WO2022117421A1 - Production of acetonitrile from ammonia and methanol - Google Patents

Production of acetonitrile from ammonia and methanol Download PDF

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WO2022117421A1
WO2022117421A1 PCT/EP2021/082934 EP2021082934W WO2022117421A1 WO 2022117421 A1 WO2022117421 A1 WO 2022117421A1 EP 2021082934 W EP2021082934 W EP 2021082934W WO 2022117421 A1 WO2022117421 A1 WO 2022117421A1
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catalyst
metal
process according
acetonitrile
mol
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French (fr)
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Kasper Rode NIELSEN
Thoa Thi Minh NGUYEN
Philip MALCHO
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Topsoe A/S
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C255/03—Mononitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • Embodiments of the invention generally relate to a process for selectively producing a product gas comprising acetonitrile from a feed stream comprising ammonia and methanol in the presence of a solid catalyst and a catalyst for catalyzing reactions producing selectively acetonitrile from a feed stream comprising ammonia and methanol.
  • Aliphatic nitriles are important starting materials for polymers as well as for the synthesis of e.g., pharmaceuticals and pesticides. Nitriles are additionally good solvents for both polar and nonpolar solutes.
  • Nitriles may be produced by reaction of nitrogen-free precursors (such as alkanes, olefins, alcohols, aldehydes, or acids) with ammonia.
  • nitrogen-free precursors such as alkanes, olefins, alcohols, aldehydes, or acids
  • gas phase reaction of olefins with ammonia in the presence of oxygen (ammoxidation) and oxidation catalysts has attained the greatest industrial importance for the production of acrylonitrile from propene and methacrylonitrile from isobutene.
  • This process is known as the SOHIO process.
  • the vast majority of acetonitrile is produced as a by-product of the SOHIO process.
  • the SOHIO process is an ammoxidation of propylene (or more recently propane) to yield acrylonitrile.
  • the process takes place in a fluidized bed at 400-510 °C and BO- OO kPa gauge.
  • the catalysts employed are si
  • Acetonitrile is only available as a by-product from the synthesis of acrylonitrile. So far there is no commercial process dedicated for producing acetonitrile.
  • the ratio of hydrogen cyanide by-product and acetonitrile in the product stream can be controlled by the ratio of a first metal and a second metal in a bimetallic catalyst. This is advantageous in that it ensures a minimum production of hydrogen cyanide and syngas by-products.
  • An aspect of the invention provides a process for producing selectively acetonitrile comprising reacting a feed stream comprising methanol and ammonia in the presence of a bimetallic catalyst comprising a support, and a first metal selected from Fe, Ni, Co and a second metal selected from Sn, Zn, Ge, wherein the first metal is present in an amount of between 1 and 35 weight %.
  • the support comprises oxide of aluminum or spinel of aluminum.
  • the first metal is Co and the second metal is Sn.
  • the mol ratio of the first and the second metal is preferably between 0.5 and 5.
  • the molar ratio of Co/Sn is between 2 and 3 and calcining the catalyst in a hydrogen containing atmosphere .
  • the molar ratio of Co/Sn is 1 and calcining the catalyst in air.
  • the mol ratio of methanol to ammonia in the feed to the reactor is between 0.1 and 10.
  • the feed stream is reacted at a temperature of between 400 and 700 °C.
  • the bimetallic catalyst is subjected to a heat treatment in a hydrogen containing atmosphere prior to the reacting of the feed stream, preferably at a temperature of between 400 and 1000 0 C.
  • the catalyst has been subjected to a heat treatment in an atmosphere containing oxygen prior to the reacting of the feed stream, preferably at a temperature of between 400 and 1000 °C.
  • the process according to the invention is carried out at ambient pressure or higher.
  • Another aspect of the invention relates to a catalyst for catalyzing reactions producing selectively acetonitrile from a feed stream comprising ammonia and methanol, the catalyst comprising a support, a first metal and a second metal on the support, wherein the first metal is Fe, Ru or Co, and where the second metal is Sn, Zn or Ge and wherein the first metal is present in an amount of between 1 and 35 weight %.
  • the support comprises oxide of aluminum or spinel of aluminum.
  • the first metal is preferably Co and the second metal is Sn, the mol ratio of the first and the second metal is preferably between 0.5 and 5.
