JP2023143030A - Method for producing 1,3-cyclopentanediol - Google Patents
Method for producing 1,3-cyclopentanediol Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- NUUPJBRGQCEZSI-UHFFFAOYSA-N cyclopentane-1,3-diol Chemical compound OC1CCC(O)C1 NUUPJBRGQCEZSI-UHFFFAOYSA-N 0.000 title claims abstract description 15
- DHNDDRBMUVFQIZ-UHFFFAOYSA-N 4-hydroxycyclopent-2-en-1-one Chemical compound OC1CC(=O)C=C1 DHNDDRBMUVFQIZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims description 25
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 abstract description 24
- 238000000034 method Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229910000510 noble metal Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003125 aqueous solvent Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000010948 rhodium Substances 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- LOGSONSNCYTHPS-UHFFFAOYSA-N cyclopentane-1,3-dione Chemical compound O=C1CCC(=O)C1 LOGSONSNCYTHPS-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は１，３－シクロペンタンジオールの製造方法に関する。 The present invention relates to a method for producing 1,3-cyclopentanediol.
１，３－シクロペンタンジオール（ＣＰＤＬ）は、有用なポリエステルやポリウレタン用原料である。従来、１，３－シクロペンタンジオールは工業的には化石原料であるジシクロペンタジエンのハイドロボレーションで製造されている（非特許文献１，２）。
一方、バイオマス由来のフルフリルアルコールから１，３－シクロペンタンジオールを誘導できれば、ＣＯ２削減が可能であることから、カーボンニュートラルを目指す社会での開発が期待されている。
バイオマス由来のＣＰＤＬは、下記反応式に示す通り、フルフリルアルコールから誘導される４－ヒドロキシ－２－シクロペンテン－１－オン（ＨＣＰ）の水素化で合成されるが、ＣＰＤＬは２つの水酸基を有し、ｃｉｓ体とｔｒａｎｓ体の２つが生成する。
1,3-Cyclopentanediol (CPDL) is a useful raw material for polyesters and polyurethanes. Conventionally, 1,3-cyclopentanediol has been industrially produced by hydroboration of dicyclopentadiene, which is a fossil raw material (Non-Patent Documents 1 and 2).
On the other hand, if 1,3-cyclopentanediol can be derived from biomass-derived furfuryl alcohol, it is possible to reduce CO2 , so its development is expected in a society aiming for carbon neutrality.
Biomass-derived CPDL is synthesized by hydrogenation of 4-hydroxy-2-cyclopenten-1-one (HCP) derived from furfuryl alcohol, as shown in the reaction formula below, but CPDL has two hydroxyl groups. However, two forms, cis and trans, are generated.
一方、ＣＰＤＬをモノマーとして含むポリエステルが報告されているが（非特許文献２）、ｃｉｓ体は耐熱性が低いため、できるだけｔｒａｎｓ体の比率を上げることが求められている。 On the other hand, a polyester containing CPDL as a monomer has been reported (Non-Patent Document 2), but since the cis form has low heat resistance, it is required to increase the ratio of the trans form as much as possible.
また、フルフリルアルコールからのＨＣＰの合成は、水溶媒中で行われるため、ＨＣＰからＣＰＤＬの製造も、水溶媒中で行うことができるならば、溶媒を変えることなく連続してＣＰＤＬを製造することができ、工業的に有利である。 Furthermore, since the synthesis of HCP from furfuryl alcohol is carried out in an aqueous solvent, if the production of CPDL from HCP can also be carried out in an aqueous solvent, CPDL can be produced continuously without changing the solvent. It is industrially advantageous.
従来、固体触媒としてラネーニッケルを用いたＨＣＰの水素化によるＣＰＤＬの製造方法については、種々提案がなされているが（非特許文献４、特許文献１～４）、いずれもテトラヒドロジシクロペンタジエン合成の中間体としてのＣＰＤＬの製造であり、異性体比率についての検討はなされていない。
ＨＣＰを高価なＲｈ触媒を用いて１，３－シクロペンタンジオンに誘導し、これを水素化してＣＰＤＬを製造する方法も提案されているが（非特許文献５，６）、ｔｒａｎｓ比率は高くない。
Conventionally, various proposals have been made regarding the production method of CPDL by hydrogenation of HCP using Raney nickel as a solid catalyst (Non-Patent Document 4, Patent Documents 1 to 4), but all of them involve intermediate steps in the synthesis of tetrahydrodicyclopentadiene. This is the production of CPDL as an isomer, and no consideration has been given to the isomer ratio.
