JP5774180B1 - Composite catalyst for methanol production, method for producing the same, and method for producing methanol - Google Patents
Composite catalyst for methanol production, method for producing the same, and method for producing methanol Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 239000003054 catalyst Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 58
- 239000010949 copper Substances 0.000 claims abstract description 118
- 239000013259 porous coordination polymer Substances 0.000 claims abstract description 79
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000010419 fine particle Substances 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 12
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 40
- 239000011787 zinc oxide Substances 0.000 claims description 19
- 229910021645 metal ion Inorganic materials 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 21
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 239000005751 Copper oxide Substances 0.000 description 9
- 229910000431 copper oxide Inorganic materials 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000013207 UiO-66 Substances 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- OYFRNYNHAZOYNF-UHFFFAOYSA-N H2dhybdc Natural products OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- -1 ZrCl 4 Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- 239000013206 MIL-53 Substances 0.000 description 1
- 239000013118 MOF-74-type framework Substances 0.000 description 1
- 229910003962 NiZn Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
【課題】二酸化炭素からメタノールを効率的に製造するための触媒及び二酸化炭素からメタノールを製造する方法を提供する。【解決手段】銅系微粒子を多孔性配位高分子（ＰＣＰ）に担持した、メタノール製造用複合触媒。【選択図】図１A catalyst for efficiently producing methanol from carbon dioxide and a method for producing methanol from carbon dioxide are provided. A composite catalyst for methanol production, in which copper-based fine particles are supported on a porous coordination polymer (PCP). [Selection] Figure 1
Description
本発明は、メタノール製造用複合触媒及びその製造方法、並びにメタノールの製造方法に関する。 The present invention relates to a composite catalyst for producing methanol, a method for producing the same, and a method for producing methanol.
本明細書において多孔性配位高分子（Porous Coordination Polymer）を「ＰＣＰ」と略すことがある。 In the present specification, porous coordination polymer is sometimes abbreviated as “PCP”.
有機配位子と金属イオンの自己集合反応により均一なナノ細孔を持つＰＣＰは様々な物性を持っており、ゼオライト、活性炭などの細孔性材料より精密に設計でき、様々なガスを大量かつ選択的に吸着できる特性をもつことから、ガス貯蔵材、吸着材として注目されている（特許文献１〜３）。 PCP with uniform nanopores due to the self-assembly reaction of organic ligands and metal ions has various physical properties, and can be designed more precisely than porous materials such as zeolite and activated carbon. It has attracted attention as a gas storage material and adsorbent because it has the property of being selectively adsorbed (Patent Documents 1 to 3).
ＰＣＰに金属ナノ粒子を担持させた複合触媒は、アルコール酸化反応、ＣＯ酸化反応などの触媒として検討されている。 A composite catalyst in which metal nanoparticles are supported on PCP has been studied as a catalyst for alcohol oxidation reaction, CO oxidation reaction and the like.
本発明は、二酸化炭素からメタノールを効率的に製造するための触媒及びその製造方法並びに二酸化炭素からメタノールを製造する方法を提供することを目的とする。 An object of this invention is to provide the catalyst for manufacturing methanol efficiently from a carbon dioxide, its manufacturing method, and the method of manufacturing methanol from a carbon dioxide.
本発明は、以下のメタノール製造用複合触媒及びその製造方法、並びにメタノールの製造方法を提供するものである。
項１． 銅系微粒子を多孔性配位高分子（ＰＣＰ）に担持した、メタノール製造用複合触媒。
項２． 銅系微粒子が酸化亜鉛と銅を含む複合微粒子又は銅ナノ粒子単独である、項１に記載のメタノール製造用複合触媒。
項３． 前記ＰＣＰを構成する金属イオンがＺｒ４＋、Ｈｆ４＋、Ａｌ３＋、Ｇａ３＋及びＩｎ３＋からなる群から選ばれる少なくとも１種を含む、項１又は２に記載のメタノール製造用複合触媒。
項４． 前記ＰＣＰがＵｉＯ６６型ＰＣＰもしくはＭＩＬ５３型ＰＣＰである、項１〜３のいずれかに記載のメタノール製造用複合触媒。
項５． 前記ＰＣＰを構成する配位子が下記式（Ｉ）
The present invention provides the following composite catalyst for methanol production, a method for producing the same, and a method for producing methanol.
Item 1. A composite catalyst for methanol production in which copper-based fine particles are supported on a porous coordination polymer (PCP).
Item 2. Item 2. The composite catalyst for methanol production according to Item 1, wherein the copper-based fine particles are composite fine particles containing zinc oxide and copper or copper nanoparticles alone.
Item 3. Item 3. The composite catalyst for methanol production according to Item 1 or 2, wherein the metal ion constituting the PCP contains at least one selected from the group consisting of Zr 4+ , Hf 4+ , Al 3+ , Ga 3+ and In 3+ .
Item 4. Item 4. The composite catalyst for methanol production according to any one of Items 1 to 3, wherein the PCP is UiO66 type PCP or MIL53 type PCP.
Item 5. The ligand constituting the PCP is represented by the following formula (I)
（式中、Ｒは、同一又は異なって水素原子、ＮＨ２又はＣＯＯＨである）。
で表される、項１〜４のいずれかに記載のメタノール製造用複合触媒。
項６． ＰＣＰを構成する配位子が下記式（ＩＡ）
(Wherein R is the same or different and is a hydrogen atom, NH 2 or COOH).
