CN104098445A - Method for extracting m-cresol from mixture of m-cresol and p-cresol - Google Patents
Method for extracting m-cresol from mixture of m-cresol and p-cresol Download PDFInfo
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- CN104098445A CN104098445A CN201410314467.3A CN201410314467A CN104098445A CN 104098445 A CN104098445 A CN 104098445A CN 201410314467 A CN201410314467 A CN 201410314467A CN 104098445 A CN104098445 A CN 104098445A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
- C07C39/06—Alkylated phenols
- C07C39/07—Alkylated phenols containing only methyl groups, e.g. cresols, xylenols
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for extracting m-cresol from a mixture of m-cresol and p-cresol. The method can be used for achieving the purpose that m-cresol with the content larger than or equal to 99.8% is recycled from a cresol mixture containing the m-cresol content of 50-90% and the p-cresol content of 10-50%, so that the use requirement for m-cresol raw materials during the production of drug and Vitamin E can be met. The method comprises the following operation steps: combining the mixture of m-cresol and p-cresol with urea into a solid, washing the obtained solid by using a mixed solvent, hydrolyzing the washed solid through adding water, separating the oil phase, and enabling the oil phase to be subjected to reduced pressure distillation, so as to obtain the m-cresol.
Description
Technical field
The invention belongs to the technical field of Chemicals separation of produced, be specifically related to a kind of method of extracting meta-cresol from M-and P-cresols mixture.
Background technology
Meta-cresol is the important organic synthesis intermediate of synthesising complex E and Multiple Pesticides, oxidation inhibitor.And the vitamin-E of production pharmaceutical grade requires the content of impurity p-cresol in stock yard cresols to be not more than 0.2%, content >=99.8% of meta-cresol.
High purity meta-cresol conventional production methods is meta-aminotoluene diazotization hydrolysis method, and this method exists the shortcoming that environmental pollution is serious, atom utilization is low, does not meet the theory of Modern Green chemical industry.
Coal chemical enterprise in process of production can a large amount of phenol products of by-product, after initial gross separation, can obtain the M-and P-cresols mixture that purity is greater than 99%, but due to 203 DEG C of meta-cresol boiling points, 202.8 DEG C of p-cresol boiling points, so be difficult to realize the separation of the two by conventional rectification method, especially want separation to obtain p-cresol content and be not more than 0.2% highly purified meta-cresol, be difficult to especially realize.
US Patent No. 3,855,195 disclose one is dissolved in the M-and P-cresols mixture of meta-cresol, p-cresol (weight ratio 2:1) in toluene, and crystallization under urea exists, and obtains the method for meta-cresol after processing through rectifying again.The pure meta-cresol of what is called preparing according to its disclosed method, content, below 99.5%, cannot meet the requirement of production pharmaceutical grade vitamin-E.And the method need to be used hypertoxic toluene as solvent, can damage and cause serious environmental pollution operator.
Japanese Patent TOHKEMY 2009-7288 discloses a kind of mixture forming from meta-cresol 65%, p-cresol 35%, under existing, urea forms crystallization, through mixed solvent (1-methylnaphthalene 50% mixes with the tetradecane 50%) washing, obtain the method for meta-cresol.The meta-cresol purity that the method obtains is up to 99.1%, also cannot reach the requirement of production pharmaceutical grade vitamin-E.
Zhejiang University of prominent domestic colleges and universities, Tongji University, University Of Tianjin, China University Of Petroleum Beijing, Beijing University of Chemical Technology, Northwest University etc. had all delivered the paper that a lot of M-and P-cresols separate in recent years, these papers mainly focus on meta-cresol and urea blend crystallization, isolate in this problem of meta-cresol, but also in laboratory stage, there is no the value of industrial applications.
Therefore,, with regard to the situation of currently available technology, also fail to solve at all and from the mixture of M-and P-cresols, extract the problem that p-cresol content is not more than 0.2% high purity meta-cresol.
Summary of the invention
The object of this invention is to provide a kind of method of extracting meta-cresol from M-and P-cresols mixture, the method can realize and from the cresols mixture of meta-cresol content 50-90%, p-cresol content 10-50%, extract the meta-cresol that obtains content >=99.8%.
In order to realize object of the present invention, contriver provides following technical scheme.
