC, and the current development trend of safety and environmental protection is met.
The research on synthesizing acetonitrile by MAC ammoniation and dehydration is relatively less, and in the early 20 th century, a highly toxic mercury compound or a radioactive compound is mostly used as a catalyst. In 2012, RUS 2440331C1 reported the use of H3PO4/r-Al2O3The catalyst is used for heterogeneous catalysis of the process for synthesizing acetonitrile by ammoniation and dehydration of ethyl acetate, but 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 carrying phosphoric acid for synthesis is worth considering. In conclusion, the process for synthesizing acetonitrile by MAC ammoniation dehydration is not mature.
Disclosure of Invention
In order to solve the problems, the invention provides a catalyst for preparing acetonitrile by ammoniation and dehydration of methyl acetate and a preparation method thereof.
A preparation method of a catalyst for preparing acetonitrile by ammoniation and dehydration of methyl acetate comprises the following steps: phosphate, nitrate and boron compound are dissolved in water. Adding carrier, dropping alkali solution at certain temperature to regulate pH to 8.5-9. Stirring for a while, filtering, washing with deionized water until the solution is neutral. Drying and calcining to obtain the catalyst for preparing acetonitrile by ammoniating and dehydrating methyl acetate.
The obtained catalyst was charged into a fixed bed reactor to evaluate the reaction. The catalyst has high efficiency in the process of catalyzing MAC ammoniation dehydration to synthesize acetonitrile.
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 or two or more of magnesium nitrate, cobalt nitrate, nickel nitrate, chromium nitrate, zinc nitrate, zirconium nitrate and bismuth nitrate. The weight of the nitrate accounts for 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-Al2O3One of silica gel, HZSM-5 molecular sieve, MCM-41 molecular sieve and total silicon molecular Sieve (SI). Silica gel is preferred. The specific surface area of the carrier is 200-600M2(ii) in terms of/g. Preferably 380-400M2/g。
Further, the alkali liquor comprises sodium bicarbonate, sodium carbonate or sodium hydroxide aqueous solution. Aqueous sodium carbonate solutions are preferred.
Further, the certain temperature is 25-100 ℃, preferably 60 ℃, and the period of time is 4-12 hours, preferably 8 hours. The concentration of the alkali solution is 2 wt% to 15 wt%, preferably 10 wt%.
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 a 20-40 mesh sieve to obtain the product.
The invention also provides a catalyst for preparing acetonitrile by ammoniation and dehydration of methyl acetate, which is prepared by the preparation method.
Detailed Description
The following detailed description of specific embodiments of the present invention is provided, but the present invention is not limited to the following description.
The catalyst is prepared by a precipitation impregnation method. The invention uses alkali solution as precipitant, then stirs and soaks at a certain temperature. The supports used are all commercially available (except for all-silicon molecular sieves). Synthesis of all-silica molecular sieves was made 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
Adding 11.5g potassium dihydrogen phosphate (KH)2PO4) 14.7g of zirconium nitrate (Zr (NO)3)4.H2O), 3.04g of boric acid was added to 160g of deionized water. Heating to 40 deg.C, stirring and dissolving. 100g of silica gel (20-40 mesh) was added thereto. After stirring for 30 minutes, 8 wt% sodium hydroxide solution was added dropwise to adjust the pH of the solution to 8.5 to 9. Stir 8 h, filter, and wash with deionized water to pH 7. Drying in an oven at 120 deg.C for 12 hr. Then, the mixture was calcined in a muffle furnace at 550 ℃ for 8 hours. The temperature was reduced to room temperature, and 5g of the mixture was charged 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 and ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactants are obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reaction composition by gas phase analysis was 12.9% MAC, 83.5% acetonitrile, 1.58% acetamide intermediate. The conversion was greater than 87.1%. After rectification and purification, the purity of the acetonitrile is more than 99 percent, and the yield is more than 84 percent.