Item 5. The composite catalyst for methanol production according to any one of Items 1 to 4, which is represented by:
Item 6. The ligand constituting PCP is represented by the following formula (IA)
（式中、Ｒは、同一又は異なってＮＨ２又はＣＯＯＨである）。
で表される、項５に記載のメタノール製造用複合触媒。
項７． ＰＣＰがＵｉＯ６６である、項１〜６のいずれかに記載のメタノール製造用複合触媒。
項８． ＲがＣＯＯＨである、項５又は６に記載のメタノール製造用複合触媒。
項９． 銅系微粒子のサイズが１〜２００ｎｍである、項１〜８のいずれかに記載のメタノール製造用複合触媒。
項１０． 銅系微粒子とＰＣＰの重量比率が、ＰＣＰ：銅系微粒子＝９５〜６５：５〜３５である、項１〜９のいずれかに記載のメタノール製造用複合触媒。
項１１． メタノール合成の原料が水素と二酸化炭素を含み、任意成分としてさらに一酸化炭素を含み得る、項１〜１０のいずれかに記載のメタノール製造用複合触媒。
項１２． 項１〜１１のいずれかに記載のメタノール製造用複合触媒についての製造方法であって、ＰＣＰを構成する金属イオンとＰＣＰを構成する配位子を含む溶液に酸化銅系微粒子を混合し、噴霧反応を行って酸化銅系微粒子をＰＣＰに担持する工程、酸化銅系微粒子を担持したＰＣＰを水素の存在下で還元して銅系微粒子をＰＣＰに担持した複合触媒を得る工程を含む、メタノール製造用複合触媒の製造方法。
項１３． 項１〜１１のいずれかに記載のメタノール製造用複合触媒についての製造方法であって、Ｃｕ（ａｃａｃ）２の有機溶媒溶液にＰＣＰを加えた後、溶媒を蒸発させてＣｕ（ａｃａｃ）２をＰＣＰに担持させる工程、Ｃｕ（ａｃａｃ）２を担持したＰＣＰを加熱してＣｕ（ａｃａｃ）２を熱分解し、Ｃｕナノ粒子をＰＣＰに担持した複合触媒を得る工程を含む、メタノール製造用複合触媒の製造方法。
項１４． 項１〜１１のいずれかに記載のメタノール製造用複合触媒の存在下に水素と二酸化炭素、任意成分としてさらに一酸化炭素を含み得る混合ガスを作用させることを特徴とする、メタノールの製造方法：
(Wherein R is the same or different and is NH 2 or COOH).
Item 6. The composite catalyst for methanol production according to Item 5, represented by:
Item 7. Item 7. The composite catalyst for methanol production according to any one of Items 1 to 6, wherein the PCP is UiO66.
Item 8. Item 7. The composite catalyst for methanol production according to Item 5 or 6, wherein R is COOH.
Item 9. Item 9. The composite catalyst for methanol production according to any one of Items 1 to 8, wherein the size of the copper-based fine particles is 1 to 200 nm.
Item 10. Item 10. The composite catalyst for methanol production according to any one of Items 1 to 9, wherein the weight ratio of the copper-based fine particles to PCP is PCP: copper-based fine particles = 95 to 65: 5-35.
Item 11. Item 11. The composite catalyst for methanol production according to any one of Items 1 to 10, wherein the raw material for methanol synthesis contains hydrogen and carbon dioxide, and may further contain carbon monoxide as an optional component.
Item 12. Item 12. A method for producing a composite catalyst for methanol production according to any one of Items 1 to 11, wherein copper oxide fine particles are mixed in a solution containing a metal ion constituting PCP and a ligand constituting PCP, and sprayed Methanol production comprising a step of carrying out a reaction to carry copper oxide fine particles on PCP, a step of reducing PCP carrying copper oxide fine particles in the presence of hydrogen to obtain a composite catalyst carrying copper fine particles on PCP For producing a composite catalyst.
Item 13. Item 12. A method for producing a composite catalyst for methanol production according to any one of Items 1 to 11, wherein after adding PCP to an organic solvent solution of Cu (acac) 2 , the solvent is evaporated to obtain Cu (acac) 2 . step to be carried on PCP, Cu a (acac) 2 was thermally decomposed by heating the PCP carrying the Cu (acac) 2, comprising the step of obtaining a composite catalyst carrying Cu nanoparticles PCP, composite catalyst for methanol production Manufacturing method.
Item 14. Item 12. A method for producing methanol, comprising reacting hydrogen, carbon dioxide, and a mixed gas that may further contain carbon monoxide as an optional component in the presence of the composite catalyst for methanol production according to any one of Items 1 to 11:
本発明の複合触媒は、気相反応において二酸化炭素と水素からメタノールを効率よく合成することができる。ＵｉＯ６６型ＰＣＰまたはＭＩＬ−５３型ＰＣＰの複合触媒の場合にメタノールの製造効率が高く、特に金属イオンがＺｒ４＋及び/又はＨｆ４＋であり、かつ、一般式（Ｉ）の配位子のＲがＣＯＯＨである複合触媒の場合にメタノールの製造効率がより高くなる。 The composite catalyst of the present invention can efficiently synthesize methanol from carbon dioxide and hydrogen in a gas phase reaction. In the case of a composite catalyst of UiO66 type PCP or MIL-53 type PCP, the production efficiency of methanol is high, in particular, the metal ion is Zr 4+ and / or Hf 4+ , and R of the ligand of the general formula (I) is In the case of a composite catalyst that is COOH, the production efficiency of methanol is higher.
本発明の複合触媒は、ＰＣＰに銅系微粒子を担持させたものである。 The composite catalyst of the present invention is obtained by supporting copper fine particles on PCP.
