JP2023508205A - 1,4-シクロヘキサンジメタノールの製造方法 - Google Patents
1,4-シクロヘキサンジメタノールの製造方法 Download PDFInfo
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- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 119
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 114
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims description 87
- 239000003054 catalyst Substances 0.000 claims description 82
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 claims description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 32
- 239000007795 chemical reaction product Substances 0.000 claims description 25
- 239000000047 product Substances 0.000 claims description 24
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- 239000006227 byproduct Substances 0.000 claims description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000010948 rhodium Substances 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 238000006317 isomerization reaction Methods 0.000 abstract description 24
- 230000008569 process Effects 0.000 abstract description 11
- 239000007858 starting material Substances 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 53
- 229910052799 carbon Inorganic materials 0.000 description 31
- 239000000376 reactant Substances 0.000 description 25
- 239000011148 porous material Substances 0.000 description 17
- 238000003756 stirring Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 6
- 235000019241 carbon black Nutrition 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 3
- -1 polyethylene terephthalate Polymers 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 241000721047 Danaus plexippus Species 0.000 description 2
- 241000509579 Draco Species 0.000 description 2
- 101000859758 Homo sapiens Cartilage-associated protein Proteins 0.000 description 2
- 101000916686 Homo sapiens Cytohesin-interacting protein Proteins 0.000 description 2
- 101000726740 Homo sapiens Homeobox protein cut-like 1 Proteins 0.000 description 2
- 101000761460 Homo sapiens Protein CASP Proteins 0.000 description 2
- 101000761459 Mesocricetus auratus Calcium-dependent serine proteinase Proteins 0.000 description 2
- 102100024933 Protein CASP Human genes 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- TTXWERZRUCSUED-UHFFFAOYSA-N [Ru].[Sn] Chemical compound [Ru].[Sn] TTXWERZRUCSUED-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000979 synthetic dye Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
- C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
- B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
- B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
- C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
- C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
本出願は、2019年12月27日付の韓国特許出願第10-2019-0176139号および2020年12月24日付の韓国特許出願第10-2020-0183548号に基づく優先権の利益を主張し、当該韓国特許出願の文献に開示された全ての内容は本明細書の一部として含まれる。
撹拌機が備えられた第1反応器にテレフタル酸(terephthalic acid)、第1水素化触媒、および水を含む反応溶液および水素気体を供給し、水素化反応を行い、シス異性体およびトランス異性体を含む1,4-シクロヘキサンジカルボン酸(1,4-cyclohexane dicarboxylic acid、CHDA)を製造する第1段階;および
撹拌機が備えられた第2反応器に前記第1段階反応生成物、第2水素化触媒、および水を含む反応溶液、および水素気体を供給し、水素化反応を行い、シス異性体およびトランス異性体を含む1,4-シクロヘキサンジメタノール(1,4-cyclohexanedimethanol、CHDM)を製造する第2段階;を含む、1,4-シクロヘキサンジメタノールの製造方法を提供する。
第1段階は、撹拌機が備えられた第1反応器にテレフタル酸(terephthalic acid)、第1水素化触媒、および水を含む反応溶液、および水素気体を供給し水素化反応を行い、シス異性体およびトランス異性体を含む1,4-シクロヘキサンジカルボン酸を製造する段階である。
第2段階は、撹拌機が備えられた第2反応器に前記第1段階反応生成物、第2水素化触媒、および水を含む反応溶液、および水素気体を供給し水素化反応を行い、シス異性体およびトランス異性体を含む1,4-シクロヘキサンジメタノール(1,4-cyclohexanedimethanol、CHDM)を製造する段階である。
本発明の一実施形態によれば、前記第2段階の反応生成物から溶媒と副生成物を除去して精製された1,4-シクロヘキサンジメタノールを回収する第3段階をさらに含むことができる。
実施例1
第1段階
ガス誘導式(gas-induced type)撹拌機を含む第1反応器を用意した。
ガス誘導式(gas-induced type)撹拌機を含む第2反応器を用意した。
第2段階反応の生成物から金属フィルターで水素化触媒を除去した1,4-シクロヘキサンジメタノール組成物に対してエバポレーター(Evaporator)で温度50~60℃、圧力10~20torrの条件で水を蒸発させて最初の水含有量に対して95%まで1次で水を除去し、前記1次の水除去段階を経た1,4-シクロヘキサンジメタノール組成物に対して蒸留(Distillation)装置で、温度100~120℃、圧力0.01~0.001torrの条件で水を蒸発させて最初の水含有量に対して99%まで2次で水を除去した。