Example 2
13.2g of sodium dihydrogen phosphate (NaH)2PO4.2H2O), 12.2g of zinc nitrate (Zn (NO)3)2.6H2O), 3.04g sodium borateAdded to 160g of deionized water. Heating to 60 deg.C, stirring and dissolving. 100g of MCM-41 molecular sieve (20-40 mesh) was added to the slurry. After stirring for 30 minutes, a 10 wt% sodium carbonate solution was added dropwise to adjust the pH of the solution to 8.5 to 9. Stirred for 12 hours, filtered and washed with deionized water to pH 7. Drying in an oven at 120 deg.C for 12 hr. Then, the mixture was calcined in a muffle furnace at 450 ℃ for 8 hours. The temperature was reduced to room temperature, and 5g of the mixture was charged 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 and ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactants are obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reaction composition, by gas phase analysis, was 15.02% MAC, 82.3% acetonitrile, 1.38% acetamide intermediate. The conversion is greater than 85%. After rectification and purification, the purity of the acetonitrile is more than 99 percent, and the yield is more than 81 percent.
Example 3
13.2g of sodium dihydrogen phosphate (NaH)2PO4.2H2O), 9.99g of nickel nitrate (Ni (NO)3)2.6H2O), 5.04g sodium borate was added to 160g deionized water. Heating to 60 deg.C, stirring and dissolving. 100g of HZSM-5 molecular sieve (20-40 mesh) was added thereto. After stirring for 30 minutes, a 10 wt% sodium carbonate solution was added dropwise to adjust the pH of the solution to 8.5 to 9. Stir 8 h, filter, and wash with deionized water to pH 7. Drying in an oven at 120 deg.C for 12 hr. Then, the mixture was calcined in a muffle furnace at 500 ℃ for 8 hours. The temperature was reduced to room temperature, and 5g of the mixture was charged 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 and ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactants are obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reaction composition, analyzed in the gas phase, contained 43.4% MAC, 51.1% acetonitrile, 2.81% acetamide intermediate. The conversion was greater than 56.6%. After rectification and purification, the purity of the acetonitrile is more than 99 percent, and the yield is more than 53 percent.
Example 4
13.87g of sodium phosphate (Na)3PO4) 2g of magnesium nitrate, 10g of cobalt nitrate (Co (NO)3)3.6H2O), 4.04g sodium borate was added to 160g deionized water. Heating to 60 deg.C, stirring and dissolving. 100g of all-silica molecular Sieve (SI) (20-40 mesh) was added thereto. After stirring for 30 minutes, a 10 wt% sodium carbonate solution was added dropwise to adjust the pH of the solution to 8.5 to 9. Stir 8 h, filter, and wash with deionized water to pH 7. Drying in an oven at 120 deg.C for 8 hr. Then, the mixture was calcined in a 600 ℃ muffle furnace for 8 hours. The temperature was reduced to room temperature, and 5g of the mixture was charged 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 and ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactants are obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reaction composition by gas phase analysis was 12.9% MAC, 83.6% acetonitrile, 1.58% acetamide intermediate. The conversion rate is more than 87.1 percent. After rectification and purification, the purity of the acetonitrile is more than 99 percent, and the yield is more than 82 percent.
Example 5
17.2g of disodium hydrogenphosphate, 5g of magnesium nitrate, 18g of cobalt nitrate (Co (NO)3)3.6H2O), 3.04g sodium borate was added to 160g deionized water. Heating to 100 deg.C, stirring and dissolving. 100g of silica gel (20-40 mesh) was added thereto. After stirring for 30 minutes, a 10 wt% sodium carbonate solution was added dropwise to adjust the pH of the solution to 8.5 to 9. Stir 8 h, filter, and wash with deionized water to pH 7. Drying in an oven at 120 deg.C for 12 hr. Then, the mixture was calcined in a muffle furnace at 500 ℃ for 6 hours. The temperature was reduced to room temperature, and 5g of the mixture was charged 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 and ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactants are obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reaction was analyzed in the gas phase and consisted of 2.4% MAC, 94.3% acetonitrile, 1.0% acetamide intermediate. The conversion was greater than 97.6%. After rectification and purification, the purity of the acetonitrile is more than 99 percent, and the yield is more than 90 percent.
