JP5827832B2 - Iridium-rhenium solid catalyst - Google Patents
Iridium-rhenium solid catalyst Download PDFInfo
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- JP5827832B2 JP5827832B2 JP2011151438A JP2011151438A JP5827832B2 JP 5827832 B2 JP5827832 B2 JP 5827832B2 JP 2011151438 A JP2011151438 A JP 2011151438A JP 2011151438 A JP2011151438 A JP 2011151438A JP 5827832 B2 JP5827832 B2 JP 5827832B2
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- iridium
- rhenium
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- silicon dioxide
- glycerin
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- YEWLVPDHCCERJH-UHFFFAOYSA-N [Re].[Ir] Chemical compound [Re].[Ir] YEWLVPDHCCERJH-UHFFFAOYSA-N 0.000 title claims description 27
- 239000011949 solid catalyst Substances 0.000 title claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 78
- 239000003054 catalyst Substances 0.000 claims description 60
- 239000000377 silicon dioxide Substances 0.000 claims description 39
- 229910052741 iridium Inorganic materials 0.000 claims description 37
- 235000012239 silicon dioxide Nutrition 0.000 claims description 37
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 36
- 229910052702 rhenium Inorganic materials 0.000 claims description 32
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 239000011148 porous material Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 150000002504 iridium compounds Chemical class 0.000 claims description 8
- 150000003282 rhenium compounds Chemical class 0.000 claims description 8
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims 1
- 229920001515 polyalkylene glycol Polymers 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 148
- 235000011187 glycerol Nutrition 0.000 description 68
- 238000006243 chemical reaction Methods 0.000 description 59
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 29
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 26
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 25
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 25
- 229940035437 1,3-propanediol Drugs 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 25
- 229910052739 hydrogen Inorganic materials 0.000 description 25
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 25
- 239000000243 solution Substances 0.000 description 23
- 230000003197 catalytic effect Effects 0.000 description 21
- 230000007423 decrease Effects 0.000 description 13
- 229910004298 SiO 2 Inorganic materials 0.000 description 11
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 235000013772 propylene glycol Nutrition 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000010828 elution Methods 0.000 description 5
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- -1 For example Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 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
Description
本発明は、イリジウム−レニウム固体触媒に関する。より詳細には、二酸化ケイ素（シリカ）にイリジウム及びレニウムが担持されたイリジウム−レニウム固体触媒に関する。この触媒は、例えば、グリセリン等の多価アルコールの水素化反応用触媒として有用である。 The present invention relates to an iridium-rhenium solid catalyst. More specifically, the present invention relates to an iridium-rhenium solid catalyst in which iridium and rhenium are supported on silicon dioxide (silica). This catalyst is useful, for example, as a catalyst for hydrogenation reaction of polyhydric alcohols such as glycerin.
イリジウム−レニウム固体触媒の存在下、グリセリンを水素化して、１，３−プロパンジオール、１，２−プロパンジオール、１−プロパノール、２−プロパノールを製造する方法が知られている（特許文献１等）。しかしながら、従来のイリジウム−レニウム固体触媒では、触媒調製中にイリジウムが溶出又は析出したり、該触媒を用いた反応中にレニウムが溶出するため、触媒活性が不十分で、しかも触媒活性が長時間持続しないという問題があった。 A method is known in which glycerol is hydrogenated in the presence of an iridium-rhenium solid catalyst to produce 1,3-propanediol, 1,2-propanediol, 1-propanol, 2-propanol (Patent Document 1, etc.) ). However, in the conventional iridium-rhenium solid catalyst, iridium elutes or precipitates during catalyst preparation or rhenium elutes during the reaction using the catalyst, so that the catalytic activity is insufficient and the catalytic activity is long. There was a problem of not lasting.
本発明の目的は、高い触媒活性を有するとともに、反応中における触媒成分の溶出が抑制され、高い触媒活性が長時間持続するイリジウム−レニウム固体触媒を提供することにある。 An object of the present invention is to provide an iridium-rhenium solid catalyst that has high catalytic activity, suppresses elution of catalyst components during the reaction, and maintains high catalytic activity for a long time.
本発明者らは、前記目的を達成するため鋭意検討した結果、細孔径が特定範囲にある粒状の二酸化ケイ素にイリジウム及びレニウムを担持した触媒によれば、高い触媒活性が発現するとともに、その高い触媒活性が長時間持続することを見出し、本発明を完成した。 As a result of intensive studies to achieve the above object, the present inventors have demonstrated that a catalyst having iridium and rhenium supported on granular silicon dioxide having a pore diameter in a specific range exhibits high catalytic activity and high The inventors have found that the catalytic activity can be maintained for a long time, and have completed the present invention.
すなわち、本発明は、細孔径が１０ｎｍ〜５０ｎｍである粒状の二酸化ケイ素にイリジウム及びレニウムが担持されたイリジウム−レニウム固体触媒を提供する。 That is, the present invention provides an iridium-rhenium solid catalyst in which iridium and rhenium are supported on granular silicon dioxide having a pore diameter of 10 nm to 50 nm.
前記イリジウム−レニウム固体触媒において、イリジウムの担持量が二酸化ケイ素に対して、イリジウム（Ｉｒ）として０．５〜１０重量％であり、レニウムの担持量が二酸化ケイ素に対して、レニウム（Ｒｅ）として２〜１５重量％であることが好ましい。 In the iridium-rhenium solid catalyst, the supported amount of iridium is 0.5 to 10% by weight as iridium (Ir) with respect to silicon dioxide, and the supported amount of rhenium is as rhenium (Re) with respect to silicon dioxide. It is preferably 2 to 15% by weight.
また、前記イリジウム−レニウム固体触媒は、細孔径が１０ｎｍ〜５０ｎｍである粒状の二酸化ケイ素に、該二酸化ケイ素に対して５〜７０重量％のイリジウム化合物含有水溶液、及び該二酸化ケイ素に対して５〜７０重量％のレニウム化合物含有水溶液を、それぞれ、完全に吸収させて担持させる方法により調製された固体触媒であるのが好ましい。 The iridium-rhenium solid catalyst is prepared by adding 5 to 70% by weight of an iridium compound-containing aqueous solution of 5 to 70% by weight with respect to the silicon dioxide and 5 to 5% of the silicon dioxide. The solid catalyst is preferably prepared by a method in which a 70 wt% rhenium compound-containing aqueous solution is completely absorbed and supported.