前記水除去段階を経た1,4-シクロヘキサンジメタノール組成物に対してDistillation装置で蒸留によって副生成物を除去して精製された1,4-シクロヘキサンジメタノールを得た。
実施例1の第1段階で、テレフタル酸(TPA)286gを使用したことを除いては、実施例1の第1段階と同様に行った。
実施例1の第1段階で、テレフタル酸(TPA)378gを使用したことを除いては、実施例1の第1段階と同様に行った。
実施例1の第1段階で、テレフタル酸(TPA)492gを使用したことを除いては、実施例1の第1段階と同様に行った。
前記実施例に対して、CHDAの収率、転換率、選択度と、CHDMの収率、転換率、選択度を計算して下記表1に示す。
転換率(conversion)=反応したTPAのモル数/供給されたTPAのモル数
選択度(selectivity)=生成されたCHDAのモル数/反応したTPAのモル数
収率(yield)=転換率×選択度
転換率(conversion)=反応したCHDAのモル数/供給されたCHDAのモル数
選択度(selectivity)=生成されたCHDMのモル数/反応したCHDAのモル数
収率(yield)=転換率×選択度
Claims (15)
- 撹拌機が備えられた第1反応器にテレフタル酸(terephthalic acid)、第1水素化触媒、および水を含む反応溶液、および水素気体を供給し、水素化反応を行い、シス異性体およびトランス異性体を含む1,4-シクロヘキサンジカルボン酸(1,4-cyclohexane dicarboxylic acid、CHDA)を製造する第1段階;および
撹拌機が備えられた第2反応器に前記第1段階反応生成物、第2水素化触媒、および水を含む反応溶液、および水素気体を供給し、水素化反応を行い、シス異性体およびトランス異性体を含む1,4-シクロヘキサンジメタノール(1,4-cyclohexanedimethanol、CHDM)を製造する第2段階;を含む、1,4-シクロヘキサンジメタノールの製造方法。 - 前記テレフタル酸は、テレフタル酸および水の総量に対して5~25重量%で含まれる、請求項1に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 第1段階の水素化反応を行う段階は、230~300℃の温度で行われる、請求項1に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 第1段階で前記水素気体は50~220barの圧力で供給する、請求項1に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 前記第1水素化触媒は、パラジウム(Pd)、ロジウム(Rh)、ルテニウム(Ru)、および白金(Pt)からなる群より選択される1種以上の金属を含む、請求項1に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 前記第1段階反応の生成物は、1,4-シクロヘキサンジカルボン酸および水を含み、前記1,4-シクロヘキサンジカルボン酸は、1,4-シクロヘキサンジカルボン酸および水の総量に対して5~30重量%で含まれる、請求項1に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 前記1,4-シクロヘキサンジカルボン酸は、トランス異性体を60重量%以上で含む、請求項6に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 第2段階の水素化反応を行う段階は、230~300℃の温度で行われる、請求項1に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 第2段階で前記水素気体は50~220barの圧力で供給する、請求項1に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 前記第2水素化触媒は、パラジウム(Pd)、ロジウム(Rh)、およびルテニウム(Ru)からなる群より選択される1種以上の金属、および
スズ(Sn)、鉄(Fe)、レニウム(Re)、およびガリウム(Ga)からなる群より選択される1種以上の金属をそれぞれ含む、請求項1に記載の1,4-シクロヘキサンジメタノールの製造方法。 - 前記第2水素化触媒は、ルテニウム(Ru)およびスズ(Sn)を含む、請求項10に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 前記第2段階で得られる1,4-シクロヘキサンジメタノールは、トランス異性体を63重量%以上で含む、請求項1に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 前記第2段階を行う前に、前記第1段階反応の反応生成物に含まれている第1水素化触媒を除去する段階をさらに含む、請求項1に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 前記第2段階反応生成物から溶媒と副生成物を除去して精製された1,4-シクロヘキサンジメタノールを回収する第3段階をさらに含む、請求項1に記載の1,4-シクロヘキサンジメタノールの製造方法。
- 請求項1に記載の方法で製造される1,4-シクロヘキサンジメタノールを含む、組成物。
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KR1020200183548A KR102691431B1 (ko) | 2019-12-27 | 2020-12-24 | 1,4-사이클로헥산디메탄올의 제조방법 |
KR10-2020-0183548 | 2020-12-24 | ||
PCT/KR2020/019189 WO2021133138A1 (ko) | 2019-12-27 | 2020-12-28 | 1,4-사이클로헥산디메탄올의 제조방법 |
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JP2002069016A (ja) * | 2000-08-30 | 2002-03-08 | Mitsubishi Chemicals Corp | テレフタル酸の水素添加方法 |
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JP2017515656A (ja) * | 2014-04-07 | 2017-06-15 | ロッテ ケミカル コーポレーション | 複合金属触媒造成物とそれを利用した1,4−シクロへキサンジメタノールの製造方法及びその装置 |
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JP2002145824A (ja) * | 2000-08-30 | 2002-05-22 | Mitsubishi Chemicals Corp | テレフタル酸の水素添加方法 |
WO2003035597A1 (fr) * | 2001-10-26 | 2003-05-01 | Mitsubishi Chemical Corporation | Procede de production d'acide trans-1, 4- cyclohexanedicarboxylique |
KR101619399B1 (ko) * | 2013-11-29 | 2016-05-10 | 롯데케미칼 주식회사 | 1,4-사이클로헥산디메탄올의 제조 방법 |
US9346737B2 (en) * | 2013-12-30 | 2016-05-24 | Eastman Chemical Company | Processes for making cyclohexane compounds |
KR101917366B1 (ko) * | 2016-09-29 | 2018-11-09 | 롯데케미칼 주식회사 | 1,4-사이클로헥산디카르복시산의 제조 방법 및 1,4-사이클로헥산디메탄올의 제조 방법 |
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JP2014177422A (ja) * | 2013-03-14 | 2014-09-25 | Mitsubishi Chemicals Corp | シクロアルカンジメタノールの製造方法 |
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