JP6718017B2 - 1,3−シクロヘキサンジメタノールの製造方法 - Google Patents
1,3−シクロヘキサンジメタノールの製造方法 Download PDFInfo
- Publication number
- JP6718017B2 JP6718017B2 JP2019512624A JP2019512624A JP6718017B2 JP 6718017 B2 JP6718017 B2 JP 6718017B2 JP 2019512624 A JP2019512624 A JP 2019512624A JP 2019512624 A JP2019512624 A JP 2019512624A JP 6718017 B2 JP6718017 B2 JP 6718017B2
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- Prior art keywords
- compound
- cyclohexanedimethanol
- cyclohexanedicarboxylic acid
- weight
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 title claims description 52
- 238000004519 manufacturing process Methods 0.000 title claims description 51
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 78
- 239000003054 catalyst Substances 0.000 claims description 68
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 62
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 50
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 claims description 47
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 27
- 229910052697 platinum Inorganic materials 0.000 claims description 26
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 25
- 229910052718 tin Inorganic materials 0.000 claims description 25
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 24
- 229910052707 ruthenium Inorganic materials 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007795 chemical reaction product Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 150000003304 ruthenium compounds Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- -1 alicyclic carboxylic acid Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HDVSVZIJLLTMRH-UHFFFAOYSA-N 3-(3-ethyloctan-3-yloxycarbonyl)cyclohexane-1-carboxylic acid Chemical compound CCCCCC(CC)(CC)OC(=O)C1CCCC(C1)C(=O)O HDVSVZIJLLTMRH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 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
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 1
- YRUMDWGUXBZEPE-UHFFFAOYSA-N cyclohexane Chemical compound C1CCCCC1.C1CCCCC1 YRUMDWGUXBZEPE-UHFFFAOYSA-N 0.000 description 1
- KLTWJZTUJHGCSJ-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1.OC1CCCCC1 KLTWJZTUJHGCSJ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YJBKVPRVZAQTPY-UHFFFAOYSA-J tetrachlorostannane;dihydrate Chemical compound O.O.Cl[Sn](Cl)(Cl)Cl YJBKVPRVZAQTPY-UHFFFAOYSA-J 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- ZTWIEIFKPFJRLV-UHFFFAOYSA-K trichlororuthenium;trihydrate Chemical compound O.O.O.Cl[Ru](Cl)Cl ZTWIEIFKPFJRLV-UHFFFAOYSA-K 0.000 description 1
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Description
転換率(%)=[(投入された1,3−シクロヘキサンジカルボン酸の含有量(mol%))−(反応後に残った1,3−シクロヘキサンジカルボン酸の含有量(mol%))]/[投入された1,3−シクロヘキサンジカルボン酸の含有量(mol%)]*100
製造例1
塩化錫二水和物、塩化ルテニウム三水和物および塩化白金酸六水和物を称量して、0.1ノルマル濃度の塩化水素水溶液に溶解して金属前駆体溶液を製造した。シリカ担持体[比表面積:約255m2/g、全細孔容積:1.03cm3/g、平均細孔直径:110Å]の内部気孔体積ほど金属前駆体溶液を落として触媒を担持させた後、120℃で12時間乾燥させた。以降、空気条件下で600℃で焼成してルテニウム、錫、白金が複合金属形態で担持された触媒を得た(ルテニウム(Ru)、錫(Sn)および白金(Pt)の重量比は下記表1に記載の通りである)。