前記二酸化ケイ素の細孔容積は、好ましくは０．７〜３ｍＬ／ｇである。また、前記二酸化ケイ素は、直径０．５ｍｍ〜１０ｍｍの球形であるのが好ましい。 The pore volume of the silicon dioxide is preferably 0.7 to 3 mL / g. The silicon dioxide is preferably spherical with a diameter of 0.5 mm to 10 mm.
前記イリジウム−レニウム固体触媒は、多価アルコールの水素化反応用の触媒として使用できる。 The iridium-rhenium solid catalyst can be used as a catalyst for a hydrogenation reaction of a polyhydric alcohol.
本発明のイリジウム−レニウム固体触媒は、高い触媒活性を有するとともに、反応に用いた際、触媒成分（特にレニウム成分）が溶出しにくく、高い触媒活性を長時間持続できる。 The iridium-rhenium solid catalyst of the present invention has high catalytic activity, and when used in the reaction, the catalyst component (especially rhenium component) is difficult to elute and can maintain high catalytic activity for a long time.
本発明のイリジウム−レニウム固体触媒は、細孔径が１０ｎｍ〜５０ｎｍである粒状の二酸化ケイ素（ＳｉＯ2；シリカ）にイリジウム及びレニウムが担持された触媒である。 The iridium-rhenium solid catalyst of the present invention is a catalyst in which iridium and rhenium are supported on granular silicon dioxide (SiO 2 ; silica) having a pore diameter of 10 nm to 50 nm.
担体として用いられる二酸化ケイ素の細孔径が１０ｎｍ未満であると、イリジウム成分を担持する際、該イリジウム成分が担体外に溶出又は析出して、イリジウム担持量にバラツキが生じたり、担体の細孔内に十分な量のイリジウムを担持することが困難となり、所望のイリジウム担持量を有する触媒を安定に得ることができない。また、そのような触媒では、該触媒を用いた反応中に、担持したレニウム成分が溶出しやすく、触媒活性が経時で低下する。一方、二酸化ケイ素の細孔径が５０ｎｍを超えると、担体の表面積が極度に小さくなり、十分な反応場が得られないために触媒活性が低下する。 When the pore diameter of silicon dioxide used as a support is less than 10 nm, when the iridium component is supported, the iridium component is eluted or precipitated out of the support, resulting in variations in the amount of iridium supported, Thus, it is difficult to carry a sufficient amount of iridium, and a catalyst having a desired amount of iridium cannot be obtained stably. Further, in such a catalyst, the supported rhenium component is easily eluted during the reaction using the catalyst, and the catalytic activity decreases with time. On the other hand, when the pore diameter of silicon dioxide exceeds 50 nm, the surface area of the support becomes extremely small, and a sufficient reaction field cannot be obtained, so that the catalytic activity is lowered.
担体として用いる二酸化ケイ素は粒状であればその形状は特に限定されないが、取扱性や強度、均質な触媒が得られる等の点から、球形（略球形を含む）であるのが好ましい。二酸化ケイ素の大きさは、例えば、長径［球形の場合は直径（球径）］が０．５ｍｍ〜１０ｍｍ程度、好ましくは１ｍｍ〜５ｍｍ程度である。二酸化ケイ素の大きさが小さすぎると、触媒固定床型反応器に供することができないため実用面での利用が困難になりやすく、逆に大きすぎると、触媒調製の際に触媒成分の均一な担持が困難になりやすい。 The shape of silicon dioxide used as the carrier is not particularly limited as long as it is granular, but is preferably spherical (including substantially spherical) from the viewpoints of handleability, strength, and homogeneous catalyst. As for the size of silicon dioxide, for example, the major axis [diameter (spherical diameter in the case of a sphere)] is about 0.5 mm to 10 mm, preferably about 1 mm to 5 mm. If the size of silicon dioxide is too small, it cannot be used in a catalyst fixed bed reactor, so that it is difficult to use it practically. On the other hand, if it is too large, the catalyst components are uniformly supported during catalyst preparation. Tends to be difficult.
前記二酸化ケイ素の細孔容積は、一般には０．７〜３ｍＬ／ｇ、好ましくは０．８〜２ｍＬ／ｇ、さらに好ましくは０．９〜１．５ｍＬ／ｇである。細孔容積が小さすぎる場合には、触媒活性が低かったり、触媒活性の持続性が低下しやすくなる。また、細孔容積が大きすぎると、触媒の機械的強度が低下しやすくなる。 The pore volume of the silicon dioxide is generally 0.7 to 3 mL / g, preferably 0.8 to 2 mL / g, and more preferably 0.9 to 1.5 mL / g. When the pore volume is too small, the catalytic activity is low or the sustainability of the catalytic activity tends to decrease. On the other hand, if the pore volume is too large, the mechanical strength of the catalyst tends to decrease.
本発明のイリジウム−レニウム固体触媒において、イリジウムの担持量は、担体である二酸化ケイ素に対して、Ｉｒとして、０．５〜１０重量％、好ましくは１〜６重量％、さらに好ましくは２〜５重量％である。また、レニウムの担持量は、担体である二酸化ケイ素に対して、Ｒｅとして、２〜１５重量％、好ましくは３〜１２重量％、さらに好ましくは４〜１０重量％である。イリジウムの担持量が少なすぎると、触媒活性が低下しやすく、またレニウムの溶出を促進しやすくなり、逆に担持量が多すぎると、金属量当たりの活性が低くなり、高価なイリジウムを用いる面では不利になりやすい。また、レニウムの担持量が少なすぎると、触媒活性が低下しやすくなり、逆に多すぎると、イリジウムの活性点を覆う結果となり、かえって触媒活性が低下する場合がある。イリジウム及びレニウムは、それぞれ、金属単体として担持されていてもよく、金属酸化物等の金属化合物として担持されていてもよい。 In the iridium-rhenium solid catalyst of the present invention, the supported amount of iridium is 0.5 to 10% by weight, preferably 1 to 6% by weight, more preferably 2 to 5% as Ir with respect to silicon dioxide as a support. % By weight. The supported amount of rhenium is 2 to 15% by weight, preferably 3 to 12% by weight, and more preferably 4 to 10% by weight as Re with respect to silicon dioxide as a carrier. If the amount of iridium supported is too small, the catalytic activity tends to decrease and the elution of rhenium tends to be promoted. On the other hand, if the amount supported is too large, the activity per metal amount decreases, and expensive iridium is used. Then it tends to be disadvantageous. On the other hand, if the amount of rhenium supported is too small, the catalytic activity tends to decrease. On the other hand, if the amount is too large, the active point of iridium may be covered, and the catalytic activity may decrease. Each of iridium and rhenium may be supported as a single metal or may be supported as a metal compound such as a metal oxide.
