CN103848724B - The technique of Resorcinol is produced in a kind of mphenylenediamine hydrolysis - Google Patents
The technique of Resorcinol is produced in a kind of mphenylenediamine hydrolysis Download PDFInfo
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- CN103848724B CN103848724B CN201410100819.5A CN201410100819A CN103848724B CN 103848724 B CN103848724 B CN 103848724B CN 201410100819 A CN201410100819 A CN 201410100819A CN 103848724 B CN103848724 B CN 103848724B
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- resorcinol
- mphenylenediamine
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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
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
- C07C37/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen by substitution of a NH2 group
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Abstract
The present invention relates to the technique that Resorcinol is produced in the hydrolysis of a kind of mphenylenediamine, its concrete steps are as follows: 1) join in highly pressured hydrolysis reactor in proportion by mphenylenediamine, an acidic catalyst, solid super acid catalyst and water, mix, obtain mixed reaction solution; 2) reactor heating, makes mphenylenediamine be hydrolyzed and obtains Resorcinol hydrolysis reaction liquid; 3) to hydrolysis reaction liquid after filtration, solvent extraction obtains Resorcinol crude product; 4) underpressure distillation of Resorcinol crude product is obtained Resorcinol finished product.The present invention pollutes few, and discharge of wastewater is little, and processing condition are easy to control, and product yield is high.
Description
Technical field
The present invention relates to a kind of preparation technology of Resorcinol, more particularly, the present invention relates to a kind of method taking mphenylenediamine as raw material hydrolysis and prepare Resorcinol.
Background technology
Resorcinol is commonly called as resorcin, has another name called Resorcinol, 1,3-dihydroxy-benzene etc.Resorcinol is as a kind of important organic intermediate, in fields such as agricultural chemicals, dyestuff, coating, medicine, plastics, rubber, electronic chemical products, wherein mainly for the preparation of the tamanori of tire cord, use for synthetic rubber tacky resin, Plywood high performance adhesive, synthesis benzophenone ultraviolet absorption agent, Metha Amino Phenon, as sanitas etc.The route of current industrialization synthesis Resorcinol mainly contain with benzene be raw material sulfonated alkali fusion method, take m-Diisopropylbenzene as the oxidation style of raw material.
1. benzene sulfonated alkali fusion method
2. m-Diisopropylbenzene oxidation style
Sulfonation method with benzene and sulfuric acid for raw material, technique comprises the steps such as sulfonation, neutralization, alkali fusion and acidifying, the method technique is simple, equipment requirements is not high, but Production Flow Chart is tediously long, consume a large amount of strong acid (as sulfuric acid, hydrochloric acid), highly basic (as sodium hydroxide), produce a large amount of inorganic salt (as sodium sulfate, S-WAT) and waste liquid, environmentally friendly degree is low simultaneously; And oxidation style first m-Diisopropylbenzene is oxidized into Dihydroperoxide Diisopropyl Benzene, decompose in acid condition again and obtain Resorcinol and by product acetone, the waste water that the method produces, waste gas are all little, pollute also less, cost is also lower, but technical requirements is higher, and oxidation, extraction process is more complicated, simultaneously by the restriction of m-Diisopropylbenzene raw material, suitability for industrialized production not yet makes a breakthrough so far.
Mphenylenediamine hydrolysis process because raw material sources are convenient, technical process is short, good environmental protection and present good application prospect, accordingly, High Temperature High Pressure and the acidic medium operating mode of hydrolysis reaction propose higher requirement to reactor material erosion resistance.Solid super acid catalyst has the advantage of some uniquenesses, and as the simple inorganics of one, its preparation is very simple, and thus cost is low; Corrosion-free to equipment, overcome the shortcoming of many liquid acid severe corrosion equipments; Moisture-stable; Be separated easily; Regeneration easily, can reuse.
Summary of the invention
The object of the invention provides a kind of technique polluting little, that cost is low mphenylenediamine hydrolysis production Resorcinol to improve the deficiencies in the prior art.
Technical scheme of the present invention is: join in acid-resistant reactor by mphenylenediamine, acid catalyst, solid super acid catalyst and water, sealed reactor also heats mixing raw material and makes mphenylenediamine generation hydrolysis reaction and generate Resorcinol, then the material after hydrolysis reaction completes is extracted, then Resorcinol finished product is obtained to extraction phase solution distillation process.
Concrete technical scheme of the present invention is: the technique of Resorcinol is produced in a kind of mphenylenediamine hydrolysis, its concrete steps are as follows: 1) join in highly pressured hydrolysis reactor in proportion by mphenylenediamine, an acidic catalyst, solid super acid catalyst and water, mix, obtain mixed reaction solution; 2) reactor heating, makes mphenylenediamine be hydrolyzed and obtains Resorcinol hydrolysis reaction liquid; 3) to hydrolysis reaction liquid after filtration, solvent extraction obtains Resorcinol crude product; 4) underpressure distillation of Resorcinol crude product is obtained Resorcinol finished product.
Preferably described an acidic catalyst is at least the one in sulfuric acid, phosphoric acid or hydrochloric acid; Solid super acid catalyst is at least SO
4 2-/ TiO
2-L
a2o
3, SO
4 2-/ F
e2o
3, SO
4 2-/ Al
2o
3, SO
4 2-/ TiO
2-SnO
2, SO
4 2-/ ZrO
2-TiO
2, M
oo
3/ TiO
2or SiO
2/ ZrO
2in one.
The molar ratio of preferred mphenylenediamine, an acidic catalyst is mphenylenediamine: an acidic catalyst (pure)=be 1:(0.15 ~ 1.9); Weight ratio shