EP4499596A1 - Procédé photochimique de production d'alcools - Google Patents

Procédé photochimique de production d'alcools

Info

Publication number
EP4499596A1
EP4499596A1 EP23716194.8A EP23716194A EP4499596A1 EP 4499596 A1 EP4499596 A1 EP 4499596A1 EP 23716194 A EP23716194 A EP 23716194A EP 4499596 A1 EP4499596 A1 EP 4499596A1
Authority
EP
European Patent Office
Prior art keywords
photosensitizer
photochemical
light
hydrogen source
reaction
Prior art date
Legal status (The legal status 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 status listed.)
Pending
Application number
EP23716194.8A
Other languages
German (de)
English (en)
Inventor
Bettina BAUMGARTNER
Alina MEINDL
Bernhard Lendl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fachhochschule Salzburg GmbH
Original Assignee
Fachhochschule Salzburg GmbH
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 Fachhochschule Salzburg GmbH filed Critical Fachhochschule Salzburg GmbH
Publication of EP4499596A1 publication Critical patent/EP4499596A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C07C29/15—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 oxides of carbon exclusively
    • 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
    • C07C29/15—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 oxides of carbon exclusively
    • C07C29/151—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/1512—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by reaction conditions
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/123—Ultraviolet light
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/127—Sunlight; Visible light
    • 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
    • C07C29/15—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 oxides of carbon exclusively
    • C07C29/151—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/152—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 oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the reactor used
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R19/00—Arrangements for measuring currents or voltages or for indicating presence or sign thereof
    • G01R19/25—Arrangements for measuring currents or voltages or for indicating presence or sign thereof using digital measurement techniques
    • G01R19/2513—Arrangements for monitoring electric power systems, e.g. power lines or loads; Logging
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/04—Methanol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/08—Ethanol

