WO2017078507A2 - Stabilisation de catalyseur pour la préparation d'acide acétique et procédé de préparation d'amine tertiaire anhydre - Google Patents

Stabilisation de catalyseur pour la préparation d'acide acétique et procédé de préparation d'amine tertiaire anhydre Download PDF

Info

Publication number
WO2017078507A2
WO2017078507A2 PCT/KR2016/012759 KR2016012759W WO2017078507A2 WO 2017078507 A2 WO2017078507 A2 WO 2017078507A2 KR 2016012759 W KR2016012759 W KR 2016012759W WO 2017078507 A2 WO2017078507 A2 WO 2017078507A2
Authority
WO
WIPO (PCT)
Prior art keywords
carbon monoxide
catalyst
acetic acid
iodine
mmol
Prior art date
Application number
PCT/KR2016/012759
Other languages
English (en)
Korean (ko)
Other versions
WO2017078507A3 (fr
Inventor
홍장환
Original Assignee
홍장환
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
Priority claimed from KR1020150156185A external-priority patent/KR20170067909A/ko
Priority claimed from KR1020150156186A external-priority patent/KR20170067910A/ko
Application filed by 홍장환 filed Critical 홍장환
Publication of WO2017078507A2 publication Critical patent/WO2017078507A2/fr
Publication of WO2017078507A3 publication Critical patent/WO2017078507A3/fr

Links

Images

Classifications

    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • 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
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/22—Separation; Purification; Stabilisation; Use of additives
    • C07C231/24—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/03—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C233/00—Carboxylic acid amides
    • C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the rhodium catalyst commercialized by Monsanto in 1970, showed better efficiencies of 99% (methanol) and 85% (nitrogen monoxide) at 180-220 ° C / 30-40 atmospheres, but with a high water concentration of 14- There is a limit to operating at 15 wt%.
  • Celanese and Daicel also improved the Monsanto method by adding accelerators (LiI or NaI) to allow operation at a lower water content of 4-5 wt%.
  • the catalyst of Co 2 (CO) 8 used in US3407231 is unstable in air and difficult to handle.
  • the reaction time is 16 hours under conditions of 225 ° C / 138 atm and the catalyst efficiency (TOF: 0.7 TMA / mole cat / h) is very high. low.
  • Co 2 (CO) 8 is used as the accelerator for water, which is very low as catalytic activity (5 mole TMA / mole cat / h) at 250 ° C / 170 atmospheres.
  • JP46043527 uses a mercury (HgI 2 ) catalyst at 260 ° C and JP3275656A uses rhodium (RhCl 3 ) and methyliodine (MeI) at 270 ° C with very low yield and conversion (TMA) of 56% and 72%, respectively.
  • the catalytic efficiency (19 mole TMA / mole cat./h) is superior to the cobalt catalyst.
  • CN101003491A uses rhodium halide and iridium halogen compounds.
  • the trimethylamine is an expensive accelerator (MeI, Me 4 NI, I 2 ) due to the high content of water produced as a by-product in the commercial production process. Is consumed and a side reaction, acetic acid, is produced. Therefore, the method of simultaneously improving the above problems is to remove the water of trimethylamine to increase the conversion rate of carbon monoxide, use the anhydrous trimethylamine as a solvent and a reactant, and carbonylate trimethylamine by preventing the consumption of the accelerator. All of the above-described carbonylation methods of trimethyl not only use excessive promoters (MeI, Me 4 NI, I 2 ) over catalysts, but also use a reaction solvent that is difficult to remove (NMP, bp 202-204 ° C).
  • the carbon monoxide reacts and the pressure drops, the carbon monoxide is filled with ash to maintain the reactor pressure.
  • the reference material hexamethyldisiloxane, 20 l, 15.28 mg
  • GC-MS gas chromatography-mass spectrometer
  • Catalyst in the pressure reactor 500 ml Sus 316) ⁇ [ Rh (- I) (CO) 2] 2, 1.0 g, 2.57 mmol ⁇ , methyl iodide (MeI, 2.83 g, 20.0 mmol ), trimethylamine (Me 3 N, 1.0 ml, 0.63 g, 10.6 mmol), distilled water (0.36 g, 20.0 mmol), and methanol (methanol, 25 ml) were added thereto.
  • Fill the high-pressure reactor with carbon monoxide and remove it three times to replace it with carbon monoxide and pressurize to 7 atm.
  • the reactor is batched at 200 ° C. for 1-2 hours.
  • a 500 ml Sus 316 autoclave was used. Filling and removing the autoclave with carbon monoxide was repeated 3-4 times and replaced with carbon monoxide followed by catalyst (H 2 Irl 6 6H 2 O, 1.32 g, 2.57 mmol), methyl iodine (MeI, 2.34 g, 16.4 mmol), trimethyl Add amine (Me 3 N, 1.0 ml, 0.63 g, 10.6 mmol), distilled water (0.36 g, 20.0 mmol), and methanol (methanol, 25 ml). The reactor is batched for 24 hours at room temperature under 1 atmosphere of carbon monoxide. Replace with carbon monoxide and pressurize to 7 atm. The reactor is batched at 200 ° C.
  • the reference material hexamethyldisiloxane, 20 l, 15.28 mg
  • GC-MS gas chromatography-mass spectrometer
  • Example 3 A. Water removal method of trimethylamine and tertiary amine.
  • the gaseous trimethylamine is passed through a column of potassium hydroxide (KOH) and calcium oxide (CaO) or / and calcium chloride (CaCl 2 ) in one step, and then slowly through a molecular sieve (4 molecular sieve) in two steps. .
  • trimethylamine in which the cooling trap ( iso- propanol / dry ice, acetone /, or liquid nitrogen) was passed at an appropriate rate in three stages at 0-5 C in a storage container containing molecular sieve and To the carbonylation reaction.
  • the water content of trimethylamine was found to be 30 ppm at 4,500 ppm of Karl Fisher titrimetry of Metrohm.
  • a pressurized reactor 1000 ml Sus 316 was used and a donut-shaped Pyrex glass receiver could be installed at the top of the reactor and a cooling loop was installed to allow the coolant to flow thereon.
  • a rhodium catalyst RhCl 3 3H 2 O, 1.0 g, 3.79 mmol
  • CaO calcium oxide
  • carbon monoxide 350psi
  • heat heat to 275 C.
  • stirred for 2 hours.
  • the internal pressure drops to 65 atm during the reaction, carbon monoxide is charged to 68 atm.

