A process for the production of nitrile / amine products
By using a composite catalyst consisting of acid, non-metallic oxide, and a support, and reacting with acetate under an NH3 and H2 atmosphere, the problems of high corrosivity and low conversion rate in existing acetonitrile production have been solved, achieving efficient and safe production of acetonitrile and ethylamine.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2023-05-23
- Publication Date
- 2026-07-07
AI Technical Summary
Existing acetonitrile production methods suffer from problems such as high corrosivity, complex processes, high costs, and low conversion rates.
A composite catalyst containing acid, non-metallic oxide and support is used to react with acetate in a mixed atmosphere of NH3 and H2 to generate nitrile/amine products.
It achieves non-corrosive and safe process operation, with fast reaction rate, high conversion rate and selectivity. The conversion rate of acetate can reach more than 98%, and the selectivity of nitriles and amines is also high.
Abstract
Description
Technical Field
[0001] This application relates to a method for producing nitrile / amine products, which belongs to the field of chemical preparation. Background Technology
[0002] Acetonitrile is a widely used solvent and fine chemical raw material. Currently, representative production methods include: 1) acetonitrile produced as a byproduct of propylene ammoxidation; 2) acetic acid ammoxidation synthesis; and 3) ethanol ammoxidation synthesis. In the first method, acetonitrile is derived from the ammoxidation of propylene to acrylonitrile. The separation and purification process of acetonitrile is complex and involves the handling of the highly toxic byproduct hydrogen cyanide, placing stringent requirements on equipment and process operation. The main drawback of the second method is the strong corrosiveness of acetic acid to the reaction equipment, thus it is currently largely discontinued. The third method suffers from a cost disadvantage due to the tendency of ethanol and acetonitrile to form an azeotropic system, the high cost of ethanol as a raw material, and the need for high-load catalysts such as Cu, Ni, and Co, thus preventing its practical industrial application. Summary of the Invention
[0003] According to one aspect of this application, a method for producing nitrile / amine products is provided, which is characterized by being non-corrosive, having safe operating conditions, a fast reaction rate, high reaction conversion and atom utilization, and a stable reaction.
[0004] A method for producing nitrile / amine products involves contacting a material containing acetate with a catalyst in a mixed atmosphere of NH3 and H2 to react and generate nitrile / amine products.
[0005] Optionally, the catalyst comprises an acid, a non-metallic oxide, and a support.
[0006] The catalyst of this application is a composite catalyst containing an acid, a non-metallic oxide and a support, and its preparation method can be impregnation, physical mixing and precipitation.
[0007] Optionally, the acid is selected from at least one of heteropoly acids, phosphoric acid, and oxalic acid.
[0008] Optionally, the heteropolyacid is selected from at least one of phosphotungstic acid, phosphotomolybdic acid, silicotungstic acid, and silicotomolybdic acid.
[0009] Optionally, the non-metallic oxide is selected from at least one of phosphorus pentoxide, selenium dioxide, and tellurium dioxide.
[0010] Optionally, the carrier is selected from at least one of alumina, silica, kaolin, and molecular sieve.
[0011] Optionally, the molecular sieve is selected from at least one of Y-type molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, and Beta molecular sieve.
[0012] Optionally, in the catalyst, the acid content is 1.0 to 5.0 wt%, the non-metallic oxide content is 1.0 to 15.0 wt%, and the support content is 80.0 to 98.0 wt%.
[0013] The content is calculated as a percentage of the total mass of the catalyst.
[0014] Optionally, the acid content is independently selected from any value or a range between 1.0 wt%, 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, 3.5 wt%, 4.0 wt%, 4.5 wt%, and 5.0 wt%.
[0015] Optionally, the content of the non-metallic oxide is independently selected from any value or a range between 1.0 wt%, 2.0 wt%, 3.0 wt%, 4.0 wt%, 5.0 wt%, 6.0 wt%, 7.0 wt%, 8.0 wt%, 9.0 wt%, 10.0 wt%, 11.0 wt%, 12.0 wt%, 13.0 wt%, 14.0 wt%, and 15.0 wt%.
[0016] Optionally, the content of the carrier is independently selected from any value or a range between 80.0 wt%, 82.0 wt%, 84.0 wt%, 86.0 wt%, 88.0 wt%, 90.0 wt%, 92.0 wt%, 94.0 wt%, 96.0 wt%, and 98.0 wt%.
