CN1706784A - O-ethoxyl phenol refining process - Google Patents
O-ethoxyl phenol refining process Download PDFInfo
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- CN1706784A CN1706784A CN 200510016841 CN200510016841A CN1706784A CN 1706784 A CN1706784 A CN 1706784A CN 200510016841 CN200510016841 CN 200510016841 CN 200510016841 A CN200510016841 A CN 200510016841A CN 1706784 A CN1706784 A CN 1706784A
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- toluene
- pyrocatechol
- oil phase
- ethoxyl
- monoethyl ether
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Abstract
The o-ethoxyl phenol refining process includes the following steps: alkali washing condensated o-ethoxyl phenol oil phase or o-ethoxyl phenol product obtained through catechol process with 5-20 % sodium hydroxide solution for 30 min and separating liquid; regulating pH value of the water phase after alkali washing with hydrochloric acid to 1-4, extracting with toluene, and separating liquid to collect oil phase; distilling the oil phase at 110-120 deg.c to recover toluene, lowering the temperature to 30-40 deg.c for decompression rectification to obtain o-ethoxyl phenol of purity not lower than 99.2 %, with the recovered toluene being reused. The present invention can raise the production capacity of industrial apparatus and lower production cost.
Description
Technical field
The present invention relates to a kind of process for purification of pyrocatechol, relate in particular to the process for purification of the synthetic Pyrocatechol monoethyl ether of a kind of pyrocatechol method.
Background technology
Pyrocatechol monoethyl ether claims 2-ethoxy-phenol, ethylguaiacol again, is the main raw material of synthetic vanirone, also is indispensable medicine intermediate in the pharmaceutical industry.
The main synthetic method of Pyrocatechol monoethyl ether has o-phenetidine method, pyrocatechol method.Wherein the pyrocatechol method is divided into pyrocatechol, Ethanol Method again, pyrocatechol, ethyl sulfate method and pyrocatechol, monochloroethane method.And the synthetic Pyrocatechol monoethyl ether of pyrocatechol, monochloroethane method is to be raw material with pyrocatechol, monochloroethane, under catalyst action, through contract and, post-treating and other steps and making, its chemical equation is as follows:
1, contracts and react
2, alkali cleaning reaction
3, acidification reaction
At present, the Pyrocatechol monoethyl ether of selling on the market, its purity is lower, be generally 95～98.5%, and, use the lower raw material Pyrocatechol monoethyl ether of purity for medicine with as the vanirone of foodstuff additive, all can cause detrimentally affect to the healthy of its quality product and people.Therefore, improve the great attention that its quality product has caused manufacturing enterprise and research unit, constantly improve from synthesis technique, product purification aspect.In synthetic Pyrocatechol monoethyl ether process, O-ethoxyl phenolic product that obtains simultaneously and by-product o-2-ethoxy benzene phenol boiling point only differ 1 ℃, are difficult to be separated.
Summary of the invention
The objective of the invention is to improve the deficiency that prior art exists, improve the purity of Pyrocatechol monoethyl ether, a kind of process for purification of Pyrocatechol monoethyl ether is provided
The objective of the invention is to adopt following technical scheme to realize.
The process for purification of the synthetic Pyrocatechol monoethyl ether of pyrocatechol method is characterized in that:
(1) with the condensated liquid oil phase or the O-ethoxyl phenolic product of the synthetic Pyrocatechol monoethyl ether that obtains of pyrocatechol method, with 5～20% sodium hydroxide solution alkali cleanings 30 minutes, separatory then; The water of getting after the alkali cleaning is regulated pH value to 1～4 with hydrochloric acid, then, fully extracts with toluene, and separatory is collected oil phase.
(2) oil phase that will obtain by (1) under 110～120 ℃ of temperature air distillation to reclaim toluene, when temperature is reduced to 30～40 ℃, decompression distillation then, gold-plating branch before vacuum tightness-0.090～0.092MPa, 35～80 ℃ of tower top temperatures, reflux ratio condition under are gathered at 1: 1; In reflux ratio is 2: 1～3: 1, collects product under vacuum tightness-0.094～0.096Mpa condition, stops to gather when tower top temperature rises rapidly, just makes the purified Pyrocatechol monoethyl ether.
It is the glass column of 38mm that rectifying tower adopts internal diameter, and insulation is good, the white steel triangle filler of the long 1.5mm of interior rim, and packed height is 400mm, reflux ratio adopts several conventional method estimations.Vacuum pump is that SHB-III circulation ability of swimming is used vacuum pump more.
(3) above-described alkali cleaning and extraction are fully vibrated by separating funnel and are finished.
(4) above-mentioned process for purification, the toluene of recovery is applied mechanically, and can be used as above-mentioned extraction agent again.
