WO2022117421A1 - Production d'acétonitrile à partir d'ammoniac et de méthanol - Google Patents

Production d'acétonitrile à partir d'ammoniac et de méthanol Download PDF

Info

Publication number
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
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
metal
process according
acetonitrile
mol
Prior art date
Application number
PCT/EP2021/082934
Other languages
English (en)
Inventor
Kasper Rode NIELSEN
Thoa Thi Minh NGUYEN
Philip MALCHO
Original Assignee
Topsoe A/S
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Topsoe A/S filed Critical Topsoe A/S
Publication of WO2022117421A1 publication Critical patent/WO2022117421A1/fr

Links

Classifications

    • 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.

Landscapes

  • 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

L'invention concerne un procédé et un catalyseur pour la production sélective d'acétonitrile comprenant la réaction d'un courant d'alimentation comprenant du méthanol et de l'ammoniac en présence d'un catalyseur bimétallique comprenant un support, et un premier métal choisi parmi Fe, Ni, Co et un second métal choisi parmi Sn, Zn, Ge, le premier métal étant présent en une quantité comprise entre 1 et 38 % en poids et le second métal en une quantité comprise entre 1 et 38 % en poids.
PCT/EP2021/082934 2020-12-02 2021-11-25 Production d'acétonitrile à partir d'ammoniac et de méthanol WO2022117421A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA202001366 2020-12-02
DKPA202001366 2020-12-02

Publications (1)

Publication Number Publication Date
WO2022117421A1 true WO2022117421A1 (fr) 2022-06-09

Family

ID=78821033

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2021/082934 WO2022117421A1 (fr) 2020-12-02 2021-11-25 Production d'acétonitrile à partir d'ammoniac et de méthanol

Country Status (1)

Country Link
WO (1) WO2022117421A1 (fr)

Citations (5)

* 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 (fr) * 2001-03-05 2009-11-25 Ineos Usa Llc Ammoxydation d'un melange d'alcools en un melange de nitriles, en particulier en acetonitrile et 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 (fr) * 2017-02-06 2019-12-11 Haldor Topsøe A/S Production d'acétonitrile et/ou de cyanure d'hydrogène à partir d'ammoniac et de méthanol

Patent Citations (5)

* 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 (fr) * 2001-03-05 2009-11-25 Ineos Usa Llc Ammoxydation d'un melange d'alcools en un melange de nitriles, en particulier en acetonitrile et 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 (fr) * 2017-02-06 2019-12-11 Haldor Topsøe A/S Production d'acétonitrile et/ou de cyanure d'hydrogène à partir d'ammoniac et de méthanol

Similar Documents

Publication Publication Date Title
US8003840B2 (en) Bismuth molybdate-based catalysts, method of preparing thereof and method of preparing 1,3-butadiene using thereof
US3226421A (en) Catalytic process for the preparation of nitriles
US3833638A (en) Ammoxidation of saturated hydrocarbons
KR20060132818A (ko) 메틸머캅탄의 제조방법
US20080248947A1 (en) Mixed metal oxide catalysts and catalytic processes for conversions of lower alkane hydrocarbons
CN112041299B (zh) 甲硫醇的制备方法
US4985581A (en) Catalyst and process for producing aromatic nitriles
US3956378A (en) Process for the manufacture of unsaturated aldehydes and acids from the corresponding olefins
US7919428B2 (en) Method of making mixed metal oxide catalysts for ammoxidation and/or oxidation of lower alkane hydrocarbons
EP0107639B1 (fr) Catalyseurs pour l'oxydation et l'ammoxydation d'alcools
CN105771964A (zh) 一种甲醇氨氧化制取氢氰酸的催化剂及其应用
Kalevaru et al. Synthesis of 2, 6-dichlorobenzonitrile from 2, 6-dichlorotoluene by gas phase ammoxidation over VPO catalysts
AU701924B2 (en) Process for the manufacture of acrylic acid from acrolein by a redox reaction and use of a solid mixed oxides composition as redox system in the said reaction
WO2022117421A1 (fr) Production d'acétonitrile à partir d'ammoniac et de méthanol
US11760718B2 (en) Production of acetonitrile and/or hydrogen cyanide from ammonia and methanol
US4162992A (en) Oxidation and ammoxidation catalysts
US3179694A (en) Process for the preparation of unsaturated nitriles
US3164628A (en) Method for preparing acrylonitrile
USRE31088E (en) Process for the manufacture of unsaturated aldehydes and acids from the corresponding olefins
US4388248A (en) Ammoxidation processes
US5770757A (en) Ammoxidation catalysts containing germanium to produce high yields of acrylonitrile
KR101988374B1 (ko) Ni/Al2O3 촉매상에서 에탄올의 환원성 아민화 반응에 의한 에틸아민 또는 아세토니트릴의 제조방법
Zhang et al. Study of oxide-based catalysts for the oxidative transformation of acetonitrile to acrylonitrile with CH4
USRE31364E (en) Oxidation and ammoxidation catalysis
US4055514A (en) Catalyst for preparation of 4-cyanothiazole

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21819448

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21819448

Country of ref document: EP

Kind code of ref document: A1