銅系微粒子は、銅微粒子（好ましくは銅ナノ粒子）、ＮｉＺｎ合金微粒子などの銅と同様な機能を有する合金微粒子（好ましくは合金ナノ粒子）などの金属微粒子単独であってもよく、或いは、銅又は銅と同様な機能を有する合金微粒子を担体に担持した微粒子、銅と他の金属酸化物(例えば酸化亜鉛)の複合微粒子が挙げられる。担体としては、酸化亜鉛（ＺｎＯ）が好ましく例示される。他の金属酸化物としては、酸化亜鉛（ＺｎＯ）などの担体と同様な材料が挙げられる。例えば噴霧反応法などにより酸化銅と酸化亜鉛などの他の金属酸化物の複合酸化物を調製し、水素により酸化銅を選択的に還元した場合、銅は酸化亜鉛などの他の金属酸化物に担持されたというよりは、銅と酸化亜鉛などの他の金属酸化物が混在した複合微粒子として存在する。 The copper-based fine particles may be metal fine particles alone such as copper fine particles (preferably copper nanoparticles), alloy fine particles (preferably alloy nanoparticles) having the same function as copper, such as NiZn alloy fine particles, or copper. Alternatively, fine particles in which alloy fine particles having a function similar to that of copper are supported on a carrier, and composite fine particles of copper and another metal oxide (for example, zinc oxide) can be given. Preferred examples of the carrier include zinc oxide (ZnO). Examples of the other metal oxide include materials similar to those of a carrier such as zinc oxide (ZnO). For example, when a composite oxide of other metal oxides such as copper oxide and zinc oxide is prepared by a spray reaction method, etc., and copper oxide is selectively reduced by hydrogen, copper is converted into other metal oxides such as zinc oxide. Rather than being supported, they exist as composite fine particles in which other metal oxides such as copper and zinc oxide are mixed.
銅を酸化亜鉛に担持した微粒子の場合、銅１モルに対しＺｎＯを０．０１〜１００モル、好ましくは０．１〜１０モル、より好ましくは０．２〜５モル、さらに好ましくは０．５〜２モル含む銅系微粒子が好ましい。 In the case of fine particles in which copper is supported on zinc oxide, ZnO is 0.01 to 100 mol, preferably 0.1 to 10 mol, more preferably 0.2 to 5 mol, and still more preferably 0.5 to 1 mol of copper. Copper-based fine particles containing ˜2 mol are preferred.
銅系微粒子の平均粒径は、０．１〜１０００ｎｍ程度、好ましくは０．１〜５００ｎｍ程度、より好ましくは１〜２００ｎｍ程度、より好ましくは１〜１００ｎｍ程度、特に好ましくは１〜５０ｎｍ程度である。銅系微粒子の平均粒径は小さい方が表面積が大きく、メタノールを効率的に合成できるので、好ましい。 The average particle diameter of the copper-based fine particles is about 0.1 to 1000 nm, preferably about 0.1 to 500 nm, more preferably about 1 to 200 nm, more preferably about 1 to 100 nm, and particularly preferably about 1 to 50 nm. . A smaller average particle size of the copper-based fine particles is preferable because the surface area is large and methanol can be efficiently synthesized.
銅系微粒子を担持するＰＣＰは特に限定されず広範なＰＣＰを用いることができ、例えばＵｉＯ６６型、ＵｉＯ６７型、ＭＩＬ５３型、ＭＩＬ１０１型、ＺＩＦ８型などのＰＣＰが挙げられる。好ましいＰＣＰはＵｉＯ６６型、ＭＩＬ５３型である。ＭＩＬ５３型のＰＣＰを構成する金属イオンはＡｌ３＋、Ｇａ３＋及びＩｎ３＋からなる群から選ばれる少なくとも１種であり、ＭＩＬ５３型のＰＣＰを構成する限り他の金属イオンが含まれていてもよい。ＵｉＯ６６型のＰＣＰを構成する金属イオンはＨｆ４＋及び／又はＺｒ４＋であり、ＵｉＯ６６型のＰＣＰを構成する限り他の金属イオンが含まれていてもよい。 The PCP carrying the copper-based fine particles is not particularly limited, and a wide range of PCPs can be used. Examples thereof include PCPs such as UiO66 type, UiO67 type, MIL53 type, MIL101 type, and ZIF8 type. Preferred PCPs are UiO66 type and MIL53 type. The metal ion constituting the MIL53 type PCP is at least one selected from the group consisting of Al 3+ , Ga 3+ and In 3+ , and may contain other metal ions as long as the MIL53 type PCP is constituted. The metal ions constituting the UiO66 type PCP are Hf 4+ and / or Zr 4+ , and other metal ions may be included as long as the UiO66 type PCP is constituted.
ＰＣＰを構成する配位子としては、各種配位子が使用でき、ＵｉＯ６６型、ＵｉＯ６７型、ＭＩＬ５３型、ＭＩＬ１０１型、ＺＩＦ８型などのＰＣＰの場合には、下記式（Ｉ）又は（ＩＡ） As the ligand constituting PCP, various ligands can be used. In the case of PCP such as UiO66 type, UiO67 type, MIL53 type, MIL101 type, ZIF8 type, etc., the following formula (I) or (IA)
（式中、Ｒは、同一又は異なって水素原子、ＮＨ２又はＣＯＯＨである）で表される配位子が使用できる。 (Wherein R is the same or different and each represents a hydrogen atom, NH 2 or COOH).
例えば金属イオンがＺｒ４＋又はＨｆ４＋であり、一般式（Ｉ）においてＲ＝Ｈの配位子を用いたＰＣＰはＵｉＯ６６であり、一般式（Ｉ）において一方又は両方のＲが水素ではないか、或いはＺｒ４＋とＨｆ４＋以外の金属イオンが含まれるＰＣＰはＵｉＯ６６型のＰＣＰに含まれる。 For example, the metal ion is Zr 4+ or Hf 4+ , and the PCP using a ligand of R = H in the general formula (I) is UiO66, and one or both Rs in the general formula (I) are not hydrogen Alternatively, PCP including metal ions other than Zr 4+ and Hf 4+ is included in UiO66 type PCP.