レニウムとイリジウムの担持比率としては、特に限定されないが、Ｒｅ／Ｉｒ（モル比）として、通常、１／１０〜１０／１、好ましくは１／２〜７／２、さらに好ましくは１／１〜３／１である。前記の比率が大きすぎると、例えば、本発明の触媒をグリセリンの水素化反応に用いた場合には、１，３−プロパンジオールや１，２−プロパンジオールの選択率が低下し、１−プロパノールや２−プロパノールの選択率が高くなる傾向となる。また、逆に前記の比率が小さすぎると、例えば、本発明の触媒をグリセリンの水素化反応に用いた場合には、１，３−プロパンジオールの選択率は向上するが、触媒活性が低くなり、グリセリンの転化が進みにくくなる。 The loading ratio of rhenium and iridium is not particularly limited, but as Re / Ir (molar ratio), it is usually 1/10 to 10/1, preferably 1/2 to 7/2, more preferably 1/1 to 3/1. If the ratio is too large, for example, when the catalyst of the present invention is used in a hydrogenation reaction of glycerin, the selectivity of 1,3-propanediol or 1,2-propanediol decreases, and 1-propanol And the selectivity of 2-propanol tends to be high. On the other hand, if the ratio is too small, for example, when the catalyst of the present invention is used for the hydrogenation reaction of glycerol, the selectivity of 1,3-propanediol is improved, but the catalytic activity is lowered. The conversion of glycerin is difficult to proceed.
本発明のイリジウム−レニウム固体触媒の調製法としては、特に限定されず、例えば、担体である粒状の二酸化ケイ素にイリジウム化合物含有水溶液を含浸させた後、減圧あるいは常圧で乾燥し、必要に応じて焼成及び／又は水素等による還元処理を施した後、レニウム化合物含有水溶液を含浸させ、減圧あるいは常圧で乾燥し、必要に応じて焼成することにより調製できる。また、その後、必要に応じて、水素等により還元処理してもよい。なお、先にレニウムの担持を行い、次いでイリジウムを担持する方法や、イリジウムの担持とレニウムの担持とを同時に行う方法を採用することもできるが、先にイリジウムを担持し、次いでレニウムを担持する方法が、触媒活性及び触媒活性の持続性の点から好ましい。 The method for preparing the iridium-rhenium solid catalyst of the present invention is not particularly limited. For example, after impregnating granular silicon dioxide as a support with an iridium compound-containing aqueous solution, drying is performed under reduced pressure or normal pressure, and as necessary. It is prepared by impregnating a rhenium compound-containing aqueous solution, drying it under reduced pressure or normal pressure, and firing it as necessary. Thereafter, reduction treatment with hydrogen or the like may be performed as necessary. In addition, it is possible to adopt a method in which rhenium is first supported and then iridium is supported, or a method in which iridium and rhenium are simultaneously supported. However, iridium is first supported and then rhenium is supported. The method is preferable from the viewpoint of catalytic activity and sustainability of catalytic activity.
前記イリジウム化合物含有水溶液としては、公知のイリジウム化合物の水溶液、例えば、塩化イリジウム酸水溶液を使用できる。また、前記レニウム化合物含有水溶液としては、公知のレニウム化合物の水溶液、例えば、過レニウム酸アンモニウム水溶液を使用できる。前記乾燥時の温度としては、例えば、７０〜１５０℃、好ましくは９０〜１３０℃である。また、前記焼成時の温度としては、例えば、４００〜７５０℃、好ましくは４５０〜６００℃である。焼成は、空気雰囲気下、窒素やアルゴン等の不活性ガス雰囲気下、水素等の還元性ガス雰囲気下のいずれであってもよい。 As the iridium compound-containing aqueous solution, a known aqueous solution of an iridium compound, for example, a chloroiridic acid aqueous solution can be used. Moreover, as said rhenium compound containing aqueous solution, the aqueous solution of a well-known rhenium compound, for example, ammonium perrhenate aqueous solution, can be used. As temperature at the time of the said drying, it is 70-150 degreeC, for example, Preferably it is 90-130 degreeC. Moreover, as temperature at the time of the said baking, it is 400-750 degreeC, for example, Preferably it is 450-600 degreeC. Firing may be performed in an air atmosphere, an inert gas atmosphere such as nitrogen or argon, or a reducing gas atmosphere such as hydrogen.
本発明のイリジウム−レニウム固体触媒としては、二酸化ケイ素担体の細孔にて生じる毛細管現象を利用したいわゆるポアフィリング法により調製されたものが好ましい。より具体的には、前記担体である粒状の二酸化ケイ素に、該二酸化ケイ素の細孔容積よりも少ない量のイリジウム化合物含有水溶液（例えば、該二酸化ケイ素に対して、５〜７０重量％、好ましくは８〜５０重量％、さらに好ましくは１０〜３０重量％のイリジウム化合物含有水溶液）、及び該二酸化ケイ素の細孔容積よりも少ない量のレニウム化合物含有水溶液（例えば、該二酸化ケイ素に対して、５〜７０重量％、好ましくは８〜５０重量％、さらに好ましくは１０〜３０重量％のレニウム化合物含有水溶液）を、それぞれ、完全に吸収させて担持させる方法により調製された固体触媒であるのが好ましい。なお、前記「完全に」とは、厳密に１００％という意味ではなく、ほぼ完全に吸収されていればよく、例えば容器等に微量の液滴が付着している場合を除外するものではない。 As the iridium-rhenium solid catalyst of the present invention, a catalyst prepared by a so-called pore filling method utilizing a capillary phenomenon generated in the pores of a silicon dioxide support is preferable. More specifically, to the granular silicon dioxide as the carrier, an aqueous solution containing an iridium compound in an amount smaller than the pore volume of the silicon dioxide (for example, 5 to 70% by weight, preferably 8 to 50% by weight, more preferably 10 to 30% by weight of an iridium compound-containing aqueous solution), and a rhenium compound-containing aqueous solution in an amount smaller than the pore volume of the silicon dioxide (for example, 70% by weight, preferably 8 to 50% by weight, more preferably 10 to 30% by weight of the rhenium compound-containing aqueous solution) is preferably a solid catalyst prepared by a method of completely absorbing and supporting each. Note that the term “completely” does not mean strictly 100%, and it is sufficient that the liquid is almost completely absorbed. For example, it does not exclude the case where a small amount of liquid droplets are attached to a container or the like.