  • the catalyst is subjected to a heat treatment in an atmosphere containing hydrogen, preferably at a temperature between 400 and 1000 0 C.
  • the catalyst is subjected to a heat treatment in an atmosphere containing oxygen, preferably a temperature between 400 and 1000 0 C.
  • the final catalyst had a Co content of 4.75 wt% and an Sn content of 13.8 wt%, giving a Co/Sn ratio of 0.69 mol/mol.
  • This catalyst was denoted Co5Snl5-6O.
  • the final catalyst had a Co content of 4.65 wt% and an Sn content of 9.31 wt%, giving a Co/Sn ratio of 1.01 mol/mol.
  • This catalyst was denoted Co5SnlO-60.
  • the final catalyst had a Co content of 4.83 wt% and an Sn content of 5.24 wt%, giving a Co/Sn ratio of 1.84 mol/mol.
  • This catalyst was denoted Co5Sn5-6O.
  • the final catalyst had a Co content of 4.97 wt% and an Sn content of 3.66 %, giving a Co/Sn ratio of 2.66 mol/mol.
  • This catalyst was denoted Co5Sn3-6O.
  • examples 5-8 the same raw materials as in examples 1-4 were used. However, instead of calcining 20 g at 600 °C air, 4 g of the materials were treated at 600 °C for 2 hours in a flowing atmosphere comprising 2 vol% H2 in Ar.
  • Examples 9-12 have been prepared the same way as in examples 5-8 but instead of treating the catalysts at 600 °C in 2 vol% H2 in Ar for 2 hours, the catalysts were treated at 800°C in 2 vol% H2 in Ar for 2 hours.
  • the tests were performed in three steps each having a total flow of reactants of 50 Nml/min and a temperature of 550 °C.
  • the first step had a methanokammonia molar ratio of 1.4
  • the second step had a methanokammonia molar ratio of 2.6
  • the third step had a methanokammonia molar ratio of 3.8 - with N2 being added as an inert gas.
  • Fig.l summarizes the results from the second step for the 4 catalysts described in examples 1-4.
  • Fig.2 shows the effluent concentrations of HCN and acetonitrile for Co5SnlO-60 and Co5Sn5-6O, respectively, for each step in the test procedure described in example 13.
  • Reaction conditions Amount of catalyst: 300 mg, total flow: 50 Nml/min (N2, NH3 and CH3OH), temperature: 550 °C.
  • the catalysts prepared according to examples 5-8 were heated to 550 °C in 50 Nml/min N2 and tested similarly to the procedure described in example 13.
  • ACN acetonitrile
  • HCN hydrogen cyanide
  • the catalysts prepared according to examples 9-12 were heated to 550 °C in 50 Nml/min N2 and tested similarly to the procedure described in example 13.
  • the trends are the same as for the catalysts treated at 600 °C in Fh/Ar but this time the acetonitrile concentration was higher for all the samples and this was also true for the total nitrile concentration.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Process and catalyst for producing selectively acetonitrile comprising reacting a feed stream comprising methanol and ammonia in presence of a bimetallic catalyst com-prising a support, and a first metal selected from Fe, Ni, Co and a second metal se-lected from Sn, Zn, Ge, wherein the first metal is present in an amount of between 1 and 38 weight % and the second metal in an amount of between 1 and 38 weight %.

Description

Title: Production of acetonitrile from ammonia and methanol
FIELD OF THE INVENTION
Embodiments of the invention generally relate to a process for selectively producing a product gas comprising acetonitrile from a feed stream comprising ammonia and methanol in the presence of a solid catalyst and a catalyst for catalyzing reactions producing selectively acetonitrile from a feed stream comprising ammonia and methanol.
BACKGROUND
Aliphatic nitriles are important starting materials for polymers as well as for the synthesis of e.g., pharmaceuticals and pesticides. Nitriles are additionally good solvents for both polar and nonpolar solutes.