金属イオンがＡｌ３＋、Ｇａ３＋及びＩｎ３＋からなる群から選ばれる少なくとも１種であり、一般式（Ｉ）においてＲ＝Ｈの配位子を用いたＰＣＰはＭＩＬ５３であり、一般式（Ｉ）において一方又は両方のＲが水素ではないか、或いはＡｌ３＋、Ｇａ３＋及びＩｎ３＋以外の金属イオンが含まれるＰＣＰはＭＩＬ５３型のＰＣＰに含まれる。 The metal ion is at least one selected from the group consisting of Al 3+ , Ga 3+ and In 3+ , and in the general formula (I), PCP using a ligand of R = H is MIL53, and the general formula (I) In PCM, one or both Rs are not hydrogen, or PCPs containing metal ions other than Al 3+ , Ga 3+ and In 3+ are included in MIL53 type PCPs.
金属イオンがＣｒ３＋、Ｍｏ３＋及びＷ３＋からなる群から選ばれる少なくとも１種であり、一般式（Ｉ）においてＲ＝Ｈの配位子を用いたＰＣＰはＭＩＬ１０１であり、一般式（Ｉ）において一方又は両方のＲが水素ではないか、或いはＣｒ３＋、Ｍｏ３＋及びＷ３＋以外の金属イオンが含まれるＰＣＰはＭＩＬ１０１型のＰＣＰに含まれる。 The metal ion is at least one selected from the group consisting of Cr 3+ , Mo 3+ and W 3+ , and in the general formula (I), PCP using a ligand of R = H is MIL101, and the general formula (I) In PCL, one or both Rs are not hydrogen, or PCP containing metal ions other than Cr 3+ , Mo 3+ and W 3+ is included in MIL101 type PCP.
金属イオンがＺｎ２＋、Ｃｄ２＋及びＨｇ２＋からなる群から選ばれる少なくとも１種であり、一般式（Ｉ）においてＲ＝Ｈの配位子を用いたＰＣＰはＺＩＦ８であり、一般式（Ｉ）において一方又は両方のＲが水素ではないか、或いはＺｎ２＋、Ｃｄ２＋及びＨｇ２＋以外の金属イオンが含まれるＰＣＰはＺＩＦ８型のＰＣＰに含まれる。 The metal ion is at least one selected from the group consisting of Zn 2+ , Cd 2+ and Hg 2+ , and in the general formula (I), PCP using a ligand of R = H is ZIF8, and the general formula (I) In PCF, one or both Rs are not hydrogen, or a PCP containing metal ions other than Zn 2+ , Cd 2+ and Hg 2+ is included in the ZIF8 type PCP.
一般式（Ｉ）の配位子において、好ましいＲはＣＯＯＨであり、一方のＲが水素原子であり、他方のＲがＣＯＯＨである配位子（１，２，４-ベンゼントリカルボン酸）がより好ましい。 In the ligand of the general formula (I), a preferable R is COOH, and a ligand (1,2,4-benzenetricarboxylic acid) in which one R is a hydrogen atom and the other R is COOH is more preferable. preferable.
ＰＣＰと銅系微粒子の重量比率は、好ましくはＰＣＰ：銅系微粒子＝９５〜６５：５〜３５であり、より好ましくは９０〜７０：１０〜３０であり、さらに好ましくは８５〜７５：１５〜２５である。銅系微粒子の割合が低すぎるとメタノールの製造効率が低下し、銅系微粒子の比率が大きすぎると複合錯体の耐熱性が低下する。 The weight ratio of PCP and copper-based fine particles is preferably PCP: copper-based fine particles = 95 to 65: 5-35, more preferably 90 to 70:10 to 30, and still more preferably 85 to 75:15. 25. If the ratio of the copper-based fine particles is too low, the production efficiency of methanol decreases, and if the ratio of the copper-based fine particles is too large, the heat resistance of the composite complex decreases.
ＰＣＰは公知であるか、公知の方法に従い容易に製造でき、例えば、ＺｒＣｌ４、ＨｆＣｌ４、ＡｌＣｌ３、ＧａＣｌ３、ＩｎＣｌ３などの水溶性の金属化合物１モルに対し一般式（Ｉ）の配位子を２モル程度〜過剰量使用し、水溶液中で１〜４８時間反応させることでＰＣＰを得ることができる。 PCP is known or can be easily produced according to a known method. For example, a compound of the general formula (I) is added to 1 mol of a water-soluble metal compound such as ZrCl 4 , HfCl 4 , AlCl 3 , GaCl 3 , InCl 3. PCP can be obtained by using a ligand in an amount of about 2 mol to an excess amount and reacting in an aqueous solution for 1 to 48 hours.
銅系微粒子のＰＣＰへの担持は、例えばＣｕ（ａｃａｃ）２のアセトン溶液にＰＣＰを加えて撹拌し、減圧乾固した後、２５０〜５００℃、好ましくは３５０℃で真空下に１０分間〜１０時間加熱することにより行うことができる。ａｃａｃはアセチルアセトンである。 For supporting copper fine particles on PCP, for example, PCP is added to an acetone solution of Cu (acac) 2 and stirred and dried under reduced pressure, and then 250 to 500 ° C., preferably 350 ° C. under vacuum for 10 minutes to 10 minutes. This can be done by heating for a period of time. acac is acetylacetone.