イリジウム及びレニウムを担体に担持するときに用いる触媒成分含有水溶液（イリジウム化合物含有水溶液、レニウム化合物含有水溶液）の液量を少なくして、二酸化ケイ素担体の細孔容積よりも少ない量の触媒成分含有水溶液を用い、触媒成分含有水溶液を担体に完全に吸収させて担持させることにより、触媒調製時におけるイリジウム成分等の溶出、析出を防止することができる。また、所定量の触媒成分を設計値通り確実に、しかも均一に担体の細孔内に担持させることができる。このような方法で調製された触媒では、イリジウムとレニウムが担体細孔内表面に均一に分布しているので、ＩｒとＲｅとの相互作用（結合）が確実に起こり、高い触媒活性が得られるだけでなく、該触媒を用いた反応時において、触媒成分、特にレニウム成分の溶出を抑制できるので、そのような高い触媒活性を長時間保持できる。なお、触媒調製時に、触媒成分含有水溶液を多量に用いて担体を浸漬する方法を採用すると、担体の外部にイリジウム等が析出しやすくなり、触媒活性が低下しやすくなる。 Reduce the amount of the catalyst component-containing aqueous solution (iridium compound-containing aqueous solution, rhenium compound-containing aqueous solution) used when supporting iridium and rhenium on the carrier, and the catalyst component-containing aqueous solution in an amount smaller than the pore volume of the silicon dioxide carrier And the catalyst component-containing aqueous solution is completely absorbed and supported on the carrier, thereby preventing elution and precipitation of the iridium component and the like during catalyst preparation. In addition, a predetermined amount of the catalyst component can be reliably and uniformly supported in the pores of the support as designed. In the catalyst prepared by such a method, since iridium and rhenium are uniformly distributed on the inner surface of the support pores, the interaction (bonding) between Ir and Re surely occurs, and high catalytic activity is obtained. In addition, since elution of the catalyst component, particularly the rhenium component, can be suppressed during the reaction using the catalyst, such a high catalytic activity can be maintained for a long time. In addition, when a method of immersing the support using a large amount of the catalyst component-containing aqueous solution at the time of catalyst preparation, iridium or the like is likely to be deposited outside the support, and the catalytic activity is likely to be lowered.
本発明のイリジウム−レニウム固体触媒は、例えばグリセリン等の多価アルコールの水素化反応用の触媒として好適に使用できる。本発明のイリジウム−レニウム固体触媒を用いた代表的な反応として、グリセリンの水素化（水素化分解）により１，３−プロパンジオール等を得る反応が挙げられる。以下、この反応について説明する。 The iridium-rhenium solid catalyst of the present invention can be suitably used as a catalyst for hydrogenation reaction of a polyhydric alcohol such as glycerin. A typical reaction using the iridium-rhenium solid catalyst of the present invention is a reaction for obtaining 1,3-propanediol or the like by hydrogenation (hydrogenolysis) of glycerol. Hereinafter, this reaction will be described.
本発明のイリジウム−レニウム固体触媒の存在下でグリセリンと水素とを反応させると、主に１，３−プロパンジオールが生成する。この場合、１，２−プロパンジオール、１−プロパノール、２−プロパノールも同時に生成することが多い。この反応を利用して、グリセリンから１，３−プロパンジオール、１，２−プロパンジオール、１−プロパノール、２−プロパノールを製造することができる。 When glycerin and hydrogen are reacted in the presence of the iridium-rhenium solid catalyst of the present invention, 1,3-propanediol is mainly produced. In this case, 1,2-propanediol, 1-propanol and 2-propanol are often generated at the same time. By utilizing this reaction, 1,3-propanediol, 1,2-propanediol, 1-propanol and 2-propanol can be produced from glycerin.
上記触媒の存在下におけるグリセリンと水素との反応は、特に限定されず、液状グリセリンと水素ガスと上記触媒との三相系（気液固三相系）で進行させてもよいし、グリセリンガスと水素ガスと上記触媒との二相系（気固二相系）で進行させてもよい。中でも、グリセリンの炭素−炭素結合が切断されてエチレングリコール、エタノール、メタノール、メタン等が生成する副反応の進行を抑制する観点からは、上記反応を三相系（気液固三相系）で進行させることが好ましい。 The reaction of glycerin and hydrogen in the presence of the catalyst is not particularly limited, and may proceed in a three-phase system (gas-liquid solid three-phase system) of liquid glycerin, hydrogen gas and the catalyst, or glycerin gas. It is also possible to proceed in a two-phase system (gas-solid two-phase system) of hydrogen, hydrogen gas and the above catalyst. Above all, from the viewpoint of suppressing the progress of side reactions in which the carbon-carbon bond of glycerin is broken to produce ethylene glycol, ethanol, methanol, methane, etc., the above reaction is a three-phase system (gas-liquid-solid three-phase system). It is preferable to proceed.
なお、上記反応を三相系（気液固三相系）で進行させる場合には、グリセリンを水や有機溶媒などに溶解させたグリセリン溶液を原料として好ましく使用することができる。上記有機溶媒としては、特に限定されないが、例えば、メタノール、エタノール、イソプロパノール、ｎ−ブタノールなどが使用できる。上記の中でも、反応性の観点で、上記グリセリン溶液としてグリセリンの水溶液を使用することが好ましい。 When the above reaction proceeds in a three-phase system (gas-liquid solid three-phase system), a glycerin solution in which glycerin is dissolved in water or an organic solvent can be preferably used as a raw material. Although it does not specifically limit as said organic solvent, For example, methanol, ethanol, isopropanol, n-butanol etc. can be used. Among these, from the viewpoint of reactivity, it is preferable to use an aqueous solution of glycerin as the glycerin solution.
上記グリセリン溶液（特に、グリセリン水溶液）におけるグリセリンの濃度（グリセリン溶液１００重量％に対する濃度）は、特に限定されないが、２０〜９８重量％が好ましく、より好ましくは２０〜９０重量％、さらに好ましくは４０〜９０重量％、特に好ましくは６０〜８０重量％である。グリセリンの濃度が２０重量％未満であると、グリセリンの反応率（転化率）が低下する場合がある。一方、グリセリンの濃度が９８重量％を超えると、粘度が高くなり、操作が煩雑になる場合がある。 The concentration of glycerin in the glycerin solution (particularly glycerin aqueous solution) (concentration relative to 100% by weight of glycerin solution) is not particularly limited, but is preferably 20 to 98% by weight, more preferably 20 to 90% by weight, and still more preferably 40 It is -90 weight%, Most preferably, it is 60-80 weight%. When the concentration of glycerin is less than 20% by weight, the reaction rate (conversion rate) of glycerin may decrease. On the other hand, when the concentration of glycerin exceeds 98% by weight, the viscosity may increase and the operation may become complicated.