(5) employing gas-chromatography hydrogen flame method, external standard method, chemical analysis such as Pyrocatechol monoethyl ether, toluene are analyzed in the oil phase of the present invention.
The present invention has following significant effect:
(1) with the refining Pyrocatechol monoethyl ether of technical scheme of the present invention, its purity 〉=99.2%;
(2) because Pyrocatechol monoethyl ether product purity height, the cleaning cycle that can make vanirone device extraction tower is than using the import like product to prolong 1 times (in the product application test, under the same conditions, the clear tower cycle of imported product is 25 batches, handicraft product is more than 50 batches), the throughput that this will improve vanirone industrialization device reduces its production cost.
(3) yield of above-mentioned process for refining is higher.
Embodiment
Now the present invention is further described as follows by embodiment:
Get same lot number pyrocatechol, monochloroethane method synthetic contracts and oil phase, as refining raw material, carries out embodiment 1,2,3 experiment respectively.Get same lot number pyrocatechol, Ethanol Method synthetic O-ethoxyl phenolic product (purity is 98.5%, buys from French Rhodia),, carry out embodiment 4,5,6 experiments respectively as refining raw material.
Embodiment 1,2,3 is synthetic contract and the oil phase method as follows: in autoclave, add toluene 2400g, water 1500g opens stirring, open autoclave axle water coolant, add pyrocatechol 660g, yellow soda ash 60g, tetraethyl-amine bromide 27g, solid caustic soda 312g, monochloroethane 540g again, seal lid after, inflated with nitrogen is to 1.0Mpa, kept 2 minutes, check whether leak gas,, put pressure as air tight.Begin to heat up, keeping 4 hours under 120～130 ℃ of temperature, under 0.2～1.0MPa pressure, reaction is cooled to room temperature after finishing, and opens autoclave after the pressure release, feed liquid is poured in the separating funnel into separatory.Water adds hydrochloric acid and transfers pH value 5～6, after fully extracting with toluene, merges oil phase.Altogether oil phase 3270g, wherein Pyrocatechol monoethyl ether content is 21.83%.
Embodiment 1
Get above-mentioned contracting and liquid oil phase 1090g, two parts of div in par aeq are decided to be the 1st, 2 batch, carry out following steps respectively: with 5% sodium hydroxide solution 960g alkali cleaning 30 minutes, separatory then; Getting after the alkali cleaning water, to add the 31% hydrochloric acid pH value that neutralizes be 1, adds toluene 600g then and fully extract, and separatory is collected oil phase.In the distilling flask that extraction oil is added to, install condenser, tail pipe, receptor, thermometer then, be heated to 140 ℃ with oil bath and distill.When column temperature was 110 ℃～120 ℃, cat head began to have cut to flow out, and this moment, effluent mainly was a toluene, included minor amount of water.Column temperature began to descend when toluene had steamed soon, and when column temperature was 30 ℃～40 ℃, air distillation finished.Vacuum system is connected in cooling back, be-0.090 in vacuum tightness～-0.092Mpa, tower top temperature are that 70～80 ℃, reflux ratio are condition under to gather foreshot at 1: 1; In reflux ratio is 2: 1～3: 1; Vacuum tightness is-0.094～-collect product under the 0.096Mpa condition, when cat head extraction temperature began to rise rapidly, valve-off stopped to gather product, lays down vacuum, cooling.1,2 batches get product 112.3,112.8g respectively, and it is carried out purity check.The results are shown in Table the test lot number of example 1 correspondence in 1.
Embodiment 2
Get above-mentioned contracting and liquid oil phase 1090g, two parts of div in par aeq are decided to be the 3rd, 4 batch, carry out following steps respectively: with 10% sodium hydroxide solution 480g alkali cleaning 30 minutes, separatory then; Getting after the alkali cleaning water, to add the 31% hydrochloric acid pH value that neutralizes be 2, adds toluene 600g then and fully extract separatory.Collect oil phase.In the distilling flask that extraction oil is added to, install condenser, tail pipe, receptor, thermometer then, be heated to 140 ℃ with oil bath and distill.When column temperature was 110 ℃～120 ℃, cat head began to have cut to flow out, and this moment, effluent mainly was a toluene, included minor amount of water.Column temperature began to descend when toluene had steamed soon, and when column temperature was 30 ℃～40 ℃, air distillation finished.Vacuum system is connected in cooling back, be-0.090 in vacuum tightness～-0.092Mpa, tower top temperature are that 70～80 ℃, reflux ratio are condition under to gather foreshot at 1: 1; In reflux ratio is 2: 1～3: 1; Vacuum tightness is-0.094～-collect product under the 0.096Mpa condition, when cat head extraction temperature began to rise rapidly, valve-off stopped to gather product, lays down vacuum, cooling.3,4 batches get product 112.6,112.9g respectively, and it is carried out purity check.The results are shown in Table the test lot number of example 2 correspondences in 1.