Landscapes

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

Abstract

La présente invention concerne un procédé de synthèse efficace d'acide acétique en utilisant un catalyseur (rhodium, iridium, cobalt, nickel, palladium, platine ou ruthénium) qui est utilisé dans la préparation d'acide acétique et subit une réaction d'addition par oxydation avec un halogénure d'alkyle, la triméthylamine étant ajoutée de telle sorte que la stabilité du catalyseur ne soit pas limitée par la concentration d'humidité à l'intérieur d'un réacteur. La présente invention concerne en outre un procédé permettant d'utiliser une quantité extrêmement faible d'un promoteur halogène pour synthétiser le diméthylacétamide à haute efficacité catalytique sans consommation, en utilisant le même catalyseur et par carbonylation, sous pression de monoxyde de carbone, de triméthylamine anhydre avec l'humidité éliminée. La présente invention concerne en outre un procédé d'utilisation d'une quantité extrêmement faible d'un promoteur halogène pour synthétiser un amide tertiaire à haute efficacité catalytique sans consommation, par carbonylation, sous pression de monoxyde de carbone, d'une amine tertiaire anhydre avec l'humidité éliminée.
PCT/KR2016/012759 2015-11-06 2016-11-07 Stabilisation de catalyseur pour la préparation d'acide acétique et procédé de préparation d'amine tertiaire anhydre WO2017078507A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2015-0156176 2015-11-06
KR1020150156185A KR20170067909A (ko) 2015-11-06 2015-11-06 무수 상태에서 트리메틸아민의 카르보닐화 방법
KR1020150156186A KR20170067910A (ko) 2015-11-06 2015-11-06 무수 상태에서의 제3아민을 제2아미드로 카르보닐화하는 방법
KR20150156176 2015-11-06
KR10-2015-0156185 2015-11-06
KR10-2015-0156186 2015-11-06

Publications (2)

Publication Number Publication Date
WO2017078507A2 true WO2017078507A2 (fr) 2017-05-11
WO2017078507A3 WO2017078507A3 (fr) 2017-06-29

Family

ID=58662532

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2016/012759 WO2017078507A2 (fr) 2015-11-06 2016-11-07 Stabilisation de catalyseur pour la préparation d'acide acétique et procédé de préparation d'amine tertiaire anhydre

Country Status (1)

Country Link
WO (1) WO2017078507A2 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6056692B2 (ja) * 1977-09-29 1985-12-11 三菱瓦斯化学株式会社 カルボン酸及び／又はそのエステル類の製造方法
US5281751A (en) * 1983-12-02 1994-01-25 Union Carbide Chemicals And Plastics Company Inc. Synergistic production of carboxylic acids from alcohols
EP0185823B1 (fr) * 1984-12-28 1988-03-23 E.I. Du Pont De Nemours And Company Diméthylacétamide par carbonylisation de triméthylamine
EP2189441A1 (fr) * 2008-11-21 2010-05-26 Taminco Procédé de préparation d'amines secondaires par carbonylation d'amines tertiares correspondants

Also Published As

Publication number Publication date
WO2017078507A3 (fr) 2017-06-29

Similar Documents

Publication Publication Date Title
US4375566A (en) Process for producing ortho-alkylated phenols from anisoles
CN101671370A (zh) 离子液体型的铁(ⅲ)配合物及其应用
EP2640714A1 (fr) Procédé de préparation d'esters d'acide 2-oxo-[1,3]dioxolane-4-carboxylique
CA1056840A (fr) Oxydation de methylamines substituees en n pour l'obtention de formamides substitues en n
WO2017078507A2 (fr) Stabilisation de catalyseur pour la préparation d'acide acétique et procédé de préparation d'amine tertiaire anhydre
CN108276356B (zh) 3,5-二取代噻唑烷-2-硫酮类化合物制备方法
CN114478351B (zh) 一种合成α-烷基取代吲哚-3-甲醛类化合物的方法
JP2512391B2 (ja) ブタジエンのヒドロキシカルボニル化法
CN109535029B (zh) 一种2,4,4,4-四氯丁腈的合成方法
JP2000281630A (ja) 非対称ジアルキルカーボネートの製造方法
US5053541A (en) Process for the preparation of n-allyl-meta-trifluoromethyl aniline
JP2650100B2 (ja) エチリデンジアセテートの製造方法
US20120123136A1 (en) Process for the preparation of 2-oxo-[1,3] dioxolane-4-carboxylic acid esters
KR20170067909A (ko) 무수 상태에서 트리메틸아민의 카르보닐화 방법
KR101453390B1 (ko) Azo기로 공유 결합된 다공성 유기 고분자 및 그 제조방법
KR20170067910A (ko) 무수 상태에서의 제3아민을 제2아미드로 카르보닐화하는 방법
CN111440211B (zh) 一种一锅法催化合成马拉硫磷的方法
CN115125553B (zh) 一种醇的电化学合成方法
JPH08151346A (ja) ケトマロン酸の製造方法
JP3541448B2 (ja) アセトアミドの製造方法
JPH062716B2 (ja) 芳香族第二級アミノ化合物の製造方法
JPH11309377A (ja) 触媒用担体及び金属錯体触媒
JP2629272B2 (ja) ２−メトキシ−６−メチルアミノピリジンの製造方法
JPH0427971B2 (fr)
CN117430494A (zh) 一种2-羟基四氢呋喃制备丁二酸的合成方法

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: 16862522

Country of ref document: EP

Kind code of ref document: A2

NENP Non-entry into the national phase in:

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16862522

Country of ref document: EP

Kind code of ref document: A2