WO2011043151A1 - Procédé pour la production de méthanol - Google Patents

Procédé pour la production de méthanol Download PDF

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Publication number
WO2011043151A1
WO2011043151A1 PCT/JP2010/065385 JP2010065385W WO2011043151A1 WO 2011043151 A1 WO2011043151 A1 WO 2011043151A1 JP 2010065385 W JP2010065385 W JP 2010065385W WO 2011043151 A1 WO2011043151 A1 WO 2011043151A1
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water
oxide
methanol
catalyst
reaction
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PCT/JP2010/065385
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English (en)
Japanese (ja)
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友哉 後藤
雅美 村上
照典 藤田
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三井化学株式会社
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Priority to JP2011535322A priority Critical patent/JP5868178B2/ja
Publication of WO2011043151A1 publication Critical patent/WO2011043151A1/fr

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    • 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
    • C07C29/153—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 catalyst used
    • C07C29/154—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 catalyst used containing copper, silver, gold, or compounds thereof
    • 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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J23/42—Platinum
    • 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
    • B01J23/44—Palladium
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a method for producing methanol from a water-soluble organic compound having two or more oxygen atoms and water.
  • the present invention relates to a method for producing methanol from glycerin and water by-produced in a process for producing biodiesel fuel from fats and oils.
  • biodiesel fuel has attracted attention as a carbon neutral fuel made from vegetable oil.
  • Biodiesel fuel is a fatty acid ester and is synthesized by a transesterification reaction between fat (triglyceride) and alcohol.
  • fat triglyceride
  • alcohol triglyceride
  • this reaction about 10% of glycerin by weight is also by-produced with respect to biodiesel fuel.
  • Methanol is used as a raw material for chemicals and is also expected as a fuel for fuel cells. Methanol can also be used as a raw material for the transesterification reaction. Thus, since the use of methanol is very diverse, if methanol can be produced from glycerin, glycerin can be effectively utilized.
  • methanol is synthesized by catalytic reaction using carbon oxide and hydrogen as raw materials.
  • the carbon oxide contains a large amount of carbon dioxide, there is a problem that the decrease in the activity of the methanol synthesis catalyst is accelerated by water by-produced by the reaction between carbon dioxide and hydrogen (Non-patent Document 1). .
  • Patent Document 1 A manufacturing method is known (Patent Document 1). In this method, in order to suppress the production of carbon dioxide as much as possible, the reaction temperature when converting glycerin to carbon monoxide and hydrogen is set to a high temperature of 700 ° C. or higher. Therefore, a large amount of energy is required.
  • glycerin, steam, and oxygen are reacted under a condition of about 800 ° C. or higher to convert the gas into carbon monoxide and hydrogen as main components, and the gas is reduced to 60 ° C. or lower through a multi-stage heat recovery process.
  • a method is also known in which water is removed by cooling, carbon dioxide is removed if necessary, and then subjected to a methanol synthesis reaction through a compression step (Patent Document 2). This method has a multi-step process such as oxygen production, heat recovery, water removal, and carbon dioxide removal in addition to a high temperature reaction, which complicates the process and increases cost.
  • synthesis gas ie, H 2 / CO gas mixture
  • exothermic reaction eg, Fischer-Tropsch reaction
  • other exothermic reaction eg, methanol synthesis reaction, dimethyl ether synthesis reaction
  • Patent Document 3 the gasification reaction, which is an endothermic reaction, is not a high temperature but a low temperature (about 750 K or less, that is, about 477 ° C. or less) because of the balance between endotherm and heat generation.
  • the carbon dioxide production rate is higher than that required for the Fischer-Tropsch reaction or the like, compared with the gasification reaction at a high temperature. Therefore, it is not necessarily economical in terms of effective use of carbon sources.
  • the above method requires a separate carbon dioxide absorption / regeneration step using an absorbent material, and thus the process is not necessarily simplified.
  • the reaction between biomass and water vapor is performed at a high temperature (Example) of 650 ° C., energy consumption by the reaction is large.