Embodiment 3
Get above-mentioned contracting and liquid oil phase 1090g, two parts of div in par aeq are decided to be the 5th, 6 batch, carry out following steps respectively: with 20% sodium hydroxide solution 480g alkali cleaning 30 minutes, separatory then; Getting after the alkali cleaning water, to add the 31% hydrochloric acid pH value that neutralizes be 4, adds toluene 600g then and fully extract separatory.Collect oil phase.In the distilling flask that extraction oil is added to, install condenser, tail pipe, receptor, thermometer then, be heated to 140 ℃ with oil bath and distill.When column temperature was 110 ℃～120 ℃, cat head began to have cut to flow out, and this moment, effluent mainly was a toluene, included minor amount of water.Column temperature began to descend when toluene had steamed soon, and when column temperature was 30 ℃～40 ℃, air distillation finished.Vacuum system is connected in cooling back, be-0.090 in vacuum tightness～-0.092Mpa, tower top temperature are that 70 ℃～80 ℃, reflux ratio are condition under to gather foreshot at 1: 1; In reflux ratio is 2: 1～3: 1; Vacuum tightness is-0.094～-collect product under the 0.096Mpa condition, when cat head extraction temperature began to rise rapidly, valve-off stopped to gather product, lays down vacuum, cooling.5,6 batches get product 112.6,112.9g respectively, and it is carried out purity check.The results are shown in Table the test lot number of example 3 correspondences in 1.
Table 1 O-ethoxyl phenol treating test-results
| Batch | Example 1 | Example 2 | Example 3 | |||
| ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | |
| Product purity/% | ??99.6 | ??99.3 | ??99.5 | ??99.2 | ??99.4 | ??99.3 |
| Yield/% | ??94.0 | ??94.1 | ??94.2 | ??94.1 | ??94.1 | ??94.2 |
Embodiment 4
Get above-mentioned O-ethoxyl phenolic product 276.6g, two parts of div in par aeq are decided to be the 7th, 8 batch, carry out following steps respectively: being mixed with concentration with toluene is 25% solution 545g, with 5% sodium hydroxide solution 1040g alkali cleaning 30 minutes, separatory then; Getting after the alkali cleaning water, to add the 31% hydrochloric acid pH value that neutralizes be 1, adds toluene then and fully extract, and separatory is collected oil phase.In the distilling flask that extraction oil is added to, install condenser, tail pipe, receptor, thermometer then, be heated to 140 ℃ with oil bath and distill.When column temperature was 110 ℃～120 ℃, cat head began to have cut to flow out, and this moment, effluent mainly was a toluene, included minor amount of water.Column temperature began to descend when toluene had steamed soon, and when column temperature was 30 ℃～40 ℃, air distillation finished.Vacuum system is connected in cooling back, be-0.090 in vacuum tightness～-0.092Mpa, tower top temperature are that 70～80 ℃, reflux ratio are condition under to gather foreshot at 1: 1; In reflux ratio is 2: 1～3: 1; Vacuum tightness is-0.094～-collect product under the 0.096Mpa condition, when cat head extraction temperature began to rise rapidly, valve-off stopped to gather product, lays down vacuum, cooling.7,8 batches get product 129.1,129.2g respectively, and it is carried out purity check.The results are shown in Table the test lot number of example 4 correspondences in 2.
Embodiment 5
Get above-mentioned O-ethoxyl phenolic product 276.6g, two parts of div in par aeq are decided to be the 9th, 10 batch, carry out following steps respectively: being mixed with concentration with toluene is 25% solution 545g, with 10% sodium hydroxide solution 520g alkali cleaning 30 minutes, separatory then; Getting after the alkali cleaning water, to add the 31% hydrochloric acid pH value that neutralizes be 2, adds toluene then and fully extract separatory.Collect oil phase.In the distilling flask that extraction oil is added to, install condenser, tail pipe, receptor, thermometer then, be heated to 140 ℃ with oil bath and distill.When column temperature was 110 ℃～120 ℃, cat head began to have cut to flow out, and this moment, effluent mainly was a toluene, included minor amount of water.Column temperature began to descend when toluene had steamed soon, and when column temperature was 30 ℃～40 ℃, air distillation finished.Vacuum system is connected in cooling back, be-0.090 in vacuum tightness～-0.092Mpa, tower top temperature are that 70～80 ℃, reflux ratio are condition under to gather foreshot at 1: 1; In reflux ratio is 2: 1～3: 1; Vacuum tightness is-0.094～-collect product under the 0.096Mpa condition, when cat head extraction temperature began to rise rapidly, valve-off stopped to gather product, lays down vacuum, cooling.9,10 batches get product 129.2,129.4g respectively, and it is carried out purity check.The results are shown in Table the test lot number of example 5 correspondences in 2.
