JPS6332053B2 - - Google Patents
Info
- Publication number
- JPS6332053B2 JPS6332053B2 JP12836280A JP12836280A JPS6332053B2 JP S6332053 B2 JPS6332053 B2 JP S6332053B2 JP 12836280 A JP12836280 A JP 12836280A JP 12836280 A JP12836280 A JP 12836280A JP S6332053 B2 JPS6332053 B2 JP S6332053B2
- Authority
- JP
- Japan
- Prior art keywords
- aliphatic
- pyrogallol
- aqueous solution
- extraction
- cyclohexanetriol
- 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.)
- Expired
Links
- -1 cyclohexane polyol Chemical class 0.000 claims description 17
- 150000002989 phenols Chemical class 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 10
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000622 liquid--liquid extraction Methods 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 24
- 238000000605 extraction Methods 0.000 description 12
- 229940079877 pyrogallol Drugs 0.000 description 12
- 238000000034 method Methods 0.000 description 9
- IZSANPWSFUSNMY-UHFFFAOYSA-N cyclohexane-1,2,3-triol Chemical compound OC1CCCC(O)C1O IZSANPWSFUSNMY-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- PFURGBBHAOXLIO-UHFFFAOYSA-N cyclohexane-1,2-diol Chemical compound OC1CCCCC1O PFURGBBHAOXLIO-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- RMOUBSOVHSONPZ-UHFFFAOYSA-N Isopropyl formate Chemical compound CC(C)OC=O RMOUBSOVHSONPZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- RLMGYIOTPQVQJR-UHFFFAOYSA-N cyclohexane-1,3-diol Chemical compound OC1CCCC(O)C1 RLMGYIOTPQVQJR-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は多価フエノールおよびシクロヘキサン
ポリオールを含む水溶液から多価フエノールを液
―液抽出分離する方法に関するものである。
カテコール、レゾルシン、ヒドロキノン、ピロ
ガロール等の多価フエノールを製造する方法とし
て、１，２―シクロヘキサンジオール、１，３―
シクロヘキサンジオール、１，４―シクロヘキサ
ンジオール、１，２，３―シクロヘキサントリオ
ール等のシクロヘキサンポリオールを接触的に脱
水素する方法が知られている。この方法において
は、選定される反応条件により、あるいは触媒の
劣化などの理由により、しばしば脱水素反応生成
物である多価フエノール中に未反応原料であるシ
クロヘキサンポリオールが混入する。これらの化
合物は物性が近似しているために蒸留、晶析など
の手段で分離することが困難であるが、本発明者
らの検討の結果、適当な抽剤を使用することによ
り、多価フエノールおよびシクロヘキサンポリオ
ールを含む水溶液から選択的に多価フエノールを
抽出分離し得ることが見い出された。
すなわち、本発明の目的は、工業的有利に多価
フエノールおよびシクロヘキサンポリオールを含
む水溶液から多価フエノールを抽出分離する方法
を提供することにあり、この目的は、多価フエノ
ールおよびシクロヘキサンポリオールを含む水溶
液を常温で液体且つ水に難溶性の脂肪族エーテ
ル、脂肪族又は脂環式ケトンおよび脂肪族エステ
ルより選ばれる少くとも一種の抽剤と接触させる
ことにより達成される。
本発明方法により抽出分離される多価フエノー
ルは、カテコール、レゾルシン、ヒドロキノン、
ピロガロール、フロログルシンなどの主に２価お
よび３価のフオノールであり、これらのほかに
１，２―シクロヘキサンジオール、１，３―シク
ロヘキサンジオール、１，４―シクロヘキサンジ
オール、１，２，３―シクロヘキサントリオー
ル、フロログルシツトなどのシクロヘキサンポリ
オールが不純物成分として含まれている水溶液か
ら多価フエノールを抽出分離する場合に本発明方
法が適用される。特に、ピロガロールおよび１，
２，３―シクロヘキサントリオールを含む水溶液
からピロガロールを抽出分離する場合に好ましく
適用される。
抽剤としては、常温で液体且つ水に難溶性の脂
肪族エーテル、脂肪族又は脂環式ケトンおよび脂
肪族エステルが使用される。具体的には、ジエチ
ルエーテル、ジイソプロピルエーテル等の脂肪族
エーテル、イソブチルメチルケトン、シクロヘキ
サノン等の脂肪族又は脂環式ケトン、酢酸メチ
ル、酢酸エチル、酢酸ブチル、ギ酸イソプロピル
等の脂肪族エステルが挙げられる。
抽剤の使用量は、通常、多価フエノールおよび
シクロヘキサンポリオールを含む水溶液に対して
0.05〜20容量倍程度であるが、最適量は、多価フ
エノールの種類および濃度、共存するシクロヘキ
サンポリオールの濃度、抽剤の種類および水への
溶解度、操作温度などの条件により異なる。たと
えば、イソブチルメチルケトンを抽剤として用い
る場合は、水溶液に対して0.5〜５容量倍程度が
好ましい。
抽出操作温度は特に限定されるものではなく抽
剤の凝固点以上の温度で行なえばよい。通常は常
温〜80℃程度の温度で抽出操作が行なわれる。
多価フエノールは酸素との反応性が高いので、
抽出操作は窒素等の不活性気流中で行なうことが
望ましい。
本発明方法により抽出を行なえば、多価フエノ
ールが抽出されて抽剤中に移行し、シクロヘキサ
ンポリオールが水溶液中に残存する。抽出液から
蒸留などの方法によつて抽剤を分離し、再結晶等
の公知の精製手段に従つて精製を行なうことによ
り、高純度の多価フエノールを得ることができ
る。
次に本発明を実施例により更に具体的に説明す