Definitions

  • the present invention relates to a photochemical process for producing alcohols from CO2 and water.
  • the invention further relates to the use of a photosensitizer for the photochemical provision of alcohols.
  • the invention relates to a system for the photochemical reduction of CO2 to obtain alcohols.
  • Alcohols are among the most commonly produced organic chemicals. They are important starting materials and intermediate products in the chemical industry and can be used as energy sources. The simplest alcohols are methanol and ethanol. With the help of fuel cells, methanol can provide electrical energy. Alcohol can also act as a chemical (long-term) storage for solar and wind energy by using solar and wind energy to reduce CO2 (power to liquid).
  • Ci or C2 compounds include a light source, a photocatalyst, and an electron donor that is consumed in the reaction (Song et al.).
  • Water is the simplest electron donor, although alternative electron donors are also used as sacrificial reagents.
  • known processes for the photoreduction of CO2 require a semiconductor, metal semiconductor or semiconductor/metal hybrid catalyst.
  • US 10,047,027 B1 describes a process for forming methanol by exposing a reaction mixture comprising H2O, CO2 and a semiconductor photocatalyst to UV light. The action of light creates an electron-hole pair in the semiconductor photocatalyst. Holes in the conduction band of the semiconductor then oxidize water to O2 and H + . H + , electrons of the valence band and CO2 react to form methanol and H2O.
  • US 8,986,511 B1 describes a similar process in which CO2 is reduced in the presence of H2O and a photosensitizer and in which semiconductors are used. Catalysts used in the processes described are complex to produce and contain metals that are classified as harmful to health, which also represent valuable resources. For example, the same materials can also be used in solar cells, but cannot be used there due to their toxicity and cost reasons.
  • WO 2017/091857 A1 describes a process for producing hydrocarbons such as methane or substituted hydrocarbons such as methanol.
  • a catalyst is brought into contact with H2O and CO2 in order to catalyze (i) the splitting of H2O into O2 and H2 and (ii) the reaction of H2 with CO2.
  • the catalyst has Au and the very oxidation-sensitive Ru in a nanocluster on a support.
  • the reaction conditions are comparatively drastic (high pressure of 20 Torr H2O, Ar atmosphere 280 Torr). The system appears vulnerable to contamination and is resource intensive in several ways.
  • WO 2013/175311 A2 describes a process for producing methanol from CO2 in the presence of light, a ruthenium polypyridine catalyst and a co-catalyst.
  • the ruthenium catalyst is reduced under the influence of light, thereby accepting electrons from (alternative) electron donors.
  • the reduced catalyst forms an adduct with CO2 and H + and is oxidized in the process.
  • the [-CO2-H] adduct is taken over by a co-catalyst and with its help is further reduced to the end product.
  • the oxidized catalyst must be reduced again.
  • the co-catalyst described contains Co.
  • JPS5988436 A describes the use of metal-porphyrin complexes to produce methanol from CO.
  • the metallaporphyrin complex is oxidized and then has to be reduced again.
  • a Pt catalyst is used as a co-catalyst and H2.
  • the process uses metals as catalytically active centers, including an expensive co-catalyst.
  • the object of the present invention is therefore to provide a simplified system for the photoreduction of CO2, with which the use of possibly toxic and rare metals can be avoided, and with which specific short-chain metals can be produced selectively with high yield in the simplest, most resource-saving and economical possible way Allow alcohols (Ci to C10, preferably ethanol or methanol) to be produced.
  • the inventors have surprisingly found that a selective reduction of CO2 to alcohol can be carried out with the aid of light, a photosensitizer capable of converting oxygen (O2) into reactive oxygen species in the presence of light, and a hydrogen source.
  • the aforementioned object is achieved according to the invention by a photochemical process for producing alcohol from CO2 and a hydrogen source, in which CO2, a hydrogen source, O2 and a photosensitizer are brought into contact with one another, the photosensitizer being able to produce O2 in the presence of To convert light into a reactive oxygen species (ROS), and CO2, the hydrogen source, O2 and the photosensitizer are added with light until the reaction of CO2 with the hydrogen source to form the alcohol is complete.
  • ROS reactive oxygen species
  • the photosensitizer is preferably an organic or metal-organic compound, particularly preferably an organic compound.
  • Corresponding compounds are known to those skilled in the art from the literature. These include, for example, porphyrins and other compounds, which will be discussed in more detail below.
  • Reactive oxygen species is a collective term known to those skilled in the art for highly reactive oxygen compounds - such as singlet oxygen 1 O2 (open-shell and / or closed-shell) or the superoxide ion O2 - although this list is not exhaustive is. They are short-lived and difficult to detect, which is why, in the absence of more precise knowledge, the term reactive oxygen species (ROS) is commonly used.
  • ROS reactive oxygen species
  • the person skilled in the art generally understands this to be one or more reactive forms of oxygen that differ from conventional, comparatively inert triplet oxygen 3 O2.
  • Reactive oxygen species can be produced by activating ordinary triplet Generate oxygen 3 Ü2 in a resource-saving manner using a photosensitizer under the influence of light.
  • the hydrogen source in the processes according to the invention is preferably H2O.
  • H2O is not only the most cost-effective hydrogen source, but also the easiest to handle. In order to provide hydrogen, no alternative, possibly expensive sacrificial reagents are required as a hydrogen source. The use of water also has the captivating effect that when CO2 is reduced, two products from the combustion of fossil fuels can be removed from the natural material cycle.
  • the light preferably has a wavelength of 200 nm to 800 nm.
  • O2 is dissolved in water and is mixed with light.
  • CO2 is preferably dissolved in water and is mixed with light.
  • the alcohol is ethanol. According to a further preferred second embodiment of the method according to the invention, the alcohol is methanol.
  • the alcohol is ethanol, where - the molar concentration of CO2 in H2O is between 0.02 and 0.04 mol/L, preferably about 0.023 mol/L. This has proven to be beneficial for the production of ethanol.
  • the proportion of O2 in H2O in the method according to the invention according to the first embodiment is preferably between 2.4 and 4.7 ppm.
  • the amount of CO2 in H2O is 0.02 to 0.04 mol/L, preferably about 0.023 mol/L.
  • the photosensitizer is preferably an organic or metal-organic compound, particularly preferably an organic compound.
  • Corresponding compounds are known to those skilled in the art from the literature. These include, for example, compounds called porphyrins and others.
  • the photosensitizer is preferably selected from the group consisting of:
  • the photosensitizer was treated in water overnight to remove any CO2 absorbed by the photosensitizer. The concentration of dissolved CO2 was determined and the photosensitizer was added to the reaction mixture. The reaction was allowed to run for 5 h.
  • the CO2 concentration was initially 23.2 mmol/L, which decreased to 1.1 mmol/L over 5 hours.
  • 0.47 mmol/L EtOH was formed within the first hour, which increased to 8.9 mmol/L after 2 h and to 10.4 mmol/L after a reaction time of 5 h (Fig. 1 a).
  • CTE CO2-to-ethanol conversion efficiency
  • IR spectroscopy also allows a stoichiometric investigation of CO2 activation and conversion.
  • reproducibility experiments were performed using 16 mg of photoactive material/mL reaction medium. The formation of EtOH can be seen from the six reproducibility experiments in Figure 1 d.
  • the average concentration of EtOH formed during these experiments is 10.73 mM with a standard deviation of 0.94 (Table 2).
  • the photosensitizer was also exposed to direct air capture (DAC) conditions.
  • CO2 is used directly from the ambient air as a reactant without additional saturation or addition of CO2.
  • distilled water was added.
  • rapid EtOH production occurred when PCN-224 was exposed to simulated solar irradiation (white light, LED, 10 mW) in aqueous solution (pH: 5.3; DO: 4.3 ppm; temp. : 22.8 °C) under atmospheric conditions (1 atm). After just 1 hour of reaction time, significant ethanol formation occurs. The ethanol concentration produced was 16.1 mmol/L.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electromagnetism (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé photochimique pour la production sélective d'alcool à partir de CO2 et d'une source d'hydrogène, dans lequel : le CO2, une source d'hydrogène, de l'O2 et un photosensibilisateur sont mis en contact les uns avec les autres; le photosensibilisateur est capable de convertir l'O2 en une espèce réactive de l'oxygène en présence de lumière; et de la lumière est ajoutée au CO2, à la source d'hydrogène, à l'O2 et au photosensibilisateur jusqu'à ce que la réaction du CO2 avec la source d'hydrogène pour former de l'alcool soit achevée.
EP23716194.8A 2022-03-24 2023-03-24 Procédé photochimique de production d'alcools Pending EP4499596A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ATA50189/2022A AT526005B1 (de) 2022-03-24 2022-03-24 Photochemisches Verfahren zur Erzeugung von Alkoholen
PCT/EP2023/057717 WO2023180559A1 (fr) 2022-03-24 2023-03-24 Procédé photochimique de production d'alcools

Publications (1)

Publication Number Publication Date
EP4499596A1 true EP4499596A1 (fr) 2025-02-05

Family

ID=85980586

Family Applications (1)

Application Number Title Priority Date Filing Date
EP23716194.8A Pending EP4499596A1 (fr) 2022-03-24 2023-03-24 Procédé photochimique de production d'alcools

Country Status (3)

Country Link
EP (1) EP4499596A1 (fr)
AT (1) AT526005B1 (fr)
WO (1) WO2023180559A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118874551B (zh) * 2024-07-25 2026-01-30 吉林农业大学 一种MOFs限域Cu-Ag合金的核壳结构光催化剂的制备方法及其应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5988436A (ja) * 1982-11-11 1984-05-22 Nippon Mining Co Ltd メチルアルコ−ルの製造方法
US8986511B1 (en) * 2009-10-14 2015-03-24 U.S. Department Of Energy Visible light photoreduction of CO2 using heterostructured catalysts
WO2013175311A2 (fr) * 2012-05-23 2013-11-28 Bengt Norden Conversion de dioxyde de carbone en méthanol utilisant la lumière visible
WO2017091857A1 (fr) * 2015-11-30 2017-06-08 Adelaide Research And Innovation Conversion photocatalytique de dioxyde de carbone et d'eau en hydrocarbure(s) substitué(s) ou non substitué(s)
US10047027B1 (en) * 2017-11-08 2018-08-14 King Fahd University Of Petroleum And Minerals Method of forming methanol via photocatalytic reduction of carbon dioxide
CN113559934B (zh) * 2021-07-21 2022-06-17 南京工业大学 一种二氧化碳加氢制乙醇用催化剂的制备方法

Also Published As

Publication number Publication date
AT526005B1 (de) 2024-12-15
WO2023180559A1 (fr) 2023-09-28
AT526005A2 (de) 2023-10-15
AT526005A3 (de) 2024-07-15

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