Example 6
6.6g of sodium dihydrogen phosphate (NaH)2PO4.2H2O), 5g of magnesium nitrate, 18g of cobalt nitrate (Co (NO)3)3.6H2O), 3.04g sodium borate was added to 160g deionized water. Heating to 100 deg.C, stirring and dissolving. 100g of silica gel (20-40 mesh) was added thereto. After stirring for 30 minutes, a 10 wt% sodium carbonate solution was added dropwise to adjust the pH of the solution to 8.5 to 9. Stir 8 h, filter, and wash with deionized water to pH 7. Drying in an oven at 100 deg.C for 12 hr. Then, the mixture was calcined in a muffle furnace at 500 ℃ for 8 hours. The temperature was reduced to room temperature, and 5g of the mixture was charged 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 and ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactants are obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reaction composition by gas phase analysis was 6.4% MAC, 91.3% acetonitrile, 1.6% acetamide intermediate. The conversion was greater than 93.6%. After rectification and purification, the purity of the acetonitrile is more than 99 percent, and the yield is more than 86 percent.
Example 7
30.3g of disodium hydrogen phosphate (Na)2HPO4.12H2O), 5g of magnesium nitrate, 18g of bismuth nitrate (Bi (NO)3)3.5H2O), 3.04g sodium borate was added to 150g deionized water. Heating to 100 deg.C, stirring and dissolving. 100g of silica gel (20-40 mesh) was added thereto. After stirring for 30 minutes, a 10 wt% sodium carbonate solution was added dropwise to adjust the pH of the solution to 8.5 to 9. Stir 8 h, filter, and wash with deionized water to pH 7. Drying in an oven at 120 deg.C for 12 hr. Then, the mixture was calcined in a muffle furnace at 500 ℃ for 8 hours. The temperature was reduced to room temperature, and 5g of the mixture was charged 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 and ammonia gas enters from the upper end of the catalyst bed at a rate of 100mL/min, and liquid reactants are obtained through three-stage condensation after the reaction of the catalyst bed. The liquid reaction was analyzed in the gas phase and consisted of 5% MAC, 92.5% acetonitrile, 1.2% acetamide intermediate. The conversion rate is more than 95 percent. After rectification and purification, the purity of the acetonitrile is more than 99 percent, and the yield is more than 88 percent.
Claims (10)
1. A preparation method of a catalyst for preparing acetonitrile by ammoniation and dehydration of methyl acetate is characterized by comprising the following steps: the method comprises the following steps: dissolving phosphate, nitrate and boron compound into water, adding a carrier, dropwise adding an alkali solution at a certain temperature, and adjusting the 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 ammoniating and dehydrating methyl acetate.
2. The method of claim 1, wherein: the phosphate comprises one of sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate and potassium phosphate; the weight of the phosphate is 1-20% of the weight of the carrier.
3. The method of claim 1, wherein: the nitrate comprises one, two or more than two of magnesium nitrate, cobalt nitrate, nickel nitrate, chromium nitrate, zinc nitrate, zirconium nitrate and bismuth nitrate; the weight of the nitrate accounts for 1-15% of the weight of the carrier.
4. The method of claim 1, wherein: the boron compound comprises one of boric acid, sodium borate, trimethyl borate and triethyl borate; the weight of boride is 1-10% of the weight of carrier.
5. The method of claim 1, wherein: the carrier comprises r-Al2O3One of silica gel, HZSM-5 molecular sieve, MCM-41 molecular sieve and total silicon molecular Sieve (SI); the specific surface area of the carrier is 200-600M2/g。
6. The method of claim 1, wherein: the certain temperature is 25-100 ℃, the certain time is 4-12 hours, and the concentration of the alkali solution is 2-15 wt%.
7. The method of claim 1, wherein: the alkali liquor comprises sodium bicarbonate, sodium carbonate or sodium hydroxide aqueous solution.
8. The method of claim 1, wherein: 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 claim 1, wherein: cooling to room temperature after calcining, tabletting, crushing, and sieving with a 20-40 mesh sieve to obtain the final product.
10. The catalyst for preparing acetonitrile by ammoniation and dehydration of methyl acetate, which is prepared by the preparation method of any one of claims 1 to 9.
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