  • the catalyst used for methanol synthesis is copper oxide-zinc oxide, copper oxide-chromium oxide-zinc oxide, copper oxide-zinc oxide-aluminum oxide, etc. used for methanol synthesis from carbon monoxide and hydrogen. Therefore, there is a concern that the activity of the catalyst is greatly reduced by water generated by the reaction.
  • glycerin As described above, in the process of producing biodiesel fuel (fatty acid ester) from fats and oils, it is required to effectively use glycerin produced as a by-product. In addition to glycerin, it is convenient if other water-soluble organic compounds having two or more oxygen atoms can be effectively utilized. As one of the methods, production of methanol from glycerin has been studied. Generally, in order to produce methanol from glycerin, glycerin is converted into a gas containing carbon oxide and hydrogen, and the carbon oxide and hydrogen are reacted in the presence of a methanol synthesis catalyst.
  • the present invention provides a method for producing methanol from a water-soluble organic compound having two or more oxygen atoms and water, and particularly a method for producing methanol from glycerin and water. This is the issue.
  • the present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above problems can be solved by using a specific methanol synthesis catalyst that has a small activity decrease due to water and is highly active, and has completed the present invention.
  • the method for producing methanol of the present invention is a method for producing methanol from a water-soluble organic compound having two or more oxygen atoms and water, and a methanol synthesis catalyst containing copper oxide, zinc oxide and silicon oxide (A) And at least a step in which all the steps are present, and all the steps are performed at a temperature of 200 to 500 ° C.
  • the water-soluble organic compound is preferably at least one selected from polyhydric alcohols (excluding saccharides) and saccharides.
  • the water-soluble organic compound is preferably glycerin.
  • the glycerin is preferably glycerin derived from fats and oils.
  • the methanol synthesis catalyst (A) preferably further contains aluminum oxide.
  • the methanol synthesis catalyst (A) preferably further contains at least one oxide selected from gallium oxide and zirconium oxide.
  • the method for producing methanol of the present invention includes a step in which a catalyst (B) for the reaction of converting the water-soluble organic compound and water into a gas containing carbon oxide and hydrogen at a temperature of 200 to 500 ° C. is present. It is preferable.
  • the catalyst (B) is preferably a solid catalyst comprising a carrier supporting at least one selected from platinum, nickel and palladium.
  • the method for producing methanol of the present invention comprises (1) a step of converting the water-soluble organic compound and water into a gas containing carbon oxide and hydrogen at a temperature of 200 to 500 ° C., and (2) the methanol synthesis It is preferable to have a step of reacting the carbon oxide and the hydrogen in the presence of the catalyst (A).
  • the step (1) is preferably carried out in the presence of a solid catalyst comprising a carrier supporting at least one selected from platinum, nickel and palladium.
  • a method for producing methanol from a water-soluble organic compound having two or more oxygen atoms and water and particularly a method for producing methanol from glycerin and water.
  • the method for producing methanol of the present invention can perform all steps at a low temperature of 200 to 500 ° C. Therefore, for example, it is possible to provide a method in which glycerin produced as a by-product in a process of producing biodiesel fuel from fats and oils is advantageously used with low energy consumption and cost.
  • the method for producing methanol of the present invention is a method for producing methanol from a water-soluble organic compound having two or more oxygen atoms (hereinafter, also simply referred to as “water-soluble organic compound”) and water, comprising copper oxide, It has at least a step in which a methanol synthesis catalyst (A) containing zinc oxide and silicon oxide (hereinafter also simply referred to as “methanol synthesis catalyst (A)”) is present, and all the steps are performed at 200 to 500 ° C., preferably 200 It is characterized by being carried out at a temperature of ⁇ 400 ° C.
  • the “all steps” means a series of steps starting from a step of performing the following conversion reaction to a step of performing a methanol synthesis reaction. Therefore, for example, the step of preparing an aqueous solution of a water-soluble organic compound is not included in the “all steps”. In the present invention, this series of steps can be performed in a temperature range of 200 to 500 ° C., so that energy consumption can be suppressed.
  • reaction (i) a water-soluble organic compound and water are converted into a gas containing carbon oxide and hydrogen, and (ii) the carbon oxide and hydrogen are further reacted, Methanol is thought to be produced.