或いは、ＰＣＰを構成する金属イオンのアセチルアセトン（ａｃａｃ）錯体とＰＣＰを構成する配位子を含む溶液に酸化銅系微粒子を混合し、噴霧反応を行って酸化銅系微粒子をＰＣＰに担持させ、乾燥後、酸化銅を水素の存在下で１００〜２５０℃で１０分間〜１０時間加熱することにより銅に還元して銅系微粒子をＰＣＰに担持した複合触媒を得ることができる。銅系微粒子が酸化亜鉛に銅を担持した微粒子（Ｃｕ／ＺｎＯ）の製造方法を図９に示す。 Alternatively, copper oxide fine particles are mixed in a solution containing an acetylacetone (acac) complex of metal ions constituting PCP and a ligand constituting PCP, and a spray reaction is performed to support the copper oxide fine particles on PCP, followed by drying. Then, the copper oxide is reduced to copper by heating at 100 to 250 ° C. for 10 minutes to 10 hours in the presence of hydrogen to obtain a composite catalyst in which copper-based fine particles are supported on PCP. FIG. 9 shows a method for producing fine particles (Cu / ZnO) in which copper fine particles carry copper on zinc oxide.
メタノールの製造は、水素と二酸化炭素を含む混合ガス（さらに一酸化炭素を含んでいてもよい）を本発明の複合触媒と接触させることにより行うことができる。反応温度は１５０〜３００℃程度、好ましくは２００〜２５０℃程度である。圧力は１〜５気圧程度、好ましくは１〜３気圧程度である。混合ガスの流速は、1〜10000ｍｌ／ｍｉｎ程度、好ましくは1〜1000ｍｌ／ｍｉｎ程度、より好ましくは1〜200ｍｌ／ｍｉｎ程度である。 Methanol can be produced by bringing a mixed gas containing hydrogen and carbon dioxide (which may further contain carbon monoxide) into contact with the composite catalyst of the present invention. The reaction temperature is about 150 to 300 ° C, preferably about 200 to 250 ° C. The pressure is about 1 to 5 atmospheres, preferably about 1 to 3 atmospheres. The flow rate of the mixed gas is about 1 to 10000 ml / min, preferably about 1 to 1000 ml / min, more preferably about 1 to 200 ml / min.
以下、本発明を実施例に基づきより詳細に説明するが、本発明がこれら実施例に限定されないことはいうまでもない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, it cannot be overemphasized that this invention is not limited to these Examples.
実施例で使用したＰＣＰであるＭＩＬ１０１（Ｃｒ３＋とテレフタル酸），ＭＩＬ５３（Ａｌ３＋とテレフタル酸），ＺＩＦ８（Ｚｎ２＋と２−メチルイミダゾール）、ＭＯＦ７４及びＵｉＯ６６は、以下の論文に記載の方法に従って入手した：
MIL101論文名：Science 2005, 309, 2040-2042
MIL53論文名：Chem. Eur. J. 2004, 10, 1373-1382.
ZIF8論文名：PNAS 2006, 103, 10186-10191.
MOF74論文名：J. Am. Chem. Soc. 2008, 130, 10870-10871.
UiO-66論文名：Chem. Eur. J. 2011, 17, 6643-6651、Chem. Commun., 2013, 49, 3634-3636；
Chem. Commun., 2013, 49, 9449-9451；Angew. Chem. Int. Ed. 2013, 52, 10316-10320
MIL101 (Cr 3+ and terephthalic acid), MIL53 (Al 3+ and terephthalic acid), ZIF8 (Zn 2+ and 2-methylimidazole), MOF74 and UiO66 used in the examples are in accordance with the methods described in the following papers. obtained:
MIL101 paper title: Science 2005, 309, 2040-2042
MIL53 paper title: Chem. Eur. J. 2004, 10, 1373-1382.
ZIF8 paper title: PNAS 2006, 103, 10186-10191.
MOF74 paper title: J. Am. Chem. Soc. 2008, 130, 10870-10871.
UiO-66 title: Chem. Eur. J. 2011, 17, 6643-6651, Chem. Commun., 2013, 49, 3634-3636;
Chem. Commun., 2013, 49, 9449-9451; Angew. Chem. Int. Ed. 2013, 52, 10316-10320
実施例１−２及び比較例１−３
０．８２ｇのＣｕ（ａｃａｃ）２のアセトン（１００ｍｌ）溶液にＰＣＰ（ＵｉＯ６６（Ｚｒ）、ＭＩＬ５３、ＭＩＬ１０１又はＺＩＦ８）１ｇを加えて室温で撹拌し、その後アセトンを蒸発乾固により除いた。得られた残渣を３５０℃で１時間加熱することによりＣｕ（ａｃａｃ）２を熱分解し、ＰＣＰにＣｕナノ粒子が担持した複合触媒（ＵｉＯ６６（Ｚｒ）−Ｃｕ、ＭＩＬ５３−Ｃｕ、ＭＩＬ１０１−Ｃｕ又はＺＩＦ８−Ｃｕ）を得た。ＰＣＰに代えてγＡｌ２Ｏ３を使用した以外は上記と同様にしてγＡｌ２Ｏ３−Ｃｕを得た。Ｃｕは複合触媒に約２０質量％含まれていた。
Example 1-2 and Comparative Example 1-3
1 g of PCP (UiO66 (Zr), MIL53, MIL101 or ZIF8) was added to 0.82 g of a solution of Cu (acac) 2 in acetone (100 ml) and stirred at room temperature, and then acetone was removed by evaporation to dryness. The obtained residue was heated at 350 ° C. for 1 hour to thermally decompose Cu (acac) 2 , and a composite catalyst (UiO66 (Zr) -Cu, MIL53-Cu, MIL101-Cu or ZIF8-Cu) was obtained. Except using γAl 2 O 3 in place of the PCP got γAl 2 O 3 -Cu in the same manner as described above. Cu was contained in the composite catalyst in an amount of about 20% by mass.
Ｃｕの結晶子サイズを以下に示し、粉末Ｘ線回折パターンを図１に示す。
ＵｉＯ６６（Ｚｒ）−Ｃｕ（実施例１）：３０（１）ｎｍ、表面原子数割合：５％
ＭＩＬ５３−Ｃｕ（実施例２）：３２（１）ｎｍ、表面原子数割合：４．７％
ＭＩＬ１０１−Ｃｕ（比較例１）：３５．９（４）ｎｍ、表面原子数割合：４．２％
ＺＩＦ８−Ｃｕ（比較例２） ：２８（３）ｎｍ、表面原子数割合：５．４％
γＡｌ２Ｏ３−Ｃｕ（比較例３）：２９（１）ｎｍ、表面原子数割合：５．２％
The crystallite size of Cu is shown below, and the powder X-ray diffraction pattern is shown in FIG.
UiO66 (Zr) -Cu (Example 1): 30 (1) nm, surface atom number ratio: 5%
MIL53-Cu (Example 2): 32 (1) nm, surface atom number ratio: 4.7%
MIL101-Cu (Comparative Example 1): 35.9 (4) nm, surface atom number ratio: 4.2%
ZIF8-Cu (Comparative Example 2): 28 (3) nm, surface atom number ratio: 5.4%
γAl 2 O 3 —Cu (Comparative Example 3): 29 (1) nm, surface atom number ratio: 5.2%
図１により複合触媒（ＵｉＯ６６（Ｚｒ）−Ｃｕ、ＭＩＬ５３−Ｃｕ、ＭＩＬ１０１−Ｃｕ又はＺＩＦ８−Ｃｕ）はＰＣＰの構造が保持されていることが確認された。 From FIG. 1, it was confirmed that the composite catalyst (UiO66 (Zr) -Cu, MIL53-Cu, MIL101-Cu or ZIF8-Cu) retained the PCP structure.
また、複合触媒（ＵｉＯ６６（Ｚｒ）−Ｃｕ、ＭＩＬ５３−Ｃｕ、ＭＩＬ１０１−Ｃｕ又はＺＩＦ８−Ｃｕ）及びγＡｌ２Ｏ３−ＣｕのＴＥＭ像を図２に示す。 A TEM image of the composite catalyst (UiO66 (Zr) -Cu, MIL53-Cu, MIL101-Cu or ZIF8-Cu) and γAl 2 O 3 -Cu is shown in FIG.
試験例１
実施例１−２、比較例１−３で得られた複合触媒（ＵｉＯ６６（Ｚｒ）−Ｃｕ、ＭＩＬ５３−Ｃｕ、ＭＩＬ１０１−Ｃｕ、ＺＩＦ８−Ｃｕ及びγＡｌ２Ｏ３−Ｃｕ）と図３に示す固定床流通式反応装置を用い、以下の反応条件でメタノールの製造を行った。
サンプル（触媒）量：０．７ｇ〜１ｇ
混合ガス：ＣＯ２／ＣＯ／Ｈ２／Ｈｅ
反応条件：２２０℃、２ａｔｍ、１０ｍｌ／ｍｉｎ
Test example 1
Example 1-2, the resulting composite catalyst in Comparative Example 1-3 a fixed bed flow shown in (UiO66 (Zr) -Cu, MIL53 -Cu, MIL101-Cu, ZIF8-Cu and γAl2O 3 -Cu) and 3 Methanol was produced under the following reaction conditions using a chemical reactor.
Sample (catalyst) amount: 0.7 g to 1 g
Mixed gas: CO 2 / CO / H 2 / He
Reaction conditions: 220 ° C., 2 atm, 10 ml / min
得られた混合ガスのＧＣチャート及び保持時間５．９〜６分のメタノール成分の結果を図４に示す。図４の結果から、ＰＣＰ成分により銅ナノ粒子の触媒活性は大きく異なり、ＵｉＯ６６（Ｚｒ）−ＣｕとＭＩＬ５３−Ｃｕが好ましく、ＵｉＯ６６（Ｚｒ）−Ｃｕが特に好ましいことが明らかになった。 FIG. 4 shows a GC chart of the obtained mixed gas and a methanol component result having a retention time of 5.9 to 6 minutes. From the results of FIG. 4, it was found that the catalytic activity of the copper nanoparticles varies greatly depending on the PCP component, UiO66 (Zr) -Cu and MIL53-Cu are preferable, and UiO66 (Zr) -Cu is particularly preferable.
なお、上記のメタノール製造触媒反応後、ＰＣＰの骨格が維持されていることを粉末Ｘ線パターンで確認した。また、ＴＥＭ観察によりメタノール製造触媒反応前後で粒径が変化していないことを確認した。 After the above methanol production catalyst reaction, it was confirmed by a powder X-ray pattern that the skeleton of PCP was maintained. Moreover, it was confirmed by TEM observation that the particle size did not change before and after the methanol production catalyst reaction.
試験例２
実施例１、比較例２−３で得られた複合触媒（ＵｉＯ６６（Ｚｒ）−Ｃｕ、ＺＩＦ８−Ｃｕ及びγＡｌ２Ｏ３−Ｃｕ）と図３に示す固定床流通式反応装置を用い、以下の反応条件でメタノールの製造を行った。
サンプル（触媒）量：０．５ｇ
混合ガス：ＣＯ２／Ｈ２／Ｈｅ
反応条件：２２０℃、２ａｔｍ、１４、４９、９８又は１４０ｍｌ／ｍｉｎ
Test example 2
Example 1, the composite catalyst obtained in Comparative Example 2-3 (UiO66 (Zr) -Cu, ZIF8-Cu and γAl2O 3 -Cu) using a fixed bed flow reaction apparatus shown in FIG. 3, the following reaction conditions The methanol was produced.
