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WO2018163003A1 - Formaldéhyde à partir d'acide formique avec production d'oxyde métallique - Google Patents

Formaldéhyde à partir d'acide formique avec production d'oxyde métallique Download PDF

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Publication number
WO2018163003A1
WO2018163003A1 PCT/IB2018/051156 IB2018051156W WO2018163003A1 WO 2018163003 A1 WO2018163003 A1 WO 2018163003A1 IB 2018051156 W IB2018051156 W IB 2018051156W WO 2018163003 A1 WO2018163003 A1 WO 2018163003A1
Authority
WO
WIPO (PCT)
Prior art keywords
formaldehyde
formic acid
metal
transition metal
less
Prior art date
Application number
PCT/IB2018/051156
Other languages
English (en)
Inventor
Balamurugan VIDJAYACOUMAR
Khalid Al-Bahily
Sandro Gambarotta
Virginie PENEAU
Nicholas P. ALDERMAN
Original Assignee
Sabic Global Technologies B.V.
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 Sabic Global Technologies B.V. filed Critical Sabic Global Technologies B.V.
Publication of WO2018163003A1 publication Critical patent/WO2018163003A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/41—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenolysis or reduction of carboxylic groups or functional derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
    • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
    • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer

Definitions

  • the catalyst used in the process of producing hydrogen gas from formaldehyde can be any suitable catalyst known in the art, including, for example, a transition metal complex having a coordination bond between a transition metal and a leaving group, where the leaving group dissociates from the transition metal complex in response to light and/or the basic pH of the solution.
  • the catalyst can be further defined as an iron containing photocatalyst and/or a transition metal complex having a transition metal— halide bond.
  • the formic acid can be introduced into the reaction chamber in the form of an aqueous mixture.
  • the molar ratio of formic acid to water in the aqueous mixture can be about 100: 1, 50: 1, 25: 1, 10: 1, 9: 1, 8: 1, 7: 1, 6: 1, 5: 1, 4: 1, 3.5: 1, 3 : 1, 2.5: 1 2: 1, 1.5: 1, 1 : 1, 1 : 1.5, 1 :2, 1 :2.5, 1 :3, 1 :3.5, 1 :4, 1 :5, 1 :6, 1 :7, 1 :8, 1 :9, 1 : 10, 1 :25, 1 :50, or 1 : 100 or between any two of these values.
  • formate e.g., sodium formate
  • the production of hydrogen is in the homogeneous phase of the aqueous mixture.
  • the spent transition metal complex e.g., (M) a (Z n ) b
  • the spent transition metal complex can be a precipitate or be precipitated from the solution by addition of acid to increase the pH of the solution.
  • the resulting precipitate can be removed, or substantially removed, through known solid/liquid filtration methods (e.g., centrifugation, filtration, gravity settling, etc.).
  • the transition metal complex is not removed or is partially removed from the solution.
  • the formate (or formic acid), which is also dissolved in the solution, can then be reduced to formaldehyde using the methods described herein.
  • Table 1 summarizes experimental results for production of formaldehyde from formic acid using a Zn catalyst.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un procédé de production de formaldéhyde à partir d'acide formique. Le procédé selon la présente invention comprend l'obtention d'un mélange gazeux comprenant de l'acide formique et de la vapeur d'eau, et la mise en contact du mélange gazeux avec un catalyseur métallique dans une chambre de réaction dans des conditions suffisantes pour réduire l'acide formique en formaldéhyde et oxyder le métal en un oxyde métallique.
PCT/IB2018/051156 2017-03-08 2018-02-23 Formaldéhyde à partir d'acide formique avec production d'oxyde métallique WO2018163003A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762468483P 2017-03-08 2017-03-08
US62/468,483 2017-03-08

Publications (1)

Publication Number Publication Date
WO2018163003A1 true WO2018163003A1 (fr) 2018-09-13

Family

ID=61622629

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2018/051156 WO2018163003A1 (fr) 2017-03-08 2018-02-23 Formaldéhyde à partir d'acide formique avec production d'oxyde métallique

Country Status (1)

Country Link
WO (1) WO2018163003A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE185932C (de) * 1905-12-14 1907-06-07 Badische Anilin & Soda Fabrik Verfahren zur Darstellung von Aldehyden
US1648692A (en) 1926-01-20 1927-11-08 Mccarthy John Augustus Roofing shingle
WO2014130962A1 (fr) * 2013-02-24 2014-08-28 Dioxide Materials, Inc. Transformation de dioxyde de carbone en combustibles et en produits chimiques
US20160340186A1 (en) 2015-05-21 2016-11-24 Sabic Global Technologies B.V. LIGHT-SWITCHABLE CATALYST FOR THE HYDROGEN PRODUCTION FROM para-FORMALDEHYDE

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE185932C (de) * 1905-12-14 1907-06-07 Badische Anilin & Soda Fabrik Verfahren zur Darstellung von Aldehyden
US1648692A (en) 1926-01-20 1927-11-08 Mccarthy John Augustus Roofing shingle
WO2014130962A1 (fr) * 2013-02-24 2014-08-28 Dioxide Materials, Inc. Transformation de dioxyde de carbone en combustibles et en produits chimiques
US20160340186A1 (en) 2015-05-21 2016-11-24 Sabic Global Technologies B.V. LIGHT-SWITCHABLE CATALYST FOR THE HYDROGEN PRODUCTION FROM para-FORMALDEHYDE

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
HENRY JOHN HORSTMAN FENTON: "The reduction of carbon dioxide to formaldehyde in aqueous solution", JOURNAL OF THE CHEMICAL SOCIETY, TRANSACTIONS, vol. 91, 1907, pages 687 - 693, XP009504944, ISSN: 0368-1645, DOI: 10.1039/CT9079100687 *
N P ALDERMAN ET AL: "Supplementary Materials", DALTON TRANSACTIONS, 31 October 2016 (2016-10-31), XP055468894, Retrieved from the Internet <URL:http://www.rsc.org/suppdata/c6/dt/c6dt03658a/c6dt03658a1.pdf> [retrieved on 20180419] *
N. P. ALDERMAN ET AL: "Photochemical water splitting mediated by a C1 shuttle", DALTON TRANSACTIONS: THE INTERNATIONAL JOURNAL FOR INORGANIC, ORGANOMETALLIC AND BIOINORGANIC CHEMISTRY, 31 October 2016 (2016-10-31), GB, XP055324420, ISSN: 1477-9226, DOI: 10.1039/C6DT03658A *

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