る。
実施例 １〜６
水９mlに所定量のピロガロールおよび１，２，
３―シクロヘキサントリオールを溶解させてメー
クアツプした抽料に所定の抽剤を添加し、窒素雰
囲気下、室温で15分間撹拌したのち分液した。抽
出液相（有機液相）およびラフイネート相（水溶
液相）に含まれるピロガロールおよび１，２，３
―シクロヘキサントリオールを定量し、下記の式
によりピロガロールおよび１，２，３―シクロヘ
キサントリオールの分配係数ならびにピロガロー
ルの抽出選択性を算出した。
mp＝c1 p／c2 p、mt＝c1 t／c2 t
mp……ピロガロールの分配係数
mt……１，２，３―シクロヘキサントリオー
ルの分配係数
c1 p……抽出液相のピロガロール濃度（mol／
ｌ）
c2 p……ラフイネート相のピロガロール濃度
（mol／ｌ）
c1 t……抽出液相の１，２，３―シクロヘキサ
ントリオール濃度（mol／ｌ）
c2 t……ラフイネート相の１，２，３―シクロ
ヘキサントリオール濃度（mol／ｌ）
α＝mp／mp＋mt×100（％）
α……ピロガロールの抽出選択性
結果はピロガロールおよび１，２，３―シクロ
ヘキサントリオール使用量ならびに抽剤の種類お
よび使用量とともに表―１に示す。
The present invention relates to a method for separating polyhydric phenols by liquid-liquid extraction from an aqueous solution containing polyhydric phenols and cyclohexane polyol. 1,2-cyclohexanediol, 1,3-
A method for catalytically dehydrogenating cyclohexane polyols such as cyclohexanediol, 1,4-cyclohexanediol, and 1,2,3-cyclohexanetriol is known. In this method, cyclohexane polyol, which is an unreacted raw material, is often mixed into polyhydric phenol, which is a dehydrogenation reaction product, due to the selected reaction conditions or due to deterioration of the catalyst. Since these compounds have similar physical properties, it is difficult to separate them by means such as distillation or crystallization. It has been found that polyhydric phenols can be selectively extracted and separated from an aqueous solution containing phenol and cyclohexane polyol. That is, an object of the present invention is to provide an industrially advantageous method for extracting and separating polyhydric phenols from an aqueous solution containing polyhydric phenols and cyclohexane polyol; This is achieved by bringing the extractant into contact with at least one extractant selected from aliphatic ethers, aliphatic or alicyclic ketones, and aliphatic esters that are liquid at room temperature and poorly soluble in water. The polyhydric phenols extracted and separated by the method of the present invention include catechol, resorcinol, hydroquinone,
Mainly divalent and trivalent phonols such as pyrogallol and phloroglucin, and in addition to these, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2,3-cyclohexanetriol The method of the present invention is applied to the case of extracting and separating polyhydric phenols from an aqueous solution containing cyclohexane polyols such as phloroglucitate and the like as impurity components. In particular, pyrogallol and 1,
It is preferably applied when extracting and separating pyrogallol from an aqueous solution containing 2,3-cyclohexanetriol. As the extraction agent, aliphatic ethers, aliphatic or alicyclic ketones, and aliphatic esters that are liquid at room temperature and poorly soluble in water are used. Specific examples include aliphatic ethers such as diethyl ether and diisopropyl ether, aliphatic or alicyclic ketones such as isobutyl methyl ketone and cyclohexanone, and aliphatic esters such as methyl acetate, ethyl acetate, butyl acetate, and isopropyl formate. . The amount of extractant used is usually for an aqueous solution containing polyhydric phenols and cyclohexane polyols.