Nitriles may be produced by reaction of nitrogen-free precursors (such as alkanes, olefins, alcohols, aldehydes, or acids) with ammonia. Gas phase reaction of olefins with ammonia in the presence of oxygen (ammoxidation) and oxidation catalysts has attained the greatest industrial importance for the production of acrylonitrile from propene and methacrylonitrile from isobutene. This process is known as the SOHIO process. The vast majority of acetonitrile is produced as a by-product of the SOHIO process. The SOHIO process is an ammoxidation of propylene (or more recently propane) to yield acrylonitrile. The process takes place in a fluidized bed at 400-510 °C and BO- OO kPa gauge. The catalysts employed are silica-supported molybdates containing elements such as Bi, P, Co, Ni, Fe and K.
In the process for producing acrylonitrile, high selectivity remains a challenge and hydrogen cyanide and acetonitrile, among others, are also produced as by-products. Since acrylonitrile is mainly used for producing diverse polymer types, the contents of these by-products are required to be in the ppm range to ensure the polymer quality. The separation of the by-products requires high energy consumption and is thus costly.
Acetonitrile is only available as a by-product from the synthesis of acrylonitrile. So far there is no commercial process dedicated for producing acetonitrile.
It is thus an object of the invention to provide a process and a catalyst for catalyzing the selective production of a product gas rich in acetonitrile from ammonia and methanol.
We have observed that the ratio of hydrogen cyanide by-product and acetonitrile in the product stream can be controlled by the ratio of a first metal and a second metal in a bimetallic catalyst. This is advantageous in that it ensures a minimum production of hydrogen cyanide and syngas by-products.
SUMMARY OF THE INVENTION
An aspect of the invention provides a process for producing selectively acetonitrile comprising reacting a feed stream comprising methanol and ammonia in the presence of a bimetallic catalyst comprising a support, and a first metal selected from Fe, Ni, Co and a second metal selected from Sn, Zn, Ge, wherein the first metal is present in an amount of between 1 and 35 weight %..
In an embodiment of the invention, the support comprises oxide of aluminum or spinel of aluminum.
Preferably, the first metal is Co and the second metal is Sn. The mol ratio of the first and the second metal is preferably between 0.5 and 5.
Depending on the calcination procedure a high yield of acetonitrile is obtained at a Co/Sn molar ratio of 1, when calcining the catalyst in air.
When calcining the catalyst in a hydrogen containing atmosphere, a high yield of acetonitrile is obtained at a Co/Sn molar ration of between 2 and 3.
Thus, in a preferred embodiment, the molar ratio of Co/Sn is between 2 and 3 and calcining the catalyst in a hydrogen containing atmosphere .
In a further embodiment, the molar ratio of Co/Sn is 1 and calcining the catalyst in air.
In a further embodiment, the mol ratio of methanol to ammonia in the feed to the reactor is between 0.1 and 10.
In still an embodiment, the feed stream is reacted at a temperature of between 400 and 700 °C.
In a further embodiment, the bimetallic catalyst is subjected to a heat treatment in a hydrogen containing atmosphere prior to the reacting of the feed stream, preferably at a temperature of between 400 and 10000 C.
In another embodiment the catalyst has been subjected to a heat treatment in an atmosphere containing oxygen prior to the reacting of the feed stream, preferably at a temperature of between 400 and 1000 °C.
The process according to the invention is carried out at ambient pressure or higher.
Another aspect of the invention relates to a catalyst for catalyzing reactions producing selectively acetonitrile from a feed stream comprising ammonia and methanol, the catalyst comprising a support, a first metal and a second metal on the support, wherein the first metal is Fe, Ru or Co, and where the second metal is Sn, Zn or Ge and wherein the first metal is present in an amount of between 1 and 35 weight %.
In an embodiment, the support comprises oxide of aluminum or spinel of aluminum. In still an embodiment, the first metal is preferably Co and the second metal is Sn, the mol ratio of the first and the second metal is preferably between 0.5 and 5.
In a further embodiment, the catalyst is subjected to a heat treatment in an atmosphere containing hydrogen, preferably at a temperature between 400 and 10000 C. In another embodiment, the catalyst is subjected to a heat treatment in an atmosphere containing oxygen, preferably a temperature between 400 and 10000 C.
Examples
EXAMPLE 1
To prepare a catalyst with the nominal Co content of 5 wt%, Sn content of 15 wt% and Co/Sn molar ratio of 0.67, 98.53 g of AI2O3 spheres were impregnated with a solution comprising 32.88 g CofNOsh- HzO and 38.23 g SnCl2-2H2O using the incipient wetness technique. The resulting material was then dried in a drying oven at 100 °C overnight. Subsequently, 20 g was placed in a crucible and calcined in stagnant air at 600 °C (the holding time was 2 hours).