Sample (catalyst) amount: 0.5 g
Mixed gas: CO 2 / H 2 / He
Reaction conditions: 220 ° C., 2 atm, 14, 49, 98 or 140 ml / min
得られた混合ガスのＧＣチャート及びＵｉＯ６６（Ｚｒ）−Ｃｕ（ＭｅＯＨの生成量とＧＣチャート内の生成物に対する選択率）を図５に示す。図５に示すように、ＵｉＯ６６（Ｚｒ）−Ｃｕがメタノール製造用複合触媒として高い活性を有し、流速を高くすることでＭＴＯ反応の進行を抑制し、ＭｅＯＨの高い生成量と選択率を達成できることが考えられる。 FIG. 5 shows a GC chart of the obtained mixed gas and UiO66 (Zr) -Cu (the amount of MeOH produced and the selectivity with respect to the product in the GC chart). As shown in FIG. 5, UiO66 (Zr) -Cu has high activity as a composite catalyst for methanol production, and by increasing the flow rate, the progress of the MTO reaction is suppressed, and a high production amount and selectivity of MeOH are achieved. It is possible to do it.
比較例４
MOF-74（Mg2(DOBDC)、H2DOBDC=2,5-ジヒドロキシテレフタル酸)とＣｕ（ａｃａｃ）２のアセトン溶液を用い、実施例１と同様にしてＭＯＦ７４（Ｍｇ）−Ｃｕ複合触媒を得た。Ｃｕは複合触媒に約２０質量％含まれていた。
Comparative Example 4
MOF-74 (Mg 2 (DOBDC), H 2 DOBDC = 2,5-dihydroxyterephthalic acid) and an acetone solution of Cu (acac) 2 were used in the same manner as in Example 1 to prepare a MOF 74 (Mg) -Cu composite catalyst. Obtained. Cu was contained in the composite catalyst in an amount of about 20% by mass.
試験例３
ＵｉＯ６６−Ｃｕ、ＺＩＦ８−Ｃｕ及びＭＯＦ７４（Ｍｇ）−Ｃｕを用い、以下の反応条件でメタノールの製造を行った。
サンプル（触媒）量：０．５ｇ
混合ガス：ＣＯ２／Ｈ２／Ｈｅ
反応条件：２２０℃、２ａｔｍ、１４、４９、９８、１４０ｍｌ／ｍｉｎ
Test example 3
Using UiO66-Cu, ZIF8-Cu and MOF74 (Mg) -Cu, methanol was produced under the following reaction conditions.
Sample (catalyst) amount: 0.5 g
Mixed gas: CO 2 / H 2 / He
Reaction conditions: 220 ° C., 2 atm, 14, 49, 98, 140 ml / min
得られた混合ガスのＧＣチャート及びＵｉＯ６６（Ｚｒ）−ＣｕとＭＯＦ７４（Ｍｇ）−Ｃｕによるメタノール生成量の比較を図６に示す。 FIG. 6 shows a GC chart of the obtained mixed gas and a comparison of the amount of methanol produced by UiO66 (Zr) -Cu and MOF74 (Mg) -Cu.
ＭＯＦ７４（Ｍｇ）は二酸化炭素を多量に吸着する触媒であるがメタノールの生成量は非常に少なく、二酸化炭素の吸着量と触媒活性の相関はほとんどないことが確認された。 Although MOF74 (Mg) is a catalyst that adsorbs a large amount of carbon dioxide, the amount of methanol produced was very small, and it was confirmed that there was almost no correlation between the amount of carbon dioxide adsorbed and the catalytic activity.
実施例３−４及び比較例５
一般式（Ｉ）で表される配位子として、Ｒ＝ＮＨ２（実施例３）、Ｒ＝ＣＯＯＨ（実施例４）、Ｒ＝ＯＨ（比較例５）の化合物を用い、実施例１と同様にしてＵｉＯ６６（ＮＨ２）−Ｃｕ、ＵｉＯ６６（ＣＯＯＨ）−Ｃｕ、ＵｉＯ６６（ＯＨ）−Ｃｕを得た。得られた複合触媒のＴＥＭ像を図７に示す。なお、ＵｉＯ６６はＵｉＯ６６（Ｚｒ）である。
Example 3-4 and Comparative Example 5
As the ligand represented by the general formula (I), compounds of R = NH 2 (Example 3), R = COOH (Example 4), R = OH (Comparative Example 5) were used. Similarly UiO66 (NH 2) -Cu, UiO66 (COOH) -Cu, was obtained UiO66 (OH) -Cu. A TEM image of the obtained composite catalyst is shown in FIG. UiO66 is UiO66 (Zr).
試験例４
ＵｉＯ６６（Ｈ）−Ｃｕ、ＵｉＯ６６（ＮＨ２）−Ｃｕ、ＵｉＯ６６（ＣＯＯＨ）−Ｃｕ、ＵｉＯ６６（ＯＨ）−Ｃｕを用い、以下の反応条件でメタノールの製造を行った。なお、ＵｉＯ６６はＵｉＯ６６（Ｚｒ）である。
サンプル（触媒）量：０．５ｇ
混合ガス：ＣＯ２／Ｈ２／Ｈｅ
反応条件：２２０℃、２ａｔｍ、１４、４９、９８、１４０ｍｌ／ｍｉｎ
Test example 4
UiO66 (H) -Cu, UiO66 ( NH 2) -Cu, UiO66 (COOH) -Cu, using UiO66 (OH) -Cu, was produced methanol the following reaction conditions. UiO66 is UiO66 (Zr).