A method of extracting meta-cresol from M-and P-cresols mixture, comprises operation steps:
A. the cresols mixture of meta-cresol content 50-90%, p-cresol content 10-50% and urea are dropped in reactor, in urea and cresols mixture, the mol ratio of meta-cresol is 1.00～1.30:1, under whipped state, be warming up to 85-110 DEG C, form clear solution, for subsequent use;
B. clear solution step a being obtained, is cooled to 20～25 DEG C, and maintains this temperature stirring 2 hours, the solid of separating out in filtering solution, and gained filter cake is for subsequent use;
C. in step b gained filter cake, add mixed solvent, agitator treating at 20～25 DEG C, filter, in filter cake, add mixed solvent, agitator treating at 20～25 DEG C, filters again, filter cake repetitive scrubbing repeatedly, until meta-cresol content >=99.8% in gained filter cake, described mixed solvent is selected from any one in C2-C4 alcohol and tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, trimethylbenzene;
D. will in step c gained filter cake, add water, in 20～25 DEG C of stirrings 1～4 hour, stratification, separated lower floor's oil-phase solution, for subsequent use;
E. by the rectification under vacuum of steps d gained oil-phase solution, obtain the meta-cresol of content >=99.8%.
The above-mentioned method of extracting meta-cresol from M-and P-cresols mixture, lowers the temperature in described step b preferably 4～5 hours time used.Under this condition, the speed of separating out solid is slow, and the solid particulate size of separating out is even, parcel impurity that can be not too many, and the while can not reduced the efficiency of production.
The above-mentioned method of extracting meta-cresol from M-and P-cresols mixture, the weight of at every turn washing mixed solvent used in described step c is 2～5 times of step b gained filter cake weight.Filter cake can wash fully.
The above-mentioned method of extracting meta-cresol from M-and P-cresols mixture, the number of times of repetitive scrubbing preferably 2～5 times in described step c.Contriver is through lot of experiment validation, and repetitive scrubbing 2-5 time can make content >=99.8% of meta-cresol in filter cake.
The above-mentioned method of extracting meta-cresol from M-and P-cresols mixture, the weight that adds water in described steps d is 1～3 times of step c gained filter cake weight.Water consumption herein can reach the object of abundant hydrolysis, can reach again water-saving object.
The above-mentioned method of extracting meta-cresol from M-and P-cresols mixture, in described step c, C2-C4 alcohol is selected from ethanol, Virahol, n-propyl alcohol, propyl carbinol.
The above-mentioned method of extracting meta-cresol from M-and P-cresols mixture, described trimethylbenzene is selected from 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene.
The above-mentioned method of extracting meta-cresol from M-and P-cresols mixture, described mixed solvent is the mixture of Virahol and tetrahydrofuran (THF), the weight ratio of Virahol and tetrahydrofuran (THF) is 1:1.Under this kind of ratio condition, impurity p-cresol can fully be removed, and target product meta-cresol loss is minimum, and the consumption of mixed solvent, washing times are also minimum.
The above-mentioned method of extracting meta-cresol from M-and P-cresols mixture, described mixed solvent is the mixture of Virahol and 1,2,4-trimethylbenzene, the weight ratio of Virahol and 1,2,4-trimethylbenzene is 1:1 or 2:3.Same, under this kind of ratio condition, impurity p-cresol can fully be removed, and the loss of target product meta-cresol is less, and the consumption of mixed solvent, washing times are also less.
The method of extraction meta-cresol of the present invention, there is the advantage that raw material is cheap and easy to get, production cost is low, taking full advantage of China is a coal big country, the feature that domestic coal chemical enterprise is numerous, meta-cresol content >=99.8% that extraction obtains, can meet the standard-required that pharmaceutical grade vitamin-E is produced.The extraction yield of the method is more than 60%, and solvent for use toxicity is lower, and can reclaim Reusability, has realized Zero discharge, has alleviated the pollution to environment, has higher actual application value.
Embodiment
Below in conjunction with specific embodiment, content of the present invention is further described in detail.
Gas Chromatographic Determination condition: capillary column
Carrier gas: He; Detector: FID;
Injector temperature: 200 DEG C; Detector temperature: 250 DEG C
Post case temperature: 110 DEG C (constant temperature).