上記グリセリン溶液には、本発明の効果を阻害しない範囲でその他の成分（例えば、アルコール類など）を含有させてもよい。また、上記グリセリン溶液には、例えば、グリセリンの原料に由来する不純物（例えば、長鎖脂肪酸、金属塩、チオールやチオエーテルなどの含硫黄化合物、アミンなどの含窒素化合物等）が含まれる場合があるが、このような不純物は触媒を劣化させるおそれがあるため、公知乃至慣用の方法（例えば、蒸留、吸着、イオン交換、晶析、抽出等）により、できるだけグリセリン溶液から除去することが好ましい。 The glycerin solution may contain other components (for example, alcohols) as long as the effects of the present invention are not impaired. The glycerin solution may contain, for example, impurities derived from glycerin raw materials (for example, long-chain fatty acids, metal salts, sulfur-containing compounds such as thiols and thioethers, nitrogen-containing compounds such as amines, etc.). However, since such impurities may deteriorate the catalyst, it is preferably removed from the glycerol solution as much as possible by a known or conventional method (for example, distillation, adsorption, ion exchange, crystallization, extraction, etc.).
上記グリセリン溶液は、特に限定されないが、グリセリンと、必要に応じて水や有機溶媒、その他の成分とを均一に混合することにより得られる。この場合の混合には、特に限定されないが、例えば、公知乃至慣用の攪拌機などを用いることができる。 Although the said glycerol solution is not specifically limited, It is obtained by mixing glycerol and water, an organic solvent, and another component uniformly as needed. Although mixing in this case is not particularly limited, for example, a known or conventional stirrer can be used.
グリセリンの水素化による１，３−プロパンジオール等の製造の方式は、特に限定されず、回分方式（バッチ式）、半回分方式、連続流通方式のいずれの方式によっても実施することができる。 The method for producing 1,3-propanediol and the like by hydrogenation of glycerin is not particularly limited, and can be carried out by any of a batch method (batch method), a semi-batch method, and a continuous flow method.
グリセリンの水素化による１，３−プロパンジオール等の製造を回分方式で実施する場合には、例えば、回分式の反応器に、グリセリン（又はグリセリン溶液）、上記触媒、及び水素（水素ガス）を仕込み、必要に応じて加熱し、攪拌下で反応させることによって実施することができる。 When production of 1,3-propanediol and the like by hydrogenation of glycerin is carried out in a batch system, for example, glycerin (or a glycerin solution), the above catalyst, and hydrogen (hydrogen gas) are added to a batch reactor. It can be carried out by charging, heating as necessary, and reacting under stirring.
グリセリンの水素化による１，３−プロパンジオール等の製造を回分方式で実施する場合、反応器へのグリセリンと水素の仕込み量は、特に限定されないが、グリセリンと水素のモル比［水素（ｍｏｌ）／グリセリン（ｍｏｌ）］が、１以上であることが好ましく、より好ましくは４以上、さらに好ましくは１０以上である。上記モル比が１未満であると、グリセリンの反応率（転化率）が低下する場合がある。 When production of 1,3-propanediol and the like by hydrogenation of glycerin is carried out in a batch system, the amount of glycerin and hydrogen charged into the reactor is not particularly limited, but the molar ratio of glycerin and hydrogen [hydrogen (mol) / Glycerin (mol)] is preferably 1 or more, more preferably 4 or more, and still more preferably 10 or more. If the molar ratio is less than 1, the reaction rate (conversion rate) of glycerin may decrease.
グリセリンの水素化による１，３−プロパンジオール等の製造を回分方式で実施する場合、上記触媒の使用量（仕込み量）は、特に限定されないが、グリセリン１００重量部に対し、０．０１〜５０重量部が好ましく、より好ましくは０．１〜２０重量部である。上記使用量が０．０１重量部未満であると、グリセリンの反応率（転化率）が低下する場合がある。一方、上記使用量が５０重量部を超えると、コスト面で不利となる場合がある。 When production of 1,3-propanediol and the like by hydrogenation of glycerin is carried out in a batch system, the amount of the catalyst used (amount charged) is not particularly limited, but is 0.01 to 50 with respect to 100 parts by weight of glycerin. Part by weight is preferred, more preferably 0.1 to 20 parts by weight. If the amount used is less than 0.01 parts by weight, the reaction rate (conversion rate) of glycerin may decrease. On the other hand, when the amount used exceeds 50 parts by weight, it may be disadvantageous in terms of cost.
一方、グリセリンの水素化による１，３−プロパンジオール等の製造を連続方式（連続流通方式）で実施する場合には、例えば、内部に上記触媒を滞留させた流通式反応器の一端に、グリセリン（又はグリセリン溶液）及び水素（水素ガス）を連続的に供給し、他端から上記触媒を含まない反応液を連続的に排出させる方法により、グリセリンと水素の反応を行うことができる。なお、上記流通式反応器における反応は、移動床、懸濁床、固定床など、いずれによっても行うことができる。 On the other hand, when production of 1,3-propanediol and the like by hydrogenation of glycerin is carried out in a continuous system (continuous flow system), for example, glycerin is placed at one end of a flow reactor in which the catalyst is retained. (The glycerin solution) and hydrogen (hydrogen gas) are continuously supplied, and the reaction of glycerin and hydrogen can be performed by a method of continuously discharging the reaction liquid not containing the catalyst from the other end. In addition, the reaction in the flow reactor can be performed by any of a moving bed, a suspension bed, a fixed bed, and the like.
上記の中でも、グリセリンの水素化による１，３−プロパンジオール等の製造は、連続流通方式で実施することが好ましく、特に、１，３−プロパンジオールの選択率及び収率が高く、触媒の分離プロセスが不要である点で、流通式反応器としてトリクルベッド反応器を用いることがより好ましい。なお、上記トリクルベッド反応器とは、固体触媒が充填された触媒充填層を内部に有し、該触媒充填層に対して液体（本発明では、例えば、グリセリン溶液）と気体（本発明では、水素）とを共に、反応器の上方から下向流（気液下向並流）で流通する形式の反応器（固定床連続反応装置）である。 Among these, the production of 1,3-propanediol and the like by hydrogenation of glycerin is preferably carried out in a continuous flow system, and in particular, the selectivity and yield of 1,3-propanediol are high, and the catalyst is separated. It is more preferable to use a trickle bed reactor as a flow reactor in that a process is unnecessary. The trickle bed reactor has a catalyst packed bed filled with a solid catalyst inside, and a liquid (in the present invention, for example, a glycerin solution) and a gas (in the present invention, in the present invention, Hydrogen) is a reactor (fixed bed continuous reaction apparatus) of a type that flows in a downward flow (gas-liquid downward parallel flow) from above the reactor.
上記グリセリンと水素の反応における温度（反応温度）は、特に限定されないが、８０〜３５０℃が好ましく、より好ましくは９０〜３００℃、さらに好ましくは１００〜２００℃である。反応温度が８０℃未満であると、グリセリンの反応率（転化率）が低下する場合がある。一方、反応温度が３５０℃を超えると、グリセリンの分解（例えば、炭素−炭素結合の開裂など）が生じやすく、１，３−プロパンジオールの選択率が低下する場合がある。 The temperature (reaction temperature) in the reaction between the glycerin and hydrogen is not particularly limited, but is preferably 80 to 350 ° C, more preferably 90 to 300 ° C, and still more preferably 100 to 200 ° C. When the reaction temperature is less than 80 ° C., the reaction rate (conversion rate) of glycerin may decrease. On the other hand, when reaction temperature exceeds 350 degreeC, decomposition | disassembly (for example, cleavage of a carbon-carbon bond etc.) of glycerol tends to arise, and the selectivity of 1, 3- propanediol may fall.
上記グリセリンと水素の反応における水素の圧力（反応圧力、グリセリンと水素の反応における水素圧）は、特に限定されないが、１〜５０ＭＰａが好ましく、より好ましくは３〜４０ＭＰａ、さらに好ましくは５〜３０ＭＰａである。反応圧力が１ＭＰａ未満であると、グリセリンの反応率（転化率）が低下する場合がある。一方、反応圧力が５０ＭＰａを超えると、高度な耐圧性を有する反応器が必要となるため、製造コストが高くなってしまう場合がある。 The hydrogen pressure in the reaction of glycerin and hydrogen (reaction pressure, hydrogen pressure in the reaction of glycerin and hydrogen) is not particularly limited, but is preferably 1 to 50 MPa, more preferably 3 to 40 MPa, and still more preferably 5 to 30 MPa. is there. If the reaction pressure is less than 1 MPa, the reaction rate (conversion rate) of glycerin may decrease. On the other hand, when the reaction pressure exceeds 50 MPa, a reactor having a high pressure resistance is required, which may increase the production cost.
グリセリンの水素化による１，３−プロパンジオール等の製造工程には、上述の水素とグリセリンとを反応させる工程のほか、必要に応じてその他の工程が含まれていてもよい。具体的には、例えば、グリセリンを精製したり、グリセリン溶液を調製・精製したりする工程等を含んでいてもよいし、反応により得られた反応結果物（例えば、グリセリン、水素、及びグリセリンの水素化分解物等を含む溶液）を分離したり、グリセリンの水素化分解物を精製する工程等を含んでいてもよい。 The production process of 1,3-propanediol and the like by hydrogenation of glycerin may include other processes as necessary in addition to the above-described process of reacting hydrogen and glycerin. Specifically, for example, a step of purifying glycerin, preparing / purifying a glycerin solution, or the like may be included, and a reaction product obtained by the reaction (for example, glycerin, hydrogen, and glycerin) A solution containing a hydrocracked product, etc.) or a step of purifying a hydrolyzed product of glycerin may be included.
本発明の触媒によれば、特に硫酸等の鉱酸を使用しなくても、グリセリンを高い反応率で反応させることができ、なおかつ、グリセリンの水素化分解物の中でも、特に、１，３−プロパンジオールを高い選択率及び収率で生成させることができる。また、反応後の反応液中のレニウム溶出濃度を従来の１０％以下に抑えることができる。 According to the catalyst of the present invention, glycerin can be reacted at a high reaction rate without using a mineral acid such as sulfuric acid, and among the hydrolysates of glycerin, 1,3- Propanediol can be produced with high selectivity and yield. Moreover, the rhenium elution density | concentration in the reaction liquid after reaction can be restrained to 10% or less of the past.
以下、実施例により本発明をより具体的に説明するが、本発明はこれらの実施例により限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.
実施例１
（触媒の調製）
球形の二酸化ケイ素（ＳｉＯ2）（富士シリシア化学社製、商品名「ＣＡＲｉＡＣＴＱ−１５」；球径１．１８−２．３６ｍｍ；細孔径１５ｎｍ；細孔容積０．９９ｍＬ／ｇ）を担体とした。上記担体を平底容器に薄く広げ、容器全体を直に加温しながら、塩化イリジウム酸を使用して調製したイリジウム濃度（Ｉｒ濃度）４．６重量％の水溶液を二酸化ケイ素の重量に対して２０重量％滴下して、完全に吸水させた後、加温により水分を蒸発させた。前記の滴下と乾燥を繰り返し、所定量のイリジウムを担持させた。イリジウムを担持させた担体を１１０℃で３時間乾燥させた後、上記担体に対し、過レニウム酸アンモニウムの濃度５．３重量％水溶液の滴下と乾燥を、先の塩化イリジウム酸水溶液の滴下と乾燥と同様にして行い、イリジウム（Ｉｒ）およびレニウム（Ｒｅ）の量がＳｉＯ2に対してそれぞれ３．６重量％、６．９重量％となるように担持させた。乾燥後の担体を、空気雰囲気下（大気中）、５００℃、３時間の条件で焼成して、球形シリカ担持イリジウム−レニウム触媒（Ｉｒ−Ｒｅ／ＳｉＯ2）を得た。
Example 1
(Preparation of catalyst)
Spherical silicon dioxide (SiO 2 ) (manufactured by Fuji Silysia Chemical Co., Ltd., trade name “CARiACTQ-15”; spherical diameter 1.18-2.36 mm; pore diameter 15 nm; pore volume 0.99 mL / g) was used as a carrier. . The carrier was thinly spread in a flat bottom container, and an aqueous solution having an iridium concentration (Ir concentration) of 4.6% by weight prepared using chloroiridic acid was heated to 20% with respect to the weight of silicon dioxide. After dropping by weight% to completely absorb water, the water was evaporated by heating. The above dripping and drying were repeated to carry a predetermined amount of iridium. After the carrier carrying iridium was dried at 110 ° C. for 3 hours, the aqueous solution of ammonium perrhenate having a concentration of 5.3% by weight was dropped and dried, and the aqueous solution of iridium chloride was dropped and dried. In the same manner as described above, iridium (Ir) and rhenium (Re) were supported in amounts of 3.6 wt% and 6.9 wt% with respect to SiO 2 , respectively. The dried support was calcined under the air atmosphere (in the air) at 500 ° C. for 3 hours to obtain a spherical silica-supported iridium-rhenium catalyst (Ir—Re / SiO 2 ).