Sample (catalyst) amount: 0.5 g
Mixed gas: CO 2 / H 2 / He
Reaction conditions: 220 ° C., 2 atm, 14, 49, 98, 140 ml / min
得られた混合ガス中のメタノールの生成量を示すＧＣチャート及びメタノールの選択率の結果を図８に示す。 FIG. 8 shows the GC chart showing the amount of methanol produced in the obtained mixed gas and the result of methanol selectivity.
図８の結果から、ＵｉＯ６６（ＣＯＯＨ）−Ｃｕがメタノール製造用触媒として特に優れていることが明らかになった。 From the results of FIG. 8, it was revealed that UiO66 (COOH) -Cu is particularly excellent as a catalyst for methanol production.
なお、上記のメタノール製造触媒反応後、ＰＣＰの骨格が維持されていることを粉末Ｘ線パターンで確認した。 After the above methanol production catalyst reaction, it was confirmed by a powder X-ray pattern that the skeleton of PCP was maintained.
実施例６
ＵｉＯ６６（Ｚｒ）に代えてＵｉＯ６６（Ｈｆ）を用いる以外は実施例１と同様にしてＵｉＯ６６（Ｈｆ）−Ｃｕを得た。
Example 6
UiO66 (Hf) -Cu was obtained in the same manner as in Example 1 except that UiO66 (Hf) was used instead of UiO66 (Zr).
試験例５
実施例１のＵｉＯ６６（Ｚｒ）と実施例６のＵｉＯ６６（Ｈｆ）を用い、試験例２と同様にしてメタノールを製造した。結果を図９に示す。図９に示されるように、ＵｉＯ６６（Ｈｆ）はＵｉＯ６６（Ｚｒ）よりもメタノールを約３倍多く生成することが明らかになった。
Test Example 5
Using UiO66 (Zr) of Example 1 and UiO66 (Hf) of Example 6, methanol was produced in the same manner as in Test Example 2. The results are shown in FIG. As shown in FIG. 9, it was revealed that UiO66 (Hf) produces about three times more methanol than UiO66 (Zr).
実施例６及び比較例６
二元系触媒Ｃｕ／ＺｎＯとＰＣＰ（ＵｉＯ−６６）との噴霧反応法による複合化を行った。
Example 6 and Comparative Example 6
The binary catalyst Cu / ZnO and PCP (UiO-66) were combined by a spray reaction method.
図１０に示されるように、Ｚｒ（ａｃａｃ）２（1.22ｇ）と１，４−ベンゼンジカルボン酸(1,4-bdc)（0.42ｇ）の水溶液にＣｕＯ／ＺｎＯ複合酸化物のスラリー（1.35ｇ）を加え、噴霧反応（220℃、空気中）を行い、減圧乾燥してＣｕＯ／ＺｎＯ複合酸化物を担持したＵｉＯ６６を得た。これを水素存在下で２００℃で加熱することによりＣｕＯをＣｕに還元してＣｕ／ＺｎＯからなる銅系微粒子を担持したＵｉＯ６６複合触媒を得た。 As shown in FIG. 10, a CuO / ZnO composite oxide slurry (1.35 g) in an aqueous solution of Zr (acac) 2 (1.22 g) and 1,4-benzenedicarboxylic acid (1,4-bdc) (0.42 g) was used. ) Was added, a spray reaction (220 ° C., in air) was performed, and dried under reduced pressure to obtain UiO66 carrying a CuO / ZnO composite oxide. By heating this at 200 ° C. in the presence of hydrogen, CuO was reduced to Cu to obtain a UiO66 composite catalyst carrying copper-based fine particles made of Cu / ZnO.
ＣｕＯ／ＺｎＯ複合酸化物は、Ｃｕ（ＮＯ３）２とＺｎ（ＮＯ３）２をＣｕ：Ｚｎ＝２２:１８，２３：１８、５:３２，２０:５，５：３３になるような比率で配合し、噴霧熱分解（８５０℃、空気中）を行うことで得た。ＣｕＯ／ＺｎＯ複合酸化物の平均粒径は約20-30nmであった。 The CuO / ZnO composite oxide has a ratio of Cu (NO 3 ) 2 and Zn (NO 3 ) 2 such that Cu: Zn = 22: 18, 23:18, 5:32, 20: 5, 5:33. And spray pyrolysis (850 ° C., in air). The average particle size of the CuO / ZnO composite oxide was about 20-30 nm.
ＣｕＯ／ＺｎＯ複合酸化物をγ−Ａｌ２Ｏ３に担持した複合触媒を得た（比較例６）。 A composite catalyst in which a CuO / ZnO composite oxide was supported on γ-Al 2 O 3 was obtained (Comparative Example 6).
試験例６
実施例６及び比較例６で得られた複合触媒を用いて試験例１と同様にメタノールの製造を行った。結果を図１１に示す。
Test Example 6
Methanol was produced in the same manner as in Test Example 1 using the composite catalyst obtained in Example 6 and Comparative Example 6. The results are shown in FIG.
Claims (9)
で表される、メタノール製造用複合触媒。 A composite catalyst for methanol production in which copper-based fine particles are supported on a porous coordination polymer (PCP), wherein the PCP is a UiO66 type PCP or a MIL53 type PCP, and a metal ion constituting the PCP is Zr 4+ Including at least one selected from the group consisting of Hf 4+ , Al 3+ , Ga 3+ and In 3+, the ligand constituting the PCP is represented by the following formula (I)
The composite catalyst for methanol manufacture represented by these.
で表される、請求項１又は２に記載のメタノール製造用複合触媒。 The ligand constituting PCP is represented by the following formula (IA)
The composite catalyst for methanol production of Claim 1 or 2 represented by these.
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