Embodiment 1
By 1000kg M-and P-cresols mixture (meta-cresol 65%, p-cresol 35%), 400kg urea, drop in reactor, open and stir, be warming up to 110 DEG C, stir 1 hour, after solution bleach, with circulating water cooling to 20～25 DEG C, 4 hours used times, separate out solid, and maintain this temperature continuation stirring 2 hours, obtain pulpous state liquid.
Filter pulpous state liquid, obtain 1155kg filter cake.Can carry out GC analyzing and testing to filter cake sampling, measure the content of meta-cresol, as the reference of subsequent wash operation.
1155kg filter cake is dropped in reactor, add 3465kg mixed solvent (this mixed solvent consists of Virahol: tetrahydrofuran (THF)=1:1), open and stir, at 20～25 DEG C, stir 2 hours, obtain pulpous state mixed solution, filter, gained filter cake repeats said process, then washs 3 times.After each washing finishes, can carry out GC analyzing and testing to filter cake sampling, in the time that detected result shows meta-cresol content >=99.8%, can stop washing, carry out next step operation.
Final gained 843kg filter cake is dropped in reactor, add 2529kg water, at 20～25 DEG C, stir 4 hours, stratification, the oil phase of separation lower floor, rectification under vacuum obtains meta-cresol 423kg.GC analyzes mensuration: meta-cresol content is 99.84%, and p-cresol content is 0.16%.The extraction yield of meta-cresol is 65.1%.
Embodiment 2
By 100kg M-and P-cresols mixture (meta-cresol 50%, p-cresol 50%), 27.78kg urea, drop in reactor, open and stir, be warming up to 75 DEG C, stir 1.5 hours, after solution bleach, with circulating water cooling to 20～25 DEG C, 5 hours used times, separate out solid, and maintain this temperature continuation stirring 2 hours, obtain pulpous state liquid.
Filter pulpous state liquid, obtain 80.6kg filter cake.The sampling of gained filter cake is carried out to GC and analyze mensuration, result demonstration, in filter cake, meta-cresol content is 75.8%.
80.6kg filter cake is dropped in reactor, (this mixed solvent consists of Virahol: 1 to add 161.2kg mixed solvent, 2,4-trimethylbenzene=2:3), open and stir, stir 1 hour at 20～25 DEG C, obtain pulpous state mixed solution, filter, gained filter cake repeats said process again, then washs 4 times.Final gained filter cake sampling is carried out GC and is analyzed mensuration, result demonstration, and meta-cresol content is 99.8%.
Final gained 59.6kg filter cake is dropped in reactor, add 119.2kg water, at 20～25 DEG C, stir 1 hour, stratification, the oil phase of separation lower floor, rectification under vacuum obtains meta-cresol 31.7kg.GC analyzes mensuration: meta-cresol content is 99.8%, and p-cresol content is 0.2%.The extraction yield of meta-cresol is 63.4%.
Embodiment 3
By 10kg M-and P-cresols mixture (meta-cresol 90%, p-cresol 10%), 6.5kg urea, drop in reactor, open and stir, be warming up to 90 DEG C, stir 1 hour, after solution bleach, with circulating water cooling to 20～25 DEG C, 4.5 hours used times, separate out solid, and maintain this temperature continuation stirring 2 hours, obtain pulpous state liquid.
Filter pulpous state liquid, obtain 15.5kg filter cake.The sampling of gained filter cake is carried out to GC and analyze mensuration, result demonstration, in filter cake, meta-cresol content is 76.2%.
15.5kg filter cake is dropped in reactor, add 77.5kg mixed solvent (this mixed solvent consists of Virahol: 1,2,4-trimethylbenzene=1:1), open and stir, stir 1.5 hours at 20～25 DEG C, obtain pulpous state mixed solution, filter, gained filter cake repeats said process, then washs 1 time.Final gained filter cake sampling is carried out GC and is analyzed mensuration, result demonstration, and in filter cake, meta-cresol content is 99.82%.
Final gained 12.8kg filter cake is dropped in reactor, add 12.8kg water, at 20～25 DEG C, stir 1 hour, stratification, the oil phase of separation lower floor, rectification under vacuum obtains meta-cresol 6.32kg.GC analyzes mensuration: meta-cresol content is 99.83%, and p-cresol content is 0.17%.The extraction yield of meta-cresol is 70.2%.
Can be found out by embodiment, the method for extraction meta-cresol of the present invention, operation steps is simple, not only can in laboratory, realize, and can be applied in the middle of large-scale industrial production.