ルテニウム(Ru)、錫(Sn)および白金(Pt)の重量比は下記表1のように変更したことを除いては、前記製造例1と同様にして金属触媒を製造した。
ルテニウム(Ru)、錫(Sn)および白金(Pt)の重量比は下記表1のように変更したことを除いては、前記製造例1と同様にして金属触媒を製造した。
シリカ担持体の代わりにY−ゼオライトを使用したことを除いては、前記製造例1と同様にして金属触媒を製造した。
実施例1
撹拌機を備えた500mlの高圧反応器に前記製造例1で得られた金属担持触媒、1,3−シクロヘキサンジカルボン酸、およびイオン交換水を下記表1の重量比率を満足するように充填した。前記高圧反応器内の大気を室温で窒素に変えた後、水素気体を高圧反応器内に導入しながら前記高圧反応器の内部温度を210℃に上昇させて、100barの圧力で水素添加反応を行った。このとき、前記高圧反応器内部での攪拌速度を350rpmで固定し、3時間反応を進行した。前記反応時間に到達した状態で反応器内部を常温に冷却させ、反応器を解体して反応結果物を採取した。前記反応結果物を濃縮回転蒸発器を使用して水を蒸留除去させることにより、最終結果物1,3−シクロヘキサンジメタノールを得た。
下記表1のように、1,3−CHDA 20wt%を充填し、3.5時間反応を進行したことを除いては、実施例1と同様の方法で1,3−シクロヘキサンジメタノールを製造した。
比較例1
前記製造例2で得られた金属担持触媒を充填したことを除いては、実施例1と同様の方法で1,3−シクロヘキサンジメタノールを製造した。
前記製造例3で得られた金属担持触媒を使用したことを除いては、実施例1と同様の方法で1,3−シクロヘキサンジメタノールを製造した。
前記製造例4で得られた金属担持触媒を使用したことを除いては、実施例1と同様の方法で1,3−シクロヘキサンジメタノールを製造した。
前記実施例および比較例で得られた1,3−シクロヘキサンジメタノールの物性を下記方法で測定し、その結果を表1に示した。
前記実施例および比較例で得られた最終結果物に対してガスクロマトグラフィーを使用して、反応物質(1,3−シクロヘキサンジカルボン酸)の転換率および1,3−シクロヘキサンジメタノールの選択度を測定した。
選択度(%)=[(1,3−シクロヘキサンジメタノールの含有量(mol%)/反応結果物の含有量(mol%))*100]
転換率(%)=[(投入された1,3−シクロヘキサンジカルボン酸の含有量(mol%))−(反応後に残った1,3−シクロヘキサンジカルボン酸の含有量(mol%))]/[投入された1,3−シクロヘキサンジカルボン酸の含有量(mol%)]*100
1)カラム:Agilent 19091J−413(カラム長さ:30m、内部直径:0.32mm、フィルム厚さ:0.25μm)
2)GC装置:ガスクロマトグラフィーモデルAgilent 7890
3)キャリアーガス:ヘリウム
4)検出器:水素炎イオン化検出器(FID)
Claims (13)
- シリカ担体に固定し、ルテニウム(Ru)化合物、錫(Sn)化合物および白金(Pt)化合物が1:0.8〜1.2:1.6〜2.4の重量比で含まれている金属触媒の存在下、1,3−シクロヘキサンジカルボン酸を還元させる段階を含む、1,3−シクロヘキサンジメタノールの製造方法。
- 前記金属触媒に含まれるシリカ担体は100m2/g〜500m2/gの比表面積を有する、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法。
- 前記金属触媒に含まれるシリカ担体の全細孔容積は2cm3/g以下である、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法。
- 前記金属触媒に含まれるシリカ担体の平均気孔直径は80Å〜200Åである、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法。
- 前記金属触媒に含まれるシリカ担体の含水率は0.1重量%〜10重量%である、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法。
- 前記金属触媒は、前記ルテニウム(Ru)化合物0.5重量%〜10重量%を含む、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法。
- 前記金属触媒は、前記白金(Pt)化合物100重量部対比錫(Sn)化合物40重量部〜70重量部を含む、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法。
- 前記1,3−シクロヘキサンジカルボン酸を還元させる段階は、前記1,3−シクロヘキサンジカルボン酸および水素気体を接触させる段階を含む、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法。
- 前記1,3−シクロヘキサンジカルボン酸を還元させる段階は50℃〜350℃で遂行される、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法。
- 前記1,3−シクロヘキサンジカルボン酸を還元させる段階は30bar〜150barの圧力で遂行される、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法。
- 前記1,3−シクロヘキサンジカルボン酸100重量部対比前記金属触媒10重量部〜300重量部を使用する、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法。
- 前記金属触媒は、ルテニウム(Ru)化合物、錫(Sn)化合物および白金(Pt)化合物を1:0.9〜1.1:1.6〜2.0の重量比で含む、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法。
- 下記数式によって定義される転換率は90%以上である、請求項1に記載の1,3−シクロヘキサンジメタノールの製造方法:
[数式]
転換率(%)=[(投入された1,3−シクロヘキサンジカルボン酸の含有量(mol%))−(反応後に残った1,3−シクロヘキサンジカルボン酸の含有量(mol%))]/[投入された1,3−シクロヘキサンジカルボン酸の含有量(mol%)]×100
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PCT/KR2017/009715 WO2018048175A1 (ko) | 2016-09-08 | 2017-09-05 | 1, 3-사이클로헥산디메탄올의 제조 방법 |
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