[0017] Optionally, the acetate is selected from at least one of methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.
[0018] Optionally, the nitrile / amine product is acetonitrile and ethylamine.
[0019] In this application, acetate is used as the raw material, and the resulting ammoniated products are acetonitrile and ethylamine.
[0020] Optionally, the reaction conditions are as follows:
[0021] The reaction temperature was 200–450℃, the reaction pressure was 0.1–1.0 MPa, the molar ratio of the NH3 and H2 mixture to the acetate was 1–30:1, and the mass hourly space velocity (WHSV) of the acetate was 0.1–5 h⁻¹. ～1 .
[0022] Optionally, the H2 content in the NH3 and H2 mixture is 0.01 to 20% vol.
[0023] Optionally, the reaction temperature is independently selected from any value or a range between 200°C, 220°C, 250°C, 270°C, 300°C, 320°C, 350°C, 370°C, 400°C, 420°C, and 450°C.
[0024] Optionally, the reaction pressure is independently selected from any value or a range between 0.1 MPa, 0.2 MPa, 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, and 1.0 MPa.
[0025] Optionally, the molar ratio of the NH3 and H2 mixture to the acetate is independently selected from any value or a range between 1:1, 2:1, 5:1, 7:1, 10:1, 12:1, 15:1, 17:1, 20:1, 22:1, 25:1, 27:1, and 30:1.
[0026] Optionally, the mass hourly space velocity (MSV) of the acetate is independently selected from 0.1 h⁻¹. -1 0.2h -1 0.3h -1 0.4h -1 0.5h -1 0.6h -1 0.7h -1 0.8h -1 0.9h -1 1.0h -1 1.5h -1 2.0h -1 2.5h -1 3.0h -1 3.5h -1 4.0h -1 4.5h -1 5.0h -1 Any value in the range or any value between the two.
[0027] Optionally, in the NH3 and H2 mixture, the H2 content is independently selected from any value or a range between 0.01% vol, 0.05% vol, 0.1% vol, 1% vol, 2% vol, 5% vol, 7% vol, 10% vol, 12% vol, 15% vol, 17% vol, and 20% vol.
[0028] Optionally, the reaction is carried out in a reactor, which is selected from a fixed-bed reactor, a batch reactor, a moving-bed reactor, or a fluidized-bed reactor.
[0029] The beneficial effects that this application can produce include:
[0030] The method for producing nitrile / amine products provided in this application is characterized by being non-corrosive, having safe operating conditions, a fast reaction rate, high conversion rate and atom utilization, and a stable reaction. It can directly convert acetate into a nitrile / amine product system with a high acetate conversion rate (over 98%), high selectivity for nitrile and amine, and a total selectivity for acetonitrile and ethylamine exceeding 98%. Detailed Implementation
[0031] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.
[0032] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially.
[0033] Unless otherwise specified, all test methods are standard and all instrument settings are those recommended by the manufacturer.
[0034] The analytical methods for the products in the embodiments of this application are as follows:
[0035] The reaction products were analyzed using an Agilent 7890B gas chromatograph.
[0036] In the embodiments of this application, the conversion rate and selectivity are calculated as follows:
[0037] In the embodiments of this application, the conversion rate of ethyl acetate and the selectivity of acetonitrile and ethylamine are calculated based on mass:
[0038] Ethyl acetate conversion rate = (1 - moles of acetate in the product / moles of acetate in the feed) * 100%
[0039] Selectivity of acetonitrile = (moles of acetonitrile in the product / (moles of acetate in the feed - moles of acetate in the product)) * 100%
[0040] Selectivity of ethylamine = (moles of ethylamine in the product / (moles of acetate in the feed - moles of acetate in the product)) * 100%
[0041] Example 1
[0042] 5g of selenium dioxide and 92.5g of alumina were mixed and shaped to obtain a catalyst precursor. 2.5g of phosphotungstic acid was dissolved in water and impregnated onto the catalyst precursor. The impregnated sample was dried at 120℃ for 12 hours and calcined at 500℃ for 6 hours to obtain catalyst A, wherein the content of phosphotungstic acid was 2.5wt%, the content of selenium dioxide was 5wt%, and the content of alumina was 92.5wt%.