（反応）
テフロン（登録商標）製内缶のあるＳＵＳ３１６製オートクレーブとチタン材質の撹拌軸から構成される反応器内の固定籠に上記触媒２．８ｇを充填した。この反応器内に水を入れ、１ＭＰａの水素を張り込んで、常圧まで排気する水素置換作業を３回繰り返した後、缶内が２００℃になった時に、全圧８ＭＰａになるように水素を張り込み、２００℃で１時間触媒を還元した。還元後、オートクレーブを冷却、開圧し、グリセロール２７重量％及び水７３重量％の原料溶液を反応器に入れた。再度１ＭＰａの水素で３回水素置換を行った後、１２０℃で、１２ＭＰａになるように水素を張り込み、撹拌回転数５００ｒｐｍにて、４時間反応を行った。反応器を氷冷し、反応溶液の分析を行った。分析は、ガスクロマトグラフィー（ガスクロマトグラフ装置：「ＧＣ−２０１０」、島津製作所製；カラム：ＦＦＡＰ（ＱＵＡＤＲＥＸ製）；検出器：ＦＩＤ）にて行った。
その結果、グリセロールの転化率は４０．１％で、各生成物の選択率は１，３−プロパンジオール４７．１％、１，２−プロパンジオール１５．５％、１−プロパノール２４．９％、２−プロパノール１２．５％であり、１，３−プロパンジオールの収率は１８．９％（触媒１ｇ当たりの収率６．７５％）であった。また反応後の溶液中のレニウム溶存濃度は０．２５ｐｐｍ（重量基準）であった。
(reaction)
2.8 g of the catalyst was charged in a fixed vessel in a reactor composed of a SUS316 autoclave with an inner can made of Teflon (registered trademark) and a stirring shaft made of titanium. The reactor was filled with water, filled with 1 MPa of hydrogen and evacuated to normal pressure three times. After the hydrogen replacement operation was repeated three times, when the inside of the can reached 200 ° C., the hydrogen pressure was adjusted so that the total pressure was 8 MPa. And the catalyst was reduced at 200 ° C. for 1 hour. After the reduction, the autoclave was cooled and opened, and a raw material solution containing 27% by weight of glycerol and 73% by weight of water was placed in the reactor. After performing hydrogen substitution again with 1 MPa of hydrogen three times, hydrogen was added at 120 ° C. so that the pressure became 12 MPa, and the reaction was performed at a stirring rotation speed of 500 rpm for 4 hours. The reactor was ice-cooled and the reaction solution was analyzed. The analysis was performed by gas chromatography (gas chromatograph apparatus: “GC-2010”, manufactured by Shimadzu Corporation; column: FFAP (manufactured by QUADREX); detector: FID).
As a result, the conversion of glycerol was 40.1%, and the selectivity of each product was 1,3-propanediol 47.1%, 1,2-propanediol 15.5%, 1-propanol 24.9%. 2-propanol 12.5%, and the yield of 1,3-propanediol was 18.9% (yield 6.75% per gram of catalyst). The rhenium dissolved concentration in the solution after the reaction was 0.25 ppm (weight basis).
実施例２
（触媒の調製）
担体として、球形の二酸化ケイ素（ＳｉＯ2）（富士シリシア化学社製、商品名「ＣＡＲｉＡＣＴＱ−３０」；球径１．１８−２．３６ｍｍ；細孔径３０ｎｍ；細孔容積０．９８ｍＬ／ｇ）を用いたこと以外は、実施例１と同様の操作で球形シリカ担持イリジウム−レニウム触媒（Ｉｒ−Ｒｅ／ＳｉＯ2）を調製した。
Example 2
(Preparation of catalyst)
As a carrier, spherical silicon dioxide (SiO 2 ) (manufactured by Fuji Silysia Chemical Co., Ltd., trade name “CARIACTQ-30”; spherical diameter 1.18-2.36 mm; pore diameter 30 nm; pore volume 0.98 mL / g) A spherical silica-supported iridium-rhenium catalyst (Ir—Re / SiO 2 ) was prepared in the same manner as in Example 1 except that it was used.
（反応）
触媒の使用量を２．７ｇとした以外は実施例１と同様にして反応、及び反応溶液の分析を行った。その結果、グリセロールの転化率は３６．６％で、各生成物の選択率は１，３−プロパンジオール４２．７％、１，２−プロパンジオール２１．３％、１−プロパノール２３．３％、２−プロパノール１２．８％であり、１，３−プロパンジオールの収率は１５．６％（触媒１ｇ当たりの収率５．７８％）であった。また反応後の溶液中のレニウム溶存濃度は１．０ｐｐｍ（重量基準）であった。
(reaction)
The reaction and the reaction solution were analyzed in the same manner as in Example 1 except that the amount of the catalyst used was 2.7 g. As a result, the conversion of glycerol was 36.6%, and the selectivity of each product was 1,3-propanediol 42.7%, 1,2-propanediol 21.3%, 1-propanol 23.3%. 2-propanol 12.8%, and the yield of 1,3-propanediol was 15.6% (yield 5.78% per gram of catalyst). Moreover, the rhenium dissolved concentration in the solution after the reaction was 1.0 ppm (weight basis).
比較例１
（触媒の調製）
球形の二酸化ケイ素（ＳｉＯ2）（富士シリシア化学社製、商品名「ＣＡＲｉＡＣＴＱ−６」；球径１．１８−２．３６ｍｍ；細孔径６ｎｍ；細孔容積０．６１ｍＬ／ｇ）を担体とした。上記担体を丸底容器にとり、湯浴で容器全体を加温しながら、塩化イリジウム酸を使用して調製したイリジウム濃度（Ｉｒ濃度）４．６重量％の水溶液を二酸化ケイ素の重量に対して２００重量％滴下して、上記担体全体を撹拌しながら浸漬して湿潤させた。加温により水分を蒸発させてイリジウムを担持させた後、さらに該担体を１１０℃で３時間乾燥させた。次に、上記担体に対し、過レニウム酸アンモニウムの濃度５．３重量％水溶液の滴下と乾燥を、先の塩化イリジウム酸水溶液の滴下と乾燥と同様にして行い、イリジウム（Ｉｒ）およびレニウム（Ｒｅ）の量がＳｉＯ2に対してそれぞれ３．６重量％、６．９重量％となるように担持させた。乾燥後の担体を、空気雰囲気下（大気中）、５００℃、３時間の条件で焼成して、球形シリカ担持イリジウム−レニウム触媒（Ｉｒ−Ｒｅ／ＳｉＯ2）を得た。
Comparative Example 1
(Preparation of catalyst)
Spherical silicon dioxide (SiO 2 ) (manufactured by Fuji Silysia Chemical Co., Ltd., trade name “CARIACTQ-6”; spherical diameter 1.18-2.36 mm; pore diameter 6 nm; pore volume 0.61 mL / g) was used as a carrier. . An aqueous solution having an iridium concentration (Ir concentration) of 4.6% by weight prepared using chloroiridic acid was heated to 200 wt. The carrier was dripped in weight%, and the entire support was dipped and wetted with stirring. Water was evaporated by heating to support iridium, and the carrier was further dried at 110 ° C. for 3 hours. Next, dropping and drying of an aqueous solution of ammonium perrhenate having a concentration of 5.3% by weight in the same manner as the dropping and drying of the aqueous chloroiridate solution was performed on the carrier, and iridium (Ir) and rhenium (Re ) Is 3.6% by weight and 6.9% by weight with respect to SiO 2 , respectively. The dried support was calcined under the air atmosphere (in the air) at 500 ° C. for 3 hours to obtain a spherical silica-supported iridium-rhenium catalyst (Ir—Re / SiO 2 ).