  • conversion reaction the reaction (i) is also referred to as “conversion reaction” and the reaction (ii) is also referred to as “methanol synthesis reaction”.
  • the carbon oxide examples include carbon dioxide and carbon monoxide.
  • the methanol synthesis catalyst (A) is used as a catalyst for the methanol synthesis reaction.
  • This catalyst is highly active with little decrease in activity due to water produced by the reaction between carbon dioxide and hydrogen. For this reason, it is not necessary to set the reaction conditions for the conversion reaction to conditions that are more advantageous for the production of carbon monoxide than the production of carbon dioxide as in the prior art. Therefore, in the present invention, all the steps can be performed at a temperature of 200 to 500 ° C., and no particular treatment such as heat recovery, water removal, carbon dioxide removal is required.
  • the water-soluble organic compound has two or more oxygen atoms; is composed of at least carbon atoms, hydrogen atoms and oxygen atoms, and preferably has two or more oxygen atoms; at least from carbon atoms, hydrogen atoms and oxygen atoms. More preferably, it has two or more oxygen atoms that are configured and bonded to carbon atoms.
  • Water-soluble organic compounds include polyhydric alcohols such as ethanediol, glycerin and sorbitol (excluding saccharides); ketones such as ethanedione (excluding saccharides); ketotriose (eg, dihydroxyacetone), aldo Saccharides such as triose (eg glyceraldehyde), ketotetrose, aldotetorose, ketopentose, aldopentose, ketohexose (eg fructose), aldohexose (eg glucose), saccharides such as disaccharides such as sucrose Can be mentioned.
  • the water-soluble organic compound preferably has 2 to 12 carbon atoms. These water-soluble organic compounds may be used alone or in combination of two or more.
  • polyhydric alcohols and saccharides are preferred, polyhydric alcohols are more preferred, glycerin is more preferred, and glycerin derived from fats and oils is particularly preferred.
  • fats and oils examples include rapeseed oil, sesame oil, soybean oil, corn oil, sunflower oil, palm oil, palm kernel oil, coconut oil, safflower oil, and waste cooking oils thereof.
  • glycerin derived from fats and oils examples include glycerin produced as a by-product in the process of producing fatty acid esters for biodiesel fuel, preferably fatty acid alkyl esters, more preferably fatty acid methyl esters from fats and oils.
  • the by-product glycerin may be used as it is, or may be used after removing impurities contained in the by-product glycerin.
  • the impurities include components derived from a catalyst for transesterification, methanol, fatty acids, monoglycerides, diglycerides and the like.
  • the water-soluble organic compound is preferably dissolved in water described later and supplied to the reactor in the form of an aqueous solution from the viewpoint of energy reduction.
  • glycerin when used as the water-soluble organic compound, it may be supplied to the reactor as a glycerin aqueous solution.
  • water used together with the water-soluble organic compound may be in a liquid state or water vapor. From the viewpoint of energy reduction, water is preferably used in a liquid state.
  • the amount of water used is such that the molar ratio of water-soluble organic compound to water (water / water-soluble organic compound) is preferably 2 to sufficiently convert the water-soluble organic compound to a gas containing carbon oxide and hydrogen. It may be set in a range of 600, more preferably 3 to 200. When the amount of water used is increased, the content ratio of carbon dioxide to carbon monoxide in the carbon oxide increases, but it may be disadvantageous in terms of thermal energy. In the present invention, it is not necessary to suppress the production of carbon dioxide, but it is preferable to set the molar ratio in the above range from the viewpoint of energy reduction.
  • the method for producing methanol of the present invention has at least a step in which a methanol synthesis catalyst (A) is present. Thereby, the carbon oxide produced
  • the methanol synthesis catalyst (A) contains copper oxide, zinc oxide and silicon oxide as essential components, and preferably further contains aluminum oxide.
  • the methanol synthesis catalyst (A) may further contain at least one oxide selected from gallium oxide and zirconium oxide. Further, other oxides may be included as long as the gist of the present invention is not impaired.
  • the methanol synthesis catalyst (A) is a catalyst for synthesizing methanol from carbon oxide and hydrogen, and is a catalyst having a small decrease in activity and high durability even in the presence of water produced by the methanol synthesis reaction. . There is no particular problem even if carbon monoxide is present together with carbon dioxide in the carbon oxide.