The final catalyst had a Co content of 4.75 wt% and an Sn content of 13.8 wt%, giving a Co/Sn ratio of 0.69 mol/mol. This catalyst was denoted Co5Snl5-6O.
EXAMPLE 2
To prepare a catalyst with the nominal Co content of 5 wt%, Sn content of 10 wt% and Co/Sn molar ratio of 1, 98.53 g of AI2O3 spheres were impregnated with a solution comprising 30.26 g Co(NO3)2-6H2O and 23.46 g SnCl2-2H2O using the incipient wetness technique. The resulting material was then dried in a drying oven at 100 °C overnight. Subsequently, 20 g was placed in a crucible and calcined in stagnant air at 600 °C (the holding time was 2 hours).
The final catalyst had a Co content of 4.65 wt% and an Sn content of 9.31 wt%, giving a Co/Sn ratio of 1.01 mol/mol. This catalyst was denoted Co5SnlO-60.
EXAMPLE 3
To prepare a catalyst with the nominal Co content of 5 wt%, Sn content of 5 wt% and Co/Sn molar ratio of 2, 98.53 g of AI2O3 spheres were impregnated with a solution comprising 28.03 g CofNChh-OHzO and 10.87 g SnCl2-2H2O using the incipient wetness technique. The resulting material was then dried in a drying oven at 100 °C overnight. Subsequently, 20 g was placed in a crucible and calcined in stagnant air at 600 °C (the holding time was 2 hours).
The final catalyst had a Co content of 4.83 wt% and an Sn content of 5.24 wt%, giving a Co/Sn ratio of 1.84 mol/mol. This catalyst was denoted Co5Sn5-6O.
EXAMPLE 4
To prepare a catalyst with the nominal Co content of 5 wt%, Sn content of 3 wt% and Co/Sn molar ratio of 3, 98.53 g of AI2O3 spheres were impregnated with a solution comprising 27.36 g Co(NO3)2-6H2O and 7.08 g SnCl2-2H2O using the incipient wetness technique. The resulting material was then dried in a drying oven at 100 °C overnight. Subsequently, 20 g was placed in a crucible and calcined in stagnant air at 600 °C (the holding time was 2 hours).
The final catalyst had a Co content of 4.97 wt% and an Sn content of 3.66 %, giving a Co/Sn ratio of 2.66 mol/mol. This catalyst was denoted Co5Sn3-6O. EXAMPLES 5-8
In examples 5-8, the same raw materials as in examples 1-4 were used. However, instead of calcining 20 g at 600 °C air, 4 g of the materials were treated at 600 °C for 2 hours in a flowing atmosphere comprising 2 vol% H2 in Ar.
These catalysts were denoted Co5Snl5-6H, Co2SnlO-6H, Co5Sn5-6H and Co5Sn3-6H, respectively. The Co and Sn contents as well as their molar ratios were:
- Co5Snl5-6H: Co = 5.13 wt%, Sn = 11.9 wt%, Co/Sn = 0.87 mol/mol
- Co5SnlO-6H: Co = 4.74 wt%, Sn = 8.42 wt%, Co/Sn = 1.13 mol/mol
Co5Sn5-6H: Co = 4.73 wt%, Sn = 5.48 wt%, Co/Sn = 1.74 mol/mol
Co5Sn3-6H: Co = 4.88 wt%, Sn = 3.66 wt%, Co/Sn = 2.66 mol/mol
EXAMPLES 9-12
Examples 9-12 have been prepared the same way as in examples 5-8 but instead of treating the catalysts at 600 °C in 2 vol% H2 in Ar for 2 hours, the catalysts were treated at 800°C in 2 vol% H2 in Ar for 2 hours.