The amount is approximately 0.05 to 20 times the volume, but the optimum amount varies depending on conditions such as the type and concentration of polyhydric phenol, the concentration of coexisting cyclohexane polyol, the type and solubility in water of the extractant, and the operating temperature. For example, when isobutyl methyl ketone is used as an extraction agent, it is preferably about 0.5 to 5 times the volume of the aqueous solution. The temperature of the extraction operation is not particularly limited and may be carried out at a temperature equal to or higher than the freezing point of the extraction agent. The extraction operation is usually carried out at temperatures ranging from room temperature to about 80°C. Polyhydric phenols are highly reactive with oxygen, so
The extraction operation is preferably carried out in an inert gas stream such as nitrogen. When extraction is performed according to the method of the present invention, polyhydric phenols are extracted and transferred into the extractant, and cyclohexane polyol remains in the aqueous solution. Highly pure polyhydric phenol can be obtained by separating the extractant from the extract by a method such as distillation and purifying it by a known purification method such as recrystallization. Next, the present invention will be explained in more detail with reference to Examples. Examples 1 to 6 A predetermined amount of pyrogallol and 1,2,
A predetermined extractant was added to the extract made up by dissolving 3-cyclohexanetriol, stirred for 15 minutes at room temperature under a nitrogen atmosphere, and then separated. Pyrogallol and 1,2,3 contained in the extract liquid phase (organic liquid phase) and the roughinate phase (aqueous solution phase)
-Cyclohexanetriol was quantified, and the distribution coefficient of pyrogallol and 1,2,3-cyclohexanetriol and the extraction selectivity of pyrogallol were calculated using the following formula. m p = c 1 p / c 2 p , m t = c 1 t / c 2 t m p ...Partition coefficient of pyrogallol m t ...Partition coefficient of 1,2,3-cyclohexanetriol c 1 p ...Extraction Pyrogallol concentration in liquid phase (mol/
l) c 2 p ...Pyrogallol concentration in the roughinate phase (mol/l) c 1 t ...1,2,3-cyclohexanetriol concentration in the extract phase (mol/l) c 2 t ...1, 2,3-Cyclohexanetriol concentration (mol/l) α=m p /m p +m t ×100 (%) α……Extraction selectivity of pyrogallol The results are based on the amount of pyrogallol and 1,2,3-cyclohexanetriol used and the extraction Table 1 shows the types and amounts of agents used.
【表】
実施例 ７
パラジウムおよび硫酸カリウムを活性炭に担持
した触媒を使用し、触媒上に窒素ガスを流通させ
ながら１，２，３―シクロヘキサントリオール水
溶液を反応系に供給し、常圧、300℃の条件下気
相で脱水素反応を行なつた。反応生成液120mlに
イソブチルメチルケトン240mlを添加し、実施例
１と同様に抽出を行なつた。抽出液中およびラフ
イネート中に含まれる各成分を定量した結果を表
―２に示す。[Table] Example 7 Using a catalyst in which palladium and potassium sulfate were supported on activated carbon, an aqueous solution of 1,2,3-cyclohexanetriol was supplied to the reaction system while nitrogen gas was passed over the catalyst, and the temperature was maintained at normal pressure and 300°C. The dehydrogenation reaction was carried out in the gas phase under the following conditions. 240 ml of isobutyl methyl ketone was added to 120 ml of the reaction product solution, and extraction was performed in the same manner as in Example 1. Table 2 shows the results of quantifying each component contained in the extract and the raffinate.
Claims (1)
ールを含む水溶液を常温で液体且つ水に難溶性の
脂肪族エーテル、脂肪族又は脂環式ケトンおよび
脂肪族エステルより選ばれる少くとも一種の抽剤
と接触させて多価フエノールを選択的に液―液抽
出することを特徴とする多価フエノールの分離
法。1 An aqueous solution containing a polyhydric phenol and a cyclohexane polyol is brought into contact with at least one extractant selected from aliphatic ethers, aliphatic or cycloaliphatic ketones, and aliphatic esters that are liquid at room temperature and poorly soluble in water. A separation method for polyhydric phenols characterized by selective liquid-liquid extraction of phenols.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12836280A JPS5753423A (en) | 1980-09-16 | 1980-09-16 | Separation of polyhydric phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12836280A JPS5753423A (en) | 1980-09-16 | 1980-09-16 | Separation of polyhydric phenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5753423A JPS5753423A (en) | 1982-03-30 |
| JPS6332053B2 true JPS6332053B2 (en) | 1988-06-28 |
Family
ID=14982937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12836280A Granted JPS5753423A (en) | 1980-09-16 | 1980-09-16 | Separation of polyhydric phenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5753423A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO344650B1 (en) | 2018-06-28 | 2020-02-17 | Mjoes Metallvarefabrikk As | Pump device and its use |
-
1980
- 1980-09-16 JP JP12836280A patent/JPS5753423A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5753423A (en) | 1982-03-30 |
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