  • the content ratio of each component is such that when the total amount of the methanol synthesis catalyst (A) is 100% by weight, copper oxide is usually 20 to 60% by weight, preferably 30 to 50% by weight; zinc oxide is usually 10 to 50% by weight. %, Preferably 20-40% by weight; silicon oxide is usually 0.3-0.9% by weight, preferably 0.3-0.8% by weight; aluminum oxide is usually 0-10% by weight, preferably 2 to 10% by weight, more preferably 4 to 8% by weight; gallium oxide is usually 0 to 10% by weight, preferably 0.1 to 5% by weight; zirconium oxide is usually 0 to 40% by weight, preferably 10% ⁇ 30% by weight.
  • the durability of the catalyst may be insufficient, and when it exceeds the above range, the activity of the catalyst may be insufficient and the durability of the catalyst may be insufficient.
  • the silicon oxide is preferably silicon oxide derived from colloidal silica or silica dissolved in water. Colloidal silica and water-dissolved silica may be used in combination. On the other hand, when silicon oxide produced from sodium silicate (water glass) or potassium silicate is used, a catalyst having the desired effect may not be obtained.
  • colloidal silica it is preferable to use one having a sodium oxide content of usually less than 0.1% by weight, particularly 0.06% by weight or less. Many grades of colloidal silica have a sodium oxide content of about 0.2 to 0.6% by weight.
  • silica Natural fresh water, tap water, well water, industrial water, etc. can be used as the silica dissolved in water. These waters contain about 20 to 100 ppm of silica. Dissolved silica in water is silica (commonly referred to as colorimetric silica) measured by a spectrophotometric method using a molybdenum yellow method or a molybdenum blue method.
  • the methanol synthesis catalyst (A) is preferably subjected to a calcination treatment.
  • the firing temperature is usually 480 to 690 ° C., preferably 520 to 680 ° C., particularly preferably 560 to 670 ° C. If the firing temperature is outside the above range, the activity and durability of the catalyst may be insufficient.
  • the methanol synthesis catalyst (A) may be used after reduction with a mixed gas of hydrogen and nitrogen.
  • the methanol synthesis catalyst (A) can be produced, for example, according to the description in paragraphs [0024] to [0031] and [Examples] of Japanese Patent No. 3232326.
  • the method for producing methanol of the present invention comprises a reaction catalyst (B) for converting a water-soluble organic compound and water into a gas containing carbon oxide and hydrogen at a temperature of 200 to 500 ° C. (preferably 200 to 400 ° C.). ) (Hereinafter also referred to as “conversion catalyst (B)”).
  • the conversion catalyst (B) is not particularly limited, and a platinum-based, nickel-based, palladium-based solid catalyst, or the like can be used.
  • the support supports at least one selected from platinum, nickel, and palladium.
  • a solid catalyst examples include alumina.
  • the usage forms of the conversion catalyst (B) and the methanol synthesis catalyst (A) are not particularly limited.
  • the step of performing the conversion reaction in the presence of the conversion catalyst (B) and the step of performing the methanol synthesis reaction in the presence of the methanol synthesis catalyst (A) are sequentially performed. It is preferable to implement.
  • the step in which the conversion catalyst (B) is present and the step in which the methanol synthesis catalyst (A) is present may be the same step. That is, the conversion catalyst (B) and the methanol synthesis catalyst (A) may be mixed and used, for example, and the conversion reaction and the methanol synthesis reaction may be performed simultaneously.
  • the reactor used in the present invention is not particularly limited, and for example, a fixed bed reactor or a fluidized bed reactor can be used. Specifically, the fixed bed reactor filled with the conversion catalyst (B), the fixed bed reactor filled with the methanol synthesis catalyst (A), and the conversion catalyst (B) and the methanol synthesis catalyst (A) packed. Fixed bed reactors can be used.