These catalysts were denoted Co5Snl5-8H, Co2SnlO-8H, Co5Sn5-8H and Co5Sn3-8H, respectively. The Co and Sn contents as well as their molar ratios were:
Co5Snl5-8H: Co = 5.26 wt%, Sn = 10.1 wt%, Co/Sn = 1.05 mol/mol
- Co5SnlO-8H: Co = 4.95 wt%, Sn = 7.47 wt%, Co/Sn = 1.33 mol/mol Co5Sn5-8H: Co = 4.79 wt%, Sn = 4.65 wt%, Co/Sn = 2.03 mol/mol Co5Sn3-8H: Co = 4.91 wt%, Sn = 3.16 wt%, Co/Sn = 3.05 mol/mol EXAMPLE 13
For the catalytic test of the catalysts, 300 mg of material was crushed down to a sieve fraction of 300-600 and loaded into a u-tube quartz reactor. Before initiating the acetonitrile synthesis, each catalyst was treated in an atmosphere of 10 vol% H2 in N2 at 800 °C for 3 hours (total flow 100 Nml/min).
The tests were performed in three steps each having a total flow of reactants of 50 Nml/min and a temperature of 550 °C. The first step had a methanokammonia molar ratio of 1.4, the second step had a methanokammonia molar ratio of 2.6 and the third step had a methanokammonia molar ratio of 3.8 - with N2 being added as an inert gas. Fig.l summarizes the results from the second step for the 4 catalysts described in examples 1-4. The effluent molar concentrations of hydrogen cyanide (HCN) and acetonitrile (ACN) from the reaction between ammonia and methanol over Co-Sn/A^Ch catalysts are depicted. Reaction conditions: Amount of catalyst: 300 mg, total flow: 50 Nml/min, gas composition: N2/NH3/CH3OH = 9/1/2.6 mol/mol/mol, temperature: 550 °C.
The results show that the most active acetonitrile catalyst was the one denoted Co5SnlO-60. However, it is also evident that the concentrations of hydrogen cyanide decrease with the Sn content to a point where virtually no hydrogen cyanide by-product is produced for the catalysts with a molar ratio of Co and Sn of 2 and 3. The acetonitrile concentration seems to have a maximum within the tested ranges of Co/Sn.
EXAMPLE 14
In another example of the use of the process and the catalysts, the catalysts were tested using the same procedure as in example 5. Fig.2 shows the effluent concentrations of HCN and acetonitrile for Co5SnlO-60 and Co5Sn5-6O, respectively, for each step in the test procedure described in example 13. Reaction conditions: Amount of catalyst: 300 mg, total flow: 50 Nml/min (N2, NH3 and CH3OH), temperature: 550 °C.
In the Figure, it can be seen that the catalysts produce a higher acetonitrile (ACN) concentration at higher methanol/ammonia ratios. It is also clear that Co5Sn5-6O is less active for acetonitrile production but conversely produces only trace amounts of hydrogen cyanide.
EXAMPLE 15
The catalysts prepared according to examples 5-8 were heated to 550 °C in 50 Nml/min N2 and tested similarly to the procedure described in example 13.
Fig.3 shows data from the second step of the test (Reaction conditions: Amount of catalyst: 300 mg, total flow: 50 Nml/min, gas composition: N2/NH3/CH3OH = 9/1/2.6 mol/mol/mol, temperature: 550 °C). Evidently, the concentrations of acetonitrile (ACN) and hydrogen cyanide (HCN) are highly governed by the ratio of Co and Sn in the catalyst. It also shows that this preparative procedure gives a catalyst which produces more hydrogen cyanide compared to the catalysts prepared by calcining in air. Unlike the air treated catalysts, this series have a maximum acetonitrile concentration for the sample with 5 wt% Sn (or Co/Sn = 1.74) and not for the catalyst closer to Co/Sn = 1.
EXAMPLE 16
The catalysts prepared according to examples 9-12 were heated to 550 °C in 50 Nml/min N2 and tested similarly to the procedure described in example 13.
Fig.4 shows data from the second step of the test (Reaction conditions: Amount of catalyst: 300 mg, total flow: 50 Nml/min, gas composition: N2/NH3/CH3OH = 9/1/2.6 mol/mol/mol, temperature: 550 °C). The trends are the same as for the catalysts treated at 600 °C in Fh/Ar but this time the acetonitrile concentration was higher for all the samples and this was also true for the total nitrile concentration.