A method has also been proposed in which HCP is induced into 1,3-cyclopentanedione using an expensive Rh catalyst and hydrogenated to produce CPDL (Non-Patent Documents 5, 6), but the trans ratio is not high. .
本発明は、ＨＣＰを直接水素化してｔｒａｎｓ比率の高いＣＰＤＬを高収率で製造する方法を提供することを目的とする。本発明はまた、前工程の原料ＨＣＰの合成と同様に水溶媒でそのままｔｒａｎｓ－ＣＰＤＬを高収率で製造することができる方法を提供することを目的とする。 An object of the present invention is to provide a method for directly hydrogenating HCP to produce CPDL with a high trans ratio in high yield. Another object of the present invention is to provide a method that can directly produce trans-CPDL in a high yield using an aqueous solvent, similar to the synthesis of the raw material HCP in the previous step.
本発明者は、上記課題を解決すべく検討を重ね、ＨＣＰを、ルテニウムを炭素系担体に担持した触媒の存在下に、所定の温度で水素化することにより、水溶媒中で、ｔｒａｎｓ比率の高いＣＰＤＬを高収率で製造することができることを見出した。 The present inventor has repeatedly studied to solve the above problems, and by hydrogenating HCP at a predetermined temperature in the presence of a catalyst in which ruthenium is supported on a carbon-based carrier, the trans ratio can be reduced in an aqueous solvent. It has been found that high CPDL can be produced in high yield.
本発明はこのような知見に基づいて達成されたものであり、以下を要旨とする。 The present invention has been achieved based on such knowledge, and its gist is as follows.
［１］ ４－ヒドロキシ－２－シクロペンテン－１－オンを、ルテニウムを炭素系担体に担持した触媒の存在下に、６０℃以上１５０℃以下にて水素化する、１，３－シクロペンタンジオールの製造方法。 [1] Hydrogenation of 1,3-cyclopentanediol by hydrogenating 4-hydroxy-2-cyclopenten-1-one at 60°C or higher and 150°C or lower in the presence of a catalyst in which ruthenium is supported on a carbon-based carrier. Production method.
［２］ 前記炭素系担体が、活性炭またはグラファイトである、［１］に記載の１，３－シクロペンタンジオールの製造方法。 [2] The method for producing 1,3-cyclopentanediol according to [1], wherein the carbon-based carrier is activated carbon or graphite.
［３］ 前記水素化を溶媒中で行う１，３－シクロペンタンジオールの製造方法であって、該溶媒が水、エーテル系溶媒、及びアルコール系溶媒の中から選ばれる少なくとも１つである、［１］又は［２］に記載の１，３－シクロペンタンジオールの製造方法。 [3] A method for producing 1,3-cyclopentanediol in which the hydrogenation is carried out in a solvent, the solvent being at least one selected from water, an ether solvent, and an alcohol solvent, [ 1] or the method for producing 1,3-cyclopentanediol according to [2].
本発明によれば、バイオマス由来のフルフリルアルコールから誘導されるＨＣＰの直接水素化で、ポリエステルやポリウレタン用原料として有用なＣＰＤＬ、特にｔｒａｎｓ比率の高いＣＰＤＬを高収率で製造することができる。
このため、本発明により製造されたＣＰＤＬを原料として、耐熱性等に優れたポリエステルやポリウレタンを製造することができる。
しかも、本発明によれば、水溶媒中でＨＣＰの水素化を行うことができ、フルフリルアルコールから水溶媒中で合成されたＨＣＰを、そのまま水溶媒中で連続的に水素化してＣＰＤＬを製造することができ、工業的に極めて有利である。
According to the present invention, CPDL useful as a raw material for polyesters and polyurethanes, particularly CPDL with a high trans ratio, can be produced in high yield by direct hydrogenation of HCP derived from biomass-derived furfuryl alcohol.