  • the method for producing methanol of the present invention comprises (1) a step of converting a water-soluble organic compound and water into a gas containing carbon oxide and hydrogen at a temperature of 200 to 500 ° C. (hereinafter referred to as “conversion step (1)”). And (2) a step of reacting the carbon oxide with the hydrogen in the presence of the methanol synthesis catalyst (A) (hereinafter also referred to as “methanol synthesis step (2)”). .
  • the conversion step (1) is usually carried out at a temperature of 200 to 500 ° C., preferably 200 to 400 ° C. If it is the said temperature, while the production
  • a temperature of 200 ° C. or higher is generally required.
  • a temperature of 700 ° C. or higher is required. This is because at high temperatures the equilibrium is more favorable for the production of carbon monoxide than for the production of carbon dioxide.
  • the methanol synthesis reaction is generally performed at a low temperature (for example, 350 ° C. or lower)
  • a low temperature for example, 350 ° C. or lower
  • an additional cooling step is required. Therefore, a large amount of energy is discarded.
  • the gas obtained in the conversion step (1) usually contains the water used in the conversion step (1) together with the carbon oxide and hydrogen, the activity of the catalyst when a normal methanol synthesis catalyst is used. The decline is remarkable. Therefore, from the viewpoint of removing water, the conventional technique requires a separate cooling step.
  • the methanol synthesis step (2) is carried out in the presence of a highly active methanol synthesis catalyst (A) with a small decrease in activity due to water.
  • the conversion step (1) can be performed at a low temperature of usually 500 ° C. or lower, preferably 400 ° C. or lower. Further, it is not necessary to provide a separate process for removing carbon dioxide.
  • the obtained gas can be supplied to the methanol synthesis step (2) while being maintained at 200 ° C. or higher. That is, in the present invention, the gas containing the carbon oxide and hydrogen produced in the conversion step (1) is cooled to below the reaction temperature of the methanol synthesis step (2) to completely remove water, and the methanol synthesis step ( 2) can be supplied. As a matter of course, water condensed when the reaction temperature is controlled to the methanol synthesis step (2) is removed from the gas obtained in the conversion step (1).
  • the process for producing methanol of the present invention has a simplified process as compared with the conventional process and is highly economical.
  • the conversion step (1) is usually carried out at a pressure of 0.1 to 5 MPa, preferably 0.5 to 3 MPa. If it is the said pressure, conversion of a water-soluble organic compound can fully be performed.
  • Carbon oxides obtained in the conversion step (1) comprises at least carbon dioxide (CO 2), and the molar ratio of carbon monoxide and (CO) and carbon dioxide (CO 2) (CO / CO 2) is preferably 1 or less, more preferably 0.83 or less.
  • the lower limit of the molar ratio is not particularly limited because carbon monoxide may be generated due to equilibrium restrictions in the methanol synthesis reaction, but theoretically it may be 0 (carbon dioxide is 100%).
  • the supply amount of the water-soluble organic compound per hour per 1 kg of the conversion catalyst (B) is related to the conversion rate, but is usually 5 to 5000 g.
  • the reaction conditions of the methanol synthesis step (2) vary depending on the concentrations of carbon oxide and hydrogen in the gas obtained in the conversion step (1) and the amount of methanol synthesis catalyst (A) used.
  • the reaction temperature is usually 200 to 350 ° C., preferably 200 to 300 ° C.
  • the reaction pressure is usually 1 to 30 MPa, preferably 1 to 15 MPa.
  • the amount of gas obtained in the conversion step (1) per hour for 1 L of the methanol synthesis catalyst (A) is usually 5000 to 30000 L / hr, although it depends on temperature and pressure.
  • the gas obtained in the conversion step (1) It is also possible to supply hydrogen separately.
  • the molar ratio of carbon oxide to hydrogen is usually set in the range of 0.05 to 1.0, preferably 0.1 to 0.8.
  • the temperature of the gas obtained in the conversion step (1) is controlled to the temperature in the methanol synthesis step (2) and then compressed.
  • the pressure may be reduced and then supplied to the methanol synthesis step (2).
  • the temperature may be controlled.
  • the product gas obtained in the methanol synthesis step (2) is separated into crude methanol and unreacted gas using a condenser.
  • the unreacted gas may be supplied again to the methanol synthesis step (2), or may be burned and used as thermal energy.