Claims

9 Claims
1. Process for producing selectively acetonitrile comprising reacting a feed stream comprising methanol and ammonia in presence of a bimetallic catalyst comprising a support, and a first metal selected from Fe, Ni, Co and a second metal selected from Sn, Zn, Ge, wherein the first metal is present in an amount of between 1 and 35 weight %.
2. The process according to claim 1, wherein the support comprises oxide of aluminum or spinel of aluminum.
3. The process according to any one of claims 1 to 2, wherein the first metal is Co and the second metal is Sn.
4. The process according to claim 3, wherein the mol ratio of the first and the second metal is between 0.5 and 5.
5. The process according to claim 3, wherein the molar ratio of Co/Sn between 2 and 3 and wherein the catalyst is calcined in a hydrogen containing atmosphere .
6. The process according to claim 3, wherein the molar ratio of Co/Sn is 1 and wherein the catalyst is calcined in air.
7. The process according to any one of claims 1 to 6, wherein the mol ratio of methanol to ammonia is between 0.1 and 10.
8. The process according to any one of claims 1 to 7, wherein the feed stream is reacted at a temperature of between 400 and 700 °C.
9. The process according to any one of claims 1 to 8, wherein the bimetallic catalyst is subjected to heat treatment in a hydrogen containing atmosphere prior to the reacting of the feed stream.
10. The process according to claim 9, wherein the heat treatment is carried out at a temperature of between 400 and 1000 °C.
11. The process according to any one of claims 1 to 8, wherein the bimetallic catalyst is subjected to a heat treatment in an atmosphere containing oxygen prior to the reacting of the feed stream.
12. The process according to claim 12, wherein the heat treatment is carried out at a temperature of between 400 and 10000 C.
13. Catalyst for catalyzing reactions producing selectively acetonitrile from a feed stream comprising ammonia and methanol, the catalyst comprising a support, a first metal and a second metal on the support, wherein the first metal is Fe, Ru or Co, and where the second metal is Sn, Zn or Ge and wherein the first metal is present in an amount of between 1 and 35 weight %.
14. The catalyst according to claim 11, wherein the support comprises an oxide of aluminum or a spinel of an oxide of aluminum.
15. The catalyst according to claim 11 or 12, wherein the first metal is Co and the second metal is Sn.
16. The catalyst according to claim 13, wherein the molar ratio of Co and Sn is between 0.5 and 5. 11
17. The catalyst according to any one of claims 13 to 16, wherein the catalyst is subjected to a heat treatment in an atmosphere containing hydrogen.
18. The catalyst according to claim 17, wherein the heat treatment is carried out at a temperature of between 400 and 10000 C.
19. The catalyst according to any one of claims 13 to 16, wherein the catalyst is subjected to a heat treatment in an atmosphere containing oxygen.
20. The catalyst according to claim 19, wherein the heat treatment is carried out at a temperature of between 400 and 10000 C.
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GB792575A (en) * 1954-06-25 1958-04-02 Union Carbide Corp Production of nitriles
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US20140148610A1 (en) * 2012-11-26 2014-05-29 Ineos Usa Llc Pre calcination additives for mixed metal oxide ammoxidation catalysts
US20190009252A1 (en) * 2016-01-09 2019-01-10 Ascend Performance Materials Operations Llc Catalyst compositions and process for direct production of hydrogen cyanide in an acrylonitrile reactor feed stream
EP3577073A1 (en) * 2017-02-06 2019-12-11 Haldor Topsøe A/S Production of acetonitrile and/or hydrogen cyanide from ammonia and methanol

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB792575A (en) * 1954-06-25 1958-04-02 Union Carbide Corp Production of nitriles
EP1366019B1 (en) * 2001-03-05 2009-11-25 Ineos Usa Llc Ammoxidation of a mixture of alcohols to a mixture of nitriles to acetonitrile and hcn
US20140148610A1 (en) * 2012-11-26 2014-05-29 Ineos Usa Llc Pre calcination additives for mixed metal oxide ammoxidation catalysts
US20190009252A1 (en) * 2016-01-09 2019-01-10 Ascend Performance Materials Operations Llc Catalyst compositions and process for direct production of hydrogen cyanide in an acrylonitrile reactor feed stream
EP3577073A1 (en) * 2017-02-06 2019-12-11 Haldor Topsøe A/S Production of acetonitrile and/or hydrogen cyanide from ammonia and methanol

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