Therefore, polyester and polyurethane having excellent heat resistance and the like can be produced using the CPDL produced according to the present invention as a raw material.
Moreover, according to the present invention, HCP can be hydrogenated in an aqueous solvent, and HCP synthesized from furfuryl alcohol in an aqueous solvent is continuously hydrogenated as it is in an aqueous solvent to produce CPDL. This is extremely advantageous industrially.
以下、本発明を詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施形態の代表例であり、これらの内容に限定されるものではない。 Hereinafter, the present invention will be described in detail, but the explanation of the constituent elements described below is a representative example of the embodiment of the present invention, and the present invention is not limited to these contents.
本発明の４－ヒドロキシ－２－シクロペンテン－１－オン（ＣＰＤＬ）の製造方法は、４－ヒドロキシ－２－シクロペンテン－１－オン（ＣＨＰ）を、ルテニウムを炭素系担体に担持した触媒の存在下に、６０℃以上１５０℃以下にて水素化することを特徴とするものであり、この反応は、下記反応式に従って行われる。なお、この反応では、後掲の実施例に示す通り、副生成物としてシクロペンタノオール（ＣＰＬ）が生成される。 The method for producing 4-hydroxy-2-cyclopenten-1-one (CPDL) of the present invention comprises producing 4-hydroxy-2-cyclopenten-1-one (CHP) in the presence of a catalyst in which ruthenium is supported on a carbon-based carrier. It is characterized by hydrogenation at 60° C. or higher and 150° C. or lower, and this reaction is carried out according to the following reaction formula. In addition, in this reaction, cyclopentanool (CPL) is produced as a by-product, as shown in the examples below.
特に限定されるものではないが、本発明において、ＣＰＤＬの製造原料として用いられるＨＣＰは、バイオマス由来のフルフリルアルコールから誘導されたものであることが好ましい。 Although not particularly limited, in the present invention, the HCP used as a raw material for producing CPDL is preferably one derived from biomass-derived furfuryl alcohol.
本発明においては、ＨＣＰの水素化触媒として、ルテニウムを炭素系担体に担持した触媒を用いる。
本発明で用いる水素化触媒は、ルテニウム以外の他の金属を含んでいてもよく、例えば、ルテニウム（Ｒｕ）以外の貴金属を含んでいてもよい。ルテニウム以外の貴金属としては、パラジウム、白金、ロジウム、イリジウム等が挙げられる。これらの貴金属は１種のみを用いてもよく、２種以上を用いてもよい。
本発明で用いる水素化触媒が、Ｒｕ以外の貴金属を含む場合、貴金属全量中のルテニウム以外の貴金属の割合は、好ましくは1０質量％以下であり、より好ましくは８質量％以下である。また、下限値は特にないが１質量％以上である。これらの範囲であることで、ＣＰＤＬ収率及びＣＰＤＬのｔｒａｎｓ比率を高めることができる。
In the present invention, a catalyst in which ruthenium is supported on a carbon-based carrier is used as a hydrogenation catalyst for HCP.
The hydrogenation catalyst used in the present invention may contain metals other than ruthenium, for example, may contain noble metals other than ruthenium (Ru). Examples of noble metals other than ruthenium include palladium, platinum, rhodium, and iridium. These noble metals may be used alone or in combination of two or more.
When the hydrogenation catalyst used in the present invention contains a noble metal other than Ru, the proportion of the noble metal other than ruthenium in the total amount of noble metals is preferably 10% by mass or less, and more preferably 8% by mass or less. Further, there is no particular lower limit, but it is 1% by mass or more. Within these ranges, the CPDL yield and the trans ratio of CPDL can be increased.