Embodiment 6
Get above-mentioned O-ethoxyl phenolic product 276.6g, two parts of div in par aeq are decided to be the 11st, 12 batch, carry out following steps respectively: being mixed with concentration with toluene is 25% solution 545g, with 20% sodium hydroxide solution 520g alkali cleaning 30 minutes, separatory then; Getting after the alkali cleaning water, to add the 31% hydrochloric acid pH value that neutralizes be 4, adds toluene then and fully extract separatory.Collect oil phase.In the distilling flask that extraction oil is added to, install condenser, tail pipe, receptor, thermometer then, be heated to 140 ℃ with oil bath and distill.When column temperature was 110 ℃～120 ℃, cat head began to have cut to flow out, and this moment, effluent mainly was a toluene, included minor amount of water.Column temperature began to descend when toluene had steamed soon, and when column temperature was 30 ℃～40 ℃, air distillation finished.Vacuum system is connected in cooling back, be-0.090 in vacuum tightness～-0.092Mpa, tower top temperature are that 70～80 ℃, reflux ratio are condition under to gather foreshot at 1: 1; In reflux ratio is 2: 1～3: 1; Vacuum tightness is-0.094～-collect product under the 0.096Mpa condition, when cat head extraction temperature began to rise rapidly, valve-off stopped to gather product, lays down vacuum, cooling.11,12 batches get product 129.1,129.3g respectively, and it is carried out purity check.The results are shown in Table the test lot number of example 6 correspondences in 2.
Table 2 O-ethoxyl phenol treating test-results
| Batch | Example 4 | Example 5 | Example 6 | |||
| ??7 | ??8 | ??9 | ??10 | ??11 | ??12 | |
| Product purity/% | ??99.3 | ??99.5 | ??99.3 | ??99.4 | ??99.4 | ??99.3 |
| Yield/% | ??94.2 | ??94.3 | ??94.3 | ??94.3 | ??94.2 | ??94.2 |
More than the raw materials used industrial goods that are, more easily buy from market.
Claims (2)
1, the process for purification of the synthetic Pyrocatechol monoethyl ether of pyrocatechol method is characterized in that:
(1) with the condensated liquid oil phase or the O-ethoxyl phenolic product of the synthetic Pyrocatechol monoethyl ether that obtains of pyrocatechol method, with 5～20% sodium hydroxide solution alkali cleanings 30 minutes, separatory then; The water of getting after the alkali cleaning is regulated pH value to 1～4 with hydrochloric acid; After fully extracting with toluene then, separatory is collected oil phase.
(2) oil phase that will obtain by (1) in 110 ℃～120 ℃ air distillations to reclaim toluene, when temperature is reduced to 30～40 ℃, decompression distillation then, gold-plating branch before vacuum tightness-0.090～0.092MPa, 35～80 ℃ of tower top temperatures, reflux ratio condition under are gathered at 1: 1; In reflux ratio is 2: 1～3: 1, collects product under vacuum tightness-0.094～0.096Mpa condition, stops to gather when tower top temperature rises rapidly, obtains the Pyrocatechol monoethyl ether of purity 〉=99.2%.
2, process for purification according to claim 1 is characterized in that: the toluene of recovery can be applied mechanically.
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| CNB2005100168412A CN100391924C (en) | 2005-05-24 | 2005-05-24 | O-ethoxyl phenol refining process |
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| CNB2005100168412A CN100391924C (en) | 2005-05-24 | 2005-05-24 | O-ethoxyl phenol refining process |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130486B (en) * | 2007-08-23 | 2012-03-28 | 盐城凤阳化工有限公司 | Iron removing and crystallizating method for producing benzenediol product |
| CN107652167A (en) * | 2017-10-25 | 2018-02-02 | 武汉纺织大学 | A kind of synthetic method of 3 butoxy phenol |
| CN109400447A (en) * | 2018-11-13 | 2019-03-01 | 科利生物科技（徐州）有限公司 | The preparation method of pyrogallol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056363C (en) * | 1995-10-04 | 2000-09-13 | 朱昌朋 | Extraction of 4-methyl guaiacol and 4-ethyl guaiacol from creasote |
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- 2005-05-24 CN CNB2005100168412A patent/CN100391924C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101130486B (en) * | 2007-08-23 | 2012-03-28 | 盐城凤阳化工有限公司 | Iron removing and crystallizating method for producing benzenediol product |
| CN107652167A (en) * | 2017-10-25 | 2018-02-02 | 武汉纺织大学 | A kind of synthetic method of 3 butoxy phenol |
| CN109400447A (en) * | 2018-11-13 | 2019-03-01 | 科利生物科技（徐州）有限公司 | The preparation method of pyrogallol |
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| CN100391924C (en) | 2008-06-04 |
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