JP-7856955-B2 - Screening method for catalysts used in olefin hydration reactions

Inventors

• 野村 淳子
• 宮下 昂大
• 板垣 真太朗
• 細木 康弘

Assignees

• クラサスケミカル株式会社
• 国立大学法人東京科学大学

Dates

Publication Date

20260512

Application Date

20220307

Claims (6)

1. A screening method for olefin hydration catalysts, comprising: heat-treating a catalyst on which a heteropoly acid is supported; measuring the catalyst after heat treatment by infrared spectroscopy and selecting a catalyst having an absorption band of 2200 cm⁻¹ , wherein the heat treatment temperature is 100 to 200°C .
2. The catalyst screening method according to claim 1 , wherein the heat treatment time is 0.5 to 3 hours.
3. The catalyst screening method according to claim 1 or 2 , wherein the heteropoly acid is silicic acid or phosphotungstic acid.
4. A method for screening a catalyst according to any one of claims 1 to 3 , wherein the support is silica.
5. The catalyst screening method according to any one of claims 1 to 4 , wherein the olefin is an olefin having 2 to 5 carbon atoms.
6. A method for producing alcohol by hydration reaction of an olefin, comprising the steps of: screening a catalyst by a screening method described in any one of claims 1 to 4 ; and producing an alcohol by reacting an olefin with water using the catalyst screened in the first step.

Description

This invention relates to a method for screening catalysts for olefin hydration reactions based on measurements by infrared spectroscopy, using a catalyst in which a heteropoly acid is supported on a carrier, and to a method for producing alcohol by the hydration reaction of an olefin using the catalyst. It is well known that the corresponding alcohol can be produced by hydrating lower olefins in the gas phase. It is also well known that supported catalysts, in which heteropoly acids or their salts are supported on a carrier, are useful in this reaction (Patent Documents 1 and 2). Non-patent document 1 suggests that hydroxonium ions ( H₃O⁺ , H₅O²⁺ ) are the active species in the hydration reaction of propylene using a phosphotungstic acid catalyst supported on silica. However, it does not actually investigate the correlation between hydroxonium ions and the olefin hydration reaction. Non-patent document 2 systematically evaluates the acidic properties of a silica-supported tungstic acid catalyst at various loading amounts by adsorbing benzonitrile onto the catalyst and then performing temperature-controlled desorption measurements. However, it does not investigate the correlation between the temperature-controlled desorption measurement results of benzonitrile and the olefin hydration reaction. Japanese Patent Application Publication No. 11-322646International Publication No. 2020/090756 Applied Catalysis A: General, vol. 256, p. 225-242 (2003).The Journal of Physical Chemistry C, Vol. 115, pp. 14762–14769 (2011). These are the FT-IR spectra of heteropoly acid-supported catalysts A to I measured in the examples.These are the FT-IR spectra obtained when 1-butene was reacted with heteropoly acid-supported catalysts A to I, as measured in the examples. The following describes preferred embodiments of the present invention, but it should be understood that the present invention is not limited to these embodiments, and various applications are possible within its spirit and scope of implementation. A screening method for catalysts for the hydration reaction of olefins according to one embodiment includes at least the following (1) heat treatment step and (2) selection step. (1) Heat treatment process: A process in which a catalyst supported by a heteropoly acid is heat-treated under vacuum. (2) Selection process: A process in which the catalyst after heat treatment is measured by infrared spectroscopy and a catalyst having an absorption band of 2200 cm⁻¹ is selected. Catalysts that have an absorption band at 2200 cm⁻¹ , which is attributed to protonated water of crystals, are thought to exhibit high activity in the hydration reaction of olefins. In this disclosure, the "2200 cm⁻¹ absorption band" means an absorption band having an absorption peak at wavenumbers 2100 cm⁻¹ to 2300 cm⁻¹ . [Catalyst for olefin hydration reactions] The screening method targets catalysts in which one or more heteropoly acids are supported on a carrier. A heteropoly acid is composed of a central element and surrounding elements bonded to oxygen. The central element is usually silicon or phosphorus, but can be any one element selected from groups 1 through 17 of the periodic table. Specifically, examples include, but are not limited to, cupric ions; divalent beryllium, zinc, cobalt, or nickel ions; trivalent boron, aluminum, gallium, iron, cerium, arsenic, antimony, phosphorus, bismuth, or chromium ions; tetravalent silicon, germanium, tin, titanium, zirconium, vanadium, sulfur, tellurium, manganese, nickel, thorium, hafnium, cerium ions, and other rare earth ions; pentavalent phosphorus, arsenic, vanadium, and antimony ions; hexavalent tellurium ions; and heptavalent iodide ions. Furthermore, specific examples of surrounding elements include, but are not limited to, tungsten, molybdenum, vanadium, niobium, and tantalum. Such heteropoly acids are known as "polyoxoanions," "polyoxometallic salts," or "metal oxide clusters." Some well-known anion structures are named after researchers in this field; for example, the Keggin, Wells-Dawson, and Anderson-Evans-Perloff structures are known. Further details can be found in "The Chemistry of Polyacids" (edited by the Chemical Society of Japan, Quarterly Review of Chemistry No. 20, 1993). Heteropoly acids typically have high molecular weights, for example, in the range of 700 to 8500, and include not only monomers but also dimeric complexes. A particularly preferred example of a heteropoly acid that can be used as a catalyst is siliconungstic acid H₄ [ SiW₁₂O₄O ]・xH₂O Phosphateungstic acid H3 [ PW12O40 ]・xH2O Phosphorus molybdate H₃ [ PMO₁₂O₄O ]・xH₂O Simolybdic acid H₄ [ SiMo₁₂O₄O ]・xH₂O Keibanadotungstic acid H 4 + n [SiV n W 12-n O 40 ]・xH 2 O Lymph vanadotungstic acid H3 +n [PV nW 12-n O 40 ]・xH2O Lymphanadomolybdate H3 +n [ PVnMo12 -nO40 ]・xH2O kaevanadomolybdic acid H 4 + n [SiV n Mo 12 - nO 40 ]・xH 2 O SiMolybdotungstic acid H₄ [ SiMonW₁₂ - nO₄O ]・xH₂O Phosphorus- molybdenum tungstic acid H