  • Crude methanol can be purified as appropriate. In this way, methanol can be produced.
  • Example 1 As a water-soluble organic compound, glycerin by-produced in a process for producing fatty acid methyl ester for biodiesel fuel from fats and oils was used. Water was added to glycerin such that the glycerin content was 10% by weight (here, the molar ratio (water / glycerin) was 50) to prepare an aqueous solution (hereinafter also referred to as “glycerin aqueous solution”). .
  • a gasification reaction tube made of SUS316, length 1 m, outer diameter 6.24 mm, wall thickness 1.24 mm
  • the glycerin aqueous solution is introduced at a rate of 60 mg / min with a liquid feed pump, and the reaction conditions are controlled so that the pressure is 3 MPa by operating the back pressure valve and the temperature is 225 ° C. by heating with an electric heater. The operation was continued for 5 hours.
  • the gas obtained by the conversion reaction was collected from a gas sampler and analyzed online by gas chromatography.
  • the gas composition was volume%, and excluding water, carbon dioxide: 30%, carbon monoxide: 0%, hydrogen: 65%, methane: 5%. After the operation was completed, almost no solid matter was observed inside the gasification reaction tube.
  • a methanol synthesis reaction tube having the same material, length, outer diameter, and wall thickness as the gasification reaction tube was charged with 1 mL of a methanol synthesis catalyst (A).
  • the methanol synthesis catalyst (A) is a composite oxide obtained by precipitation from metal nitrate and made of copper oxide, zinc oxide, zirconium oxide, aluminum oxide and silica, and has a particle size of 250 to 500 ⁇ m. I used the aligned ones.
  • the composition (weight percent basis) of the oxide is CuO: 45%, ZnO: 27%, ZrO 2 : 23%, Al 2 O 3 : 4.5%, and SiO 2 : 0.5%.
  • the methanol synthesis catalyst (A) was sufficiently reduced at 300 ° C. for 2 hours with 5 vol% hydrogen / 95 vol% nitrogen gas.
  • the gas obtained by the conversion reaction of the glycerin aqueous solution is pressurized with a compressor, and then introduced into the methanol synthesis reaction tube at a rate of 10 L / hr, and the back pressure valve is operated so that the pressure becomes 5 MPa.
  • the reaction conditions were controlled so that the temperature would be 250 ° C. by heating with a methanol synthesis reaction.
  • the present invention makes it possible to convert glycerin produced as a by-product in the production of biodiesel fuel into methanol at lower energy and lower costs than in the past. Since the produced methanol can be expected to be used as a raw material for chemical exchange, a fuel cell fuel, and a raw material for transesterification when producing biodiesel fuel, the present invention is extremely useful industrially.

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

Abstract

L'invention porte sur un procédé pour la production de méthanol à partir d'un composé organique hydrosoluble ayant au moins deux atomes d'oxygène et d'eau, en particulier de glycérol et d'eau, qui consomme peu d'énergie et qui est avantageux en ce qui concerne le coût. De façon spécifique, l'invention porte sur un procédé pour la production de méthanol à partir d'un composé organique hydrosoluble ayant au moins deux atomes d'oxygène et d'eau, qui est caractérisé en ce qu'au moins une étape dans laquelle un catalyseur de synthèse de méthanol (A) comprenant de l'oxyde de cuivre, de l'oxyde de zinc et de l'oxyde de silicium est présent est comprise dans le procédé et toutes les étapes comprises dans le procédé sont effectuées à des températures de 200 à 500°C.
PCT/JP2010/065385 2009-10-08 2010-09-08 Procédé pour la production de méthanol WO2011043151A1 (fr)

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CN110168153A (zh) * 2016-11-01 2019-08-23 柯利亚·库赛 以二氧化碳为原料结合整体生产方法制造可再生或部分可再生碳纤维

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Publication number Priority date Publication date Assignee Title
CN104098436A (zh) * 2013-04-02 2014-10-15 北京化工大学 一种低温合成甲醇的方法
CN110168153A (zh) * 2016-11-01 2019-08-23 柯利亚·库赛 以二氧化碳为原料结合整体生产方法制造可再生或部分可再生碳纤维

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