（反応）
触媒の使用量を４．０ｇとした以外は実施例１と同様にして反応、及び反応溶液の分析を行った。その結果、グリセロールの転化率は２８．９％で、各生成物の選択率は１，３−プロパンジオール４８．１％、１，２−プロパンジオール１９．５％、１−プロパノール２０．０％、２−プロパノール１２．４％であり、１，３−プロパンジオールの収率は１３．９％（触媒１ｇ当たりの収率３．４８％）であった。また反応後の溶液中のレニウム溶存濃度は１２．１ｐｐｍ（重量基準）であった。
(reaction)
The reaction and the reaction solution were analyzed in the same manner as in Example 1 except that the amount of the catalyst used was 4.0 g. As a result, the conversion of glycerol was 28.9%, and the selectivity of each product was 1,3-propanediol 48.1%, 1,2-propanediol 19.5%, 1-propanol 20.0%. 2-propanol 12.4%, and the yield of 1,3-propanediol was 13.9% (yield 3.48% per gram of catalyst). Moreover, the rhenium dissolved concentration in the solution after the reaction was 12.1 ppm (weight basis).
比較例２
（触媒の調製）
担体として、球形の二酸化ケイ素（ＳｉＯ2）（富士シリシア化学社製、商品名「ＣＡＲｉＡＣＴＱ−６」；球径１．１８−２．３６ｍｍ；細孔径６ｎｍ；細孔容積０．６１ｍＬ／ｇ）を用いたこと以外は、実施例１と同様の操作で球形シリカ担持イリジウム−レニウム触媒（Ｉｒ−Ｒｅ／ＳｉＯ2）を調製した。
Comparative Example 2
(Preparation of catalyst)
As a carrier, spherical silicon dioxide (SiO 2 ) (manufactured by Fuji Silysia Chemical Co., Ltd., trade name “CARIACTQ-6”; spherical diameter 1.18-2.36 mm; pore diameter 6 nm; pore volume 0.61 mL / g) A spherical silica-supported iridium-rhenium catalyst (Ir—Re / SiO 2 ) was prepared in the same manner as in Example 1 except that it was used.
（反応）
触媒の使用量を４．０ｇとした以外は実施例１と同様にして反応、及び反応溶液の分析を行った。その結果、グリセロールの転化率は３７．８％で、各生成物の選択率は１，３−プロパンジオール４５．８％、１，２−プロパンジオール１９．５％、１−プロパノール２２．０％、２−プロパノール１２．７％であり、１，３−プロパンジオールの収率は１７．３％（触媒１ｇ当たりの収率４．３３％）であった。また反応後の溶液中のレニウム溶存濃度は４．６ｐｐｍ（重量基準）であった。
(reaction)
The reaction and the reaction solution were analyzed in the same manner as in Example 1 except that the amount of the catalyst used was 4.0 g. As a result, the conversion of glycerol was 37.8%, and the selectivity for each product was 1,3-propanediol 45.8%, 1,2-propanediol 19.5%, 1-propanol 22.0%. 2-propanol 12.7%, and the yield of 1,3-propanediol was 17.3% (yield 4.33% per g of catalyst). The rhenium dissolved concentration in the solution after the reaction was 4.6 ppm (weight basis).
実施例及び比較例の結果を表１に示す。表１で用いた略号は以下の通りである。また、１，３−ＰＤ収率の欄の括弧内の数字は、触媒１ｇ当たりの収率である。
１，３−ＰＤ ： １，３−プロパンジオール
１，２−ＰＤ ： １，２−プロパンジオール
１−ＰｒＯＨ ： １−プロパノール
２−ＰｒＯＨ ： ２−プロパノール
The results of Examples and Comparative Examples are shown in Table 1. Abbreviations used in Table 1 are as follows. The number in parentheses in the 1,3-PD yield column is the yield per 1 g of the catalyst.
1,3-PD: 1,3-propanediol 1,2-PD: 1,2-propanediol 1-PrOH: 1-propanol 2-PrOH: 2-propanol
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| JPH0827210A (en) * | 1994-07-14 | 1996-01-30 | Asahi Chem Ind Co Ltd | Polymerization of olefin |
| JPH08141396A (en) * | 1994-11-28 | 1996-06-04 | Mitsubishi Chem Corp | Hydrogenation catalyst for carboxylic acid and method for hydrogenation of carboxylic acid using said catalyst |
| JP2008110931A (en) * | 2006-10-30 | 2008-05-15 | Univ Of Tsukuba | Method for reducing glycerin, and catalyst for reducing glycerin |
| JP5231786B2 (en) * | 2006-12-05 | 2013-07-10 | 花王株式会社 | Process for producing polyhydric alcohol hydrocracked product |
| JP5035790B2 (en) * | 2006-12-06 | 2012-09-26 | 独立行政法人産業技術総合研究所 | Propanediol production method |
| JP2009275029A (en) * | 2008-04-16 | 2009-11-26 | Univ Of Tsukuba | Method for producing glycerol and catalyst |
| JP5654399B2 (en) * | 2011-03-28 | 2015-01-14 | 株式会社ダイセル | Process for producing hydrolyzate of glycerin |
| JP5717535B2 (en) * | 2011-05-17 | 2015-05-13 | 株式会社ダイセル | Process for producing 1,3-propanediol and catalyst for hydrogenation reaction of glycerin |
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