[0043] 10g of catalyst A was charged into a fixed-bed reactor, and the catalyst temperature was raised to 300℃. An NH3-H2 mixture, with an H2 content of 20.0 vol%, was introduced into the reactor. Ethyl acetate was then introduced into the reactor at a mass hourly space velocity (WHSV) of 0.5 h⁻¹. -1 The molar ratio of NH3-H2 mixture to ethyl acetate was 10:1, and the reaction pressure was 1.0 MPa. After reaction, the products were collected and analyzed. The conversion rate of ethyl acetate was 97.4%. Among the amination products, the selectivity for acetonitrile was 65.7%, and the selectivity for ethylamine was 32.5%.
[0044] Example 2
[0045] 1.5 g of selenium dioxide and 97 g of silicon dioxide were mixed and shaped to obtain a catalyst precursor. 1.5 g of phosphoric acid was dissolved in water and impregnated onto the catalyst precursor. The impregnated sample was dried at 120 °C for 12 hours and calcined at 500 °C for 6 hours to obtain catalyst B, which contained 1.5 wt% phosphoric acid, 1.5 wt% selenium dioxide, and 97 wt% silicon dioxide.
[0046] 10g of catalyst B was loaded into a fixed-bed reactor, and the catalyst temperature was raised to 350℃. An NH3-H2 mixture, with an H2 content of 15.0 vol%, was introduced into the reactor. Methyl acetate was then introduced into the reactor at a mass hourly space velocity (WHSV) of 5.0 h⁻¹. -1 The molar ratio of NH3-H2 mixture to methyl acetate was 20:1, and the reaction pressure was 0.5 MPa. After reaction, product collection and analysis showed that the conversion rate of methyl acetate was 98.1%, and among the ammonia-containing products, the selectivity for acetonitrile was 72.5%, and the selectivity for ethylamine was 26.7%.
[0047] Example 3
[0048] 10g of phosphorus pentoxide and 89.5g of alumina were mixed and shaped to obtain a catalyst precursor. 0.5g of oxalic acid was dissolved in water and impregnated onto the catalyst precursor. The impregnated sample was dried at 120℃ for 12 hours and calcined at 500℃ for 6 hours to obtain catalyst C, which contained 0.5wt% oxalic acid, 10wt% phosphorus pentoxide, and 89.5wt% alumina.
[0049] 10g of catalyst C was loaded into a fixed-bed reactor, and the catalyst temperature was raised to 350℃. An NH3-H2 mixture, with an H2 content of 5.0 vol%, was introduced into the reactor. Methyl acetate was then introduced into the reactor at a mass hourly space velocity (WHSV) of 1.0 h⁻¹. -1The molar ratio of NH3-H2 mixture to methyl acetate was 15:1, and the reaction pressure was 0.2 MPa. After reaction, product collection and analysis showed that the conversion rate of methyl acetate was 98.3%, and among the ammoniated products, the selectivity for acetonitrile was 89.6%, and the selectivity for ethylamine was 9.9%.
[0050] Example 4
[0051] 1 g of tellurium dioxide and 94.0 g of alumina were mixed and shaped to obtain a catalyst precursor. 5 g of phosphomolybdic acid was dissolved in water and impregnated onto the catalyst precursor. The impregnated sample was dried at 120 °C for 12 hours and calcined at 500 °C for 6 hours to obtain catalyst D, which contained 5 wt% phosphomolybdic acid, 1 wt% tellurium dioxide, and 94 wt% alumina.
[0052] 10g of catalyst D was loaded into a fixed-bed reactor, and the catalyst temperature was raised to 400℃. An NH3-H2 mixture, with an H2 content of 0.01 vol%, was introduced into the reactor. Butyl acetate was then introduced into the reactor at a mass hourly space velocity (WHSV) of 1.5 h⁻¹. -1 The molar ratio of NH3-H2 mixture to butyl acetate was 30:1, and the reaction pressure was 0.1 MPa. After reaction, product collection and analysis showed that the conversion rate of butyl acetate was 98.4%, and among the ammoniated products, the selectivity for acetonitrile was 97.7%, and the selectivity for ethylamine was 1.2%.