Claims (9)
1. a method of extracting meta-cresol from M-and P-cresols mixture, is characterized in that, comprises operation steps:
A. the cresols mixture of meta-cresol content 50-90%, p-cresol content 10-50% and urea are dropped in reactor, in urea and cresols mixture, the mol ratio of meta-cresol is 1.00～1.30:1, under whipped state, is warming up to 85-110 DEG C, forms clear solution;
B. clear solution step a being obtained, is cooled to 20～25 DEG C, and maintains this temperature stirring 2 hours, the solid of separating out in filtering solution, and gained filter cake is for subsequent use;
C. in step b gained filter cake, add mixed solvent, agitator treating at 20～25 DEG C, filter, in filter cake, add mixed solvent, agitator treating at 20～25 DEG C, filters again, filter cake repetitive scrubbing repeatedly, until meta-cresol content >=99.8% in gained filter cake, described mixed solvent is selected from any one in C2-C4 alcohol and tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, trimethylbenzene;
D. will in step c gained filter cake, add water, in 20～25 DEG C of stirrings 1～4 hour, stratification, separated lower floor's oil-phase solution, for subsequent use;
E. by the rectification under vacuum of steps d gained oil-phase solution, obtain the meta-cresol of content >=99.8%.
2. a kind of method of extracting meta-cresol from M-and P-cresols mixture according to claim 1, is characterized in that, the time used of lowering the temperature in described step b is 4～5 hours.
3. a kind of method of extracting meta-cresol from M-and P-cresols mixture according to claim 1, is characterized in that, the weight of at every turn washing mixed solvent used in described step c is 2～5 times of step b gained filter cake weight.
4. a kind of method of extracting meta-cresol from M-and P-cresols mixture according to claim 1, is characterized in that, in described step c, the number of times of repetitive scrubbing is 2～5 times.
5. a kind of method of extracting meta-cresol from M-and P-cresols mixture according to claim 1, is characterized in that, the weight that adds water in described steps d is 1～3 times of step c gained filter cake weight.
6. a kind of method of extracting meta-cresol from M-and P-cresols mixture according to claim 1, is characterized in that, in described step c, C2-C4 alcohol is selected from ethanol, Virahol, n-propyl alcohol, propyl carbinol.
7. a kind of method of extracting meta-cresol from M-and P-cresols mixture according to claim 1, is characterized in that, described trimethylbenzene is selected from 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene.
8. a kind of method of extracting meta-cresol from M-and P-cresols mixture according to claim 1, is characterized in that, described mixed solvent is the mixture of Virahol and tetrahydrofuran (THF), and the weight ratio of Virahol and tetrahydrofuran (THF) is 1:1.
9. a kind of method of extracting meta-cresol from M-and P-cresols mixture according to claim 1, is characterized in that, described mixed solvent is the mixture of Virahol and 1,2,4-trimethylbenzene, and the weight ratio of Virahol and 1,2,4-trimethylbenzene is 1:1 or 2:3.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112745199A (en) * | 2019-10-31 | 2021-05-04 | 湖北健翔生物制药有限公司 | Preparation method of pharmaceutic adjuvant injection interstage cresol |
| CN115636735A (en) * | 2022-10-27 | 2023-01-24 | 北京化工大学 | Process method for extracting and separating m-cresol and p-cresol mixture |
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| CN102167658A (en) * | 2011-03-16 | 2011-08-31 | 北京化工大学 | Technology for complexing, crystallizing, separating and purifying metacresol |
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| JP2009007288A (en) * | 2007-06-27 | 2009-01-15 | Jfe Chemical Corp | Cleaning method for solid matter and purification method for meta-cresol |
| CN102167658A (en) * | 2011-03-16 | 2011-08-31 | 北京化工大学 | Technology for complexing, crystallizing, separating and purifying metacresol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112745199A (en) * | 2019-10-31 | 2021-05-04 | 湖北健翔生物制药有限公司 | Preparation method of pharmaceutic adjuvant injection interstage cresol |
| CN115636735A (en) * | 2022-10-27 | 2023-01-24 | 北京化工大学 | Process method for extracting and separating m-cresol and p-cresol mixture |
| CN115636735B (en) * | 2022-10-27 | 2024-05-28 | 北京化工大学 | Process method for extracting and separating m-cresol and p-cresol mixture |
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