炭素系担体へのＲｕを含む貴金属の担持量は、好ましくは０．１質量％以上、より好ましくは１質量％以上であり、好ましくは２０質量％以下、より好ましくは１０質量％である。貴金属担持量が上記下限以上であれば高い水素化反応活性を得ることができ、上記上限以下であれば水素化分解が抑制され、高収率となる。 The amount of noble metals including Ru supported on the carbon-based carrier is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass. If the noble metal supported amount is at least the above-mentioned lower limit, high hydrogenation reaction activity can be obtained, and if it is below the above-mentioned upper limit, hydrogenolysis is suppressed and a high yield is achieved.
炭素系担体としては、活性炭（ＡＣ）、グラファイト（Ｇｒａｐｈｉｔｅ）、カーボンブラック等が挙げられる。これらのうち、ＣＰＤＬ収率の観点からは、活性炭を用いることが好ましく、ｔｒａｎｓ比率の観点からはグラファイトを用いることが好ましい。炭素系担体は、１種のみを用いてもよく、２種以上を用いてもよい。 Examples of the carbon-based carrier include activated carbon (AC), graphite, carbon black, and the like. Among these, from the viewpoint of CPDL yield, it is preferable to use activated carbon, and from the viewpoint of trans ratio, it is preferable to use graphite. Only one type of carbon-based carrier may be used, or two or more types may be used.
ＨＣＰの水素化反応は、温度６０℃以上、好ましくは８０℃以上であり、１５０℃以下、好ましくは１２０℃以下で行い、水素ガス圧力は、好ましくは１ＭＰａ以上、より好ましくは２ＭＰａ以上であり、好ましくは２０ＭＰａ以下、より好ましくは１０．０ＭＰａ以下で行うことが、反応効率と副反応を抑制し、収率向上の観点から好ましい。 The hydrogenation reaction of HCP is carried out at a temperature of 60° C. or higher, preferably 80° C. or higher, and 150° C. or lower, preferably 120° C. or lower, and the hydrogen gas pressure is preferably 1 MPa or higher, more preferably 2 MPa or higher, It is preferable to conduct the reaction at a pressure of 20 MPa or less, more preferably 10.0 MPa or less, from the viewpoint of suppressing reaction efficiency and side reactions and improving yield.
水素化反応の操作方法としては、水素化触媒をＨＣＰの溶液中に懸濁させて行う、いわゆる懸濁床による方法、あるいは水素化触媒の固定床にＨＣＰの溶液を流す、いわゆる固定床による方法等が通常採用することができる。さらに、例えば懸濁床による方法おいては、耐圧容器に水素化触媒とＨＣＰを仕込み、耐圧容器内の空間を水素ガスで置換した後、所定の温度で所定時間攪拌する方法、または水素ガスで置換する代わりに水素ガスを反応容器中に吹き込む方法がある。また例えば固定床による方法おいては、水素化触媒を充填した槽（例えば充填塔）に、ＨＣＰの溶液と水素ガスを並流で通じる方法などがある。本発明においては、これらのいかなる方法をも用いることができる。 The hydrogenation reaction can be carried out by suspending the hydrogenation catalyst in a solution of HCP, a so-called suspended bed method, or by flowing an HCP solution through a fixed bed of hydrogenation catalyst, a so-called fixed bed method. etc. can usually be adopted. Furthermore, in a suspended bed method, for example, a hydrogenation catalyst and HCP are placed in a pressure vessel, the space inside the pressure vessel is replaced with hydrogen gas, and then the mixture is stirred at a predetermined temperature for a predetermined period of time; Instead of substitution, there is a method of blowing hydrogen gas into the reaction vessel. For example, in a fixed bed method, there is a method in which an HCP solution and hydrogen gas are passed in parallel flow through a tank filled with a hydrogenation catalyst (for example, a packed column). Any of these methods can be used in the present invention.
反応溶媒としては、水素化反応に不活性で、ＨＣＰを溶解し得るものであればよく、特に制限はなく、テトラヒドロフラン（ＴＨＦ）、ジオキサン等のエーテル類溶媒、メタノール、エタノール等のアルコール類溶媒、水等を用いることができる。
このうち、ＨＣＰの溶解性の観点からＴＨＦ、ジオキサン等のエーテル類溶媒が好ましく、前述の通り、フルフリルアルコールから水溶媒中で誘導されるＨＣＰについて同じ溶媒で連続的に製造するためには水を用いることが好ましい。
これらの溶媒は、１種のみを用いてもよく、２種以上を混合して用いてもよい。
The reaction solvent is not particularly limited as long as it is inert to the hydrogenation reaction and can dissolve HCP, and includes ether solvents such as tetrahydrofuran (THF) and dioxane, alcohol solvents such as methanol and ethanol, Water etc. can be used.
Among these, ether solvents such as THF and dioxane are preferred from the viewpoint of HCP solubility.As mentioned above, in order to continuously produce HCP derived from furfuryl alcohol in a water solvent using the same solvent, water It is preferable to use
These solvents may be used alone or in combination of two or more.
水素化反応に供するＨＣＰ溶液中のＨＣＰ濃度は、好ましくは５質量％以上、より好ましくは１０質量％以上であり、好ましくは５０質量％以下、より好ましくは３０質量％以下である。ＨＣＰ濃度が上記下限以上であれば溶媒の使用量が少なく、コストの点で有利であり、上記上限以下であれば触媒の劣化が抑制でき、実用的な速度での反応が可能である。 The HCP concentration in the HCP solution subjected to the hydrogenation reaction is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less. If the HCP concentration is above the above-mentioned lower limit, the amount of solvent used is small, which is advantageous in terms of cost, and when it is below the above-mentioned upper limit, deterioration of the catalyst can be suppressed and the reaction can be carried out at a practical rate.
水素化触媒の使用量には特に制限はないが、例えば、懸濁床による方法において、水素化触媒は、ＨＣＰに対して、好ましくは２質量％以上、より好ましくは５質量％以上であり、好ましくは３０質量％以下、より好ましくは２０質量％以下で用いることが反応時間を短縮でき、経済性の観点から好ましい。 There is no particular restriction on the amount of the hydrogenation catalyst used, but for example, in a method using a suspended bed, the hydrogenation catalyst is preferably 2% by mass or more, more preferably 5% by mass or more, based on the HCP. Preferably, it is used in an amount of 30% by mass or less, more preferably 20% by mass or less, since the reaction time can be shortened, and this is preferable from the viewpoint of economical efficiency.
反応時間は、反応温度や水素ガス圧力等の条件によっても異なるが、通常０．５～５時間程度で、ＨＣＰの水素化を行ってＣＰＤＬとすることができる。 Although the reaction time varies depending on conditions such as reaction temperature and hydrogen gas pressure, HCP can be hydrogenated to CPDL in usually about 0.5 to 5 hours.
水素化反応後、目的物のＣＰＤＬは触媒をろ過することにより分離回収することができ、必要に応じて蒸留により精製することができる。 After the hydrogenation reaction, the target product CPDL can be separated and recovered by filtering the catalyst, and if necessary, purified by distillation.
本発明のＣＰＤＬの製造方法によれば、例えば、後述の実施例に示すように、ＣＰＤＬ収率９０％以上で、ＣＰＤＬの異性体比率（ｃｉｓ／ｔｒａｎｓ）６６／３４以下、好ましくは６０／４０以下でｔｒａｎｓ比率の高いＣＰＤＬを製造することができる。 According to the method for producing CPDL of the present invention, for example, as shown in Examples below, the CPDL yield is 90% or more and the isomer ratio (cis/trans) of CPDL is 66/34 or less, preferably 60/40. A CPDL with a high trans ratio can be manufactured as follows.
以下、実施例により本発明を更に詳しく説明するが、本発明は、その要旨を超えない限り、以下の実施例に何ら限定されるものではない。 EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.
［水素化反応液の分析］
以下の実施例及び比較例において、水素化反応液の分析は次の条件下におけるガスクロマトグラフィー分析により行った。
＜分析条件＞
カラム：アジレント製ＤＢ－ＷＡＸ、長さ３０ｍ、フィルム厚さ ０．２５μｍ、直径０．２５ｍｍ
注入温度：２５０℃
検出温度：２８０℃
昇温プログラム条件：８０℃→１０℃／分→２５０℃（５分保持）
キャリアガス：１．８ｍＬ／ｍｉｎ
スプリット比：１２
検出器：ＦＩＤ
[Analysis of hydrogenation reaction solution]
In the following Examples and Comparative Examples, the hydrogenation reaction solution was analyzed by gas chromatography under the following conditions.
<Analysis conditions>
Column: Agilent DB-WAX, length 30m, film thickness 0.25μm, diameter 0.25mm
Injection temperature: 250℃
Detection temperature: 280℃
Temperature increase program conditions: 80℃ → 10℃/min → 250℃ (held for 5 minutes)
Carrier gas: 1.8mL/min
Split ratio: 12
Detector: FID
［原料］
原料のＨＣＰとしては、Ｃｏｍｂｉ－Ｂｌｏｃｋｓ社製の４－ヒドロキシ－２－シクロペンテン－１－オンを使用した。
[material]
As the raw HCP, 4-hydroxy-2-cyclopenten-1-one manufactured by Combi-Blocks was used.
［実施例１］
７０ｍＬ容量のスピナー攪拌式ステンレス製オートクレーブにＨＣＰ ０．１０ｇ（１．０ｍｍｏｌ）、５質量％Ｒｕ／ＡＣ触媒（エヌ・イーケムキャット製Ａ－Ｔｙｐｅ）０．０２ｇ、水５ｍＬと攪拌子を入れて蓋をし、室温で水素ガスを３ＭＰａ圧入した。攪拌しながら８０℃に昇温し、２時間反応した。反応後、室温まで冷却し、水素ガスをパージした。得られた反応液のガスクロマトグラフィー分析を行い、ＣＰＤＬとＣＰＬの定量を行って、原料転化率、ＣＰＤＬ収率、ＣＰＬ収率及びＣＰＤＬの異性体比率（ｃｉｓ／ｔｒａｎｓ）を算出した。結果を表－１に示す。 Put 0.10 g (1.0 mmol) of HCP, 0.02 g of 5 mass % Ru/AC catalyst (A-Type manufactured by N.E. Chemcat), 5 mL of water, and a stirrer into a 70 mL capacity spinner-stirred stainless steel autoclave, and close the lid. Then, hydrogen gas was injected under pressure at 3 MPa at room temperature. The temperature was raised to 80° C. while stirring, and the mixture was reacted for 2 hours. After the reaction, the reaction mixture was cooled to room temperature and hydrogen gas was purged. The obtained reaction solution was analyzed by gas chromatography, CPDL and CPL were quantified, and the raw material conversion rate, CPDL yield, CPL yield, and CPDL isomer ratio (cis/trans) were calculated. The results are shown in Table 1.
［実施例２］
触媒として、５質量％Ｒｕ／グラファイト触媒（エヌ・イーケムキャット製）を用いた以外は実施例１と同様の方法で行った。結果を表－１に示す。
[Example 2]
The same method as in Example 1 was conducted except that a 5% by mass Ru/graphite catalyst (manufactured by N.E. Chemcat) was used as the catalyst. The results are shown in Table-1.
［実施例３］
反応温度を１２０℃としたこと以外は実施例１と同様の方法で行った。結果を表－１に示す。
[Example 3]
The same method as in Example 1 was carried out except that the reaction temperature was 120°C. The results are shown in Table-1.
［実施例４］
水の替わりにテトラヒドロフラン（ＴＨＦ）５ｍＬを用いた以外は実施例１と同様の方法で行った。結果を表－１に示す。
[Example 4]
The same method as in Example 1 was conducted except that 5 mL of tetrahydrofuran (THF) was used instead of water. The results are shown in Table-1.
［実施例５］
水の替わりにメタノール（ＭｅＯＨ）５ｍＬを用いた以外は実施例１と同様の方法で行った。結果を表－１に示す。
[Example 5]
The same method as in Example 1 was carried out except that 5 mL of methanol (MeOH) was used instead of water. The results are shown in Table-1.
［比較例１］
触媒として、５質量％Ｒｕ／Ａｌ２Ｏ３触媒（エヌ・イーケムキャット製）を用いた以外は実施例１と同様の方法で行った。結果を表－１に示す。
[Comparative example 1]
The same method as in Example 1 was conducted except that a 5% by mass Ru/Al 2 O 3 catalyst (manufactured by N.E. Chemcat) was used as the catalyst. The results are shown in Table-1.
［比較例２］
４０．０質量％塩化ルテニウム０．２５１ｇを水２．４１ｇに溶解させた中に、ＳｉＯ２（富士シリシア化学社製 Ｃａｒｉａｃｔ－１５、表面積２００ｍ２／ｇ）１．９１ｇを加えて含浸担持した。その後、減圧下溶媒を除去し、アルゴン流通下１５０℃で２時間乾燥した。これを水素ガス流通下３００℃で２時間気相還元した後、５．８％Ｏ２／Ｎ２ガスで徐酸化を行い、５質量％Ｒｕ／ＳｉＯ２触媒を得た。
触媒として、この５質量％Ｒｕ／ＳｉＯ２触媒を用いた以外は実施例１と同様の方法で行った。結果を表－１に示す。
[Comparative example 2]
Into a solution of 0.251 g of 40.0% by mass ruthenium chloride in 2.41 g of water, 1.91 g of SiO 2 (Cariact-15 manufactured by Fuji Silysia Chemical Co., Ltd., surface area 200 m 2 /g) was added and supported by impregnation. Thereafter, the solvent was removed under reduced pressure, and the mixture was dried at 150° C. for 2 hours under argon flow. This was reduced in a gas phase at 300° C. for 2 hours under hydrogen gas flow, and then slowly oxidized with 5.8% O 2 /N 2 gas to obtain a 5% by mass Ru/SiO 2 catalyst.
The same method as in Example 1 was carried out except that this 5 mass % Ru/SiO 2 catalyst was used as the catalyst. The results are shown in Table-1.
［比較例３］
４１．９質量％塩化ルテニウム０．２４２ｇを水４．３３ｇに溶解させた中に、ＴｉＯ２（堺化学工業社製 ＳＴＲ－１００Ｎ）１．９０ｇを加えて含浸担持した。その後、減圧下溶媒を除去し、アルゴン流通下１５０℃で２時間乾燥した。これを水素ガス流通下３００℃で２時間気相還元した後、５．８％Ｏ２／Ｎ２ガスで徐酸化を行い、５質量％Ｒｕ／ＴｉＯ２触媒を得た。
触媒として、この５質量％Ｒｕ／ＴｉＯ２触媒を用いた以外は実施例１と同様の方法で行った。結果を表－１に示す。
[Comparative example 3]
Into a solution of 0.242 g of 41.9% by mass ruthenium chloride in 4.33 g of water, 1.90 g of TiO 2 (STR-100N manufactured by Sakai Chemical Industries, Ltd.) was added and supported by impregnation. Thereafter, the solvent was removed under reduced pressure, and the mixture was dried at 150° C. for 2 hours under argon flow. This was reduced in a gas phase at 300° C. for 2 hours under hydrogen gas flow, and then slowly oxidized with 5.8% O 2 /N 2 gas to obtain a 5% by mass Ru/TiO 2 catalyst.
The same method as in Example 1 was carried out except that this 5 mass % Ru/TiO 2 catalyst was used as the catalyst. The results are shown in Table-1.
［比較例４］
４１．９質量％塩化ルテニウム０．２４３ｇを水２．３０ｇに溶解させた中に、ＺｒＯ２（Ｓａｉｎｔ－Ｇｏｂａｉｎ社製、ＳＺ３１１６４）１．９０ｇを加えて含浸担持した。その後、減圧下溶媒を除去し、アルゴン流通下１５０℃で２時間乾燥した。これを水素ガス流通下３００℃で２時間気相還元した後、５．８％Ｏ２／Ｎ２ガスで徐酸化を行い、５質量％Ｒｕ／ＺｒＯ２触媒を得た。
触媒として、この５質量％Ｒｕ／ＺｒＯ２触媒を用いた以外は実施例１と同様の方法で行った。結果を表－１に示す。
[Comparative example 4]
Into a solution of 0.243 g of 41.9% by mass ruthenium chloride in 2.30 g of water, 1.90 g of ZrO 2 (manufactured by Saint-Gobain, SZ31164) was added and supported by impregnation. Thereafter, the solvent was removed under reduced pressure, and the mixture was dried at 150° C. for 2 hours under argon flow. This was reduced in a gas phase at 300° C. for 2 hours under hydrogen gas flow, and then slowly oxidized with 5.8% O 2 /N 2 gas to obtain a 5% by mass Ru/ZrO 2 catalyst.
The same method as in Example 1 was carried out except that this 5 mass % Ru/ZrO 2 catalyst was used as the catalyst. The results are shown in Table-1.
［比較例５］
反応温度を１６０℃としたこと以外は実施例１と同様の方法で行った。結果を表－１に示す。
[Comparative example 5]
The same method as in Example 1 was carried out except that the reaction temperature was 160°C. The results are shown in Table-1.
［比較例６］
触媒として、５質量％Ｒｈ／ＡＣ触媒（エヌ・イーケムキャット製ＮＸ－Ｔｙｐｅ）を用いた以外は実施例１と同様の方法で行った。結果を表－１に示す。
[Comparative example 6]
The same method as in Example 1 was conducted except that a 5% by mass Rh/AC catalyst (NX-Type, manufactured by N.E. Chemcat) was used as the catalyst. The results are shown in Table-1.
［比較例７］
触媒として、５質量％Ｐｄ／ＡＣ触媒（エヌ・イーケムキャット製Ｅ－Ｔｙｐｅ）を用いた以外は実施例１と同様の方法で行った。結果を表－１に示す。
[Comparative Example 7]
The same method as in Example 1 was conducted except that a 5% by mass Pd/AC catalyst (E-Type manufactured by N.E. Chemcat) was used as the catalyst. The results are shown in Table-1.
表－１より次のことが分かる。
Ｒｕを炭素系担体に担持した触媒を用いて６０～１５０℃でＨＣＰの水素化を行った実施例１～５では、ｔｒａｎｓ比率の高いＣＰＤＬをｃｉｓ／ｔｒａｎｓ比率が低く、高収率で得ることができた。
The following can be seen from Table 1.
In Examples 1 to 5, in which HCP was hydrogenated at 60 to 150 °C using a catalyst in which Ru was supported on a carbon-based carrier, CPDL with a high trans ratio was obtained with a low cis/trans ratio and in high yield. was completed.
これに対して、担体として炭素系担体を用いていない比較例１～４のうち、比較例１～３では、ｃｉｓ／ｔｒａｎｓ比率が高く、ｔｒａｎｓ比率の高いＣＰＤＬを製造することはできず、特に比較例４ではＣＰＤＬ自体の収率も低い。
水素化反応温度が高過ぎる比較例５では、ＣＰＤＬ収率が非常に低い。
触媒貴金属としてＲｈを用いた比較例６ではＣＰＤＬを殆ど製造できず、ｔｒａｎｓ比率も著しく低い。
触媒貴金属としてＰｄを用いた比較例７では、ｔｒａｎｓ比率は高いがＣＰＤＬ収率が非常に低い。
On the other hand, among Comparative Examples 1 to 4 in which a carbon-based carrier is not used as a carrier, Comparative Examples 1 to 3 have a high cis/trans ratio and cannot produce CPDL with a high trans ratio. In Comparative Example 4, the yield of CPDL itself was also low.
In Comparative Example 5, where the hydrogenation reaction temperature is too high, the CPDL yield is very low.
In Comparative Example 6 in which Rh was used as the catalytic noble metal, almost no CPDL could be produced, and the trans ratio was also extremely low.
In Comparative Example 7 in which Pd was used as the catalyst noble metal, the trans ratio was high, but the CPDL yield was very low.
Claims (3)
A method for producing 1,3-cyclopentanediol in which the hydrogenation is carried out in a solvent, wherein the solvent is at least one selected from water, an ether solvent, and an alcohol solvent. 2. The method for producing 1,3-cyclopentanediol according to 2.
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