[0053] Example 5
[0054] 2g of tellurium dioxide and 94.0g of kaolin were mixed and shaped to obtain a catalyst precursor. 4g of phosphoric acid was dissolved in water and impregnated onto the catalyst precursor. The impregnated sample was dried at 120℃ for 12 hours and calcined at 500℃ for 6 hours to obtain catalyst E, which contained 4wt% phosphoric acid, 2wt% tellurium dioxide, and 94wt% kaolin.
[0055] 10g of catalyst E was loaded into a fixed-bed reactor, and the catalyst temperature was raised to 200℃. An NH3-H2 mixture, with an H2 content of 10.0 vol%, was introduced into the reactor. Methyl acetate was then introduced into the reactor at a mass hourly space velocity (WHSV) of 1.0 h⁻¹. -1 The molar ratio of NH3-H2 mixture to methyl acetate was 5:1, and the reaction pressure was 0.2 MPa. After reaction, product collection and analysis showed that the conversion rate of methyl acetate was 97.8%, and among the ammonia-containing products, the selectivity for acetonitrile was 87.7%, and the selectivity for ethylamine was 11.8%.
[0056] Example 6
[0057] 4g of phosphorus pentoxide was mixed with 92.0g of Y-type molecular sieve and shaped to obtain a catalyst precursor. 4g of oxalic acid was dissolved in water and impregnated onto the catalyst precursor. The impregnated sample was dried at 120℃ for 12 hours and calcined at 500℃ for 6 hours to obtain catalyst F, which contained 4wt% oxalic acid, 4wt% phosphorus pentoxide, and 92wt% Y-type molecular sieve.
[0058] 10g of catalyst F was loaded into a fixed-bed reactor, and the catalyst temperature was raised to 450℃. An NH3-H2 mixture, with an H2 content of 5.0 vol%, was introduced into the reactor. Methyl acetate was then introduced into the reactor at a mass hourly space velocity (WHSV) of 0.1 h⁻¹. -1 The molar ratio of NH3-H2 mixture to methyl acetate was 1:1, and the reaction pressure was 0.1 MPa. After reaction, product collection and analysis showed that the conversion rate of methyl acetate was 97.5%, and among the ammonia-containing products, the selectivity for acetonitrile was 91.6%, and the selectivity for ethylamine was 7.5%.
[0059] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and all fall within the scope of the technical solution.
Claims
1. A method for producing nitrile / amine products, characterized in that, Materials containing acetate are reacted with a catalyst in a mixed atmosphere of NH3 and H2 to produce nitrile / amine products. The catalyst comprises an acid, a non-metallic oxide, and a support; The acid is selected from at least one of heteropoly acids, phosphoric acid, and oxalic acid; the heteropoly acid is selected from at least one of phosphotungstic acid, phosphomolybdic acid, silicotungstic acid, and silicotomolybdic acid. The non-metallic oxide is selected from at least one of phosphorus pentoxide, selenium dioxide, and tellurium dioxide; The carrier is selected from at least one of alumina, silica, kaolin, and molecular sieve; the molecular sieve is selected from at least one of Y-type molecular sieve, ZSM-5 molecular sieve, ZSM-35 molecular sieve, and Beta molecular sieve. The nitrile / amine products are acetonitrile and ethylamine; The reaction is carried out in a reactor, which is selected from a fixed-bed reactor, a batch reactor, a moving-bed reactor, or a fluidized-bed reactor.
2. The method according to claim 1, characterized in that, The catalyst contains 1.0–5.0 wt% acid, 1.0–15.0 wt% non-metallic oxides, and 80.0–98.0 wt% support. The content is calculated as a percentage of the total mass of the catalyst.
3. The method according to claim 1, characterized in that, The acetate is selected from at least one of methyl acetate, ethyl acetate, propyl acetate, and butyl acetate.
4. The method according to claim 1, characterized in that, The conditions for the reaction are: The reaction temperature is 200~450°C o C, the reaction pressure is 0.1~1.0 MPa, the molar ratio of the NH3 and H2 mixture to the acetate is 1~30:1, and the mass hourly space velocity of the acetate is 0.1~5 h⁻¹. ~1 .
5. The method according to claim 1, characterized in that, In the mixture of NH3 and H2, the H2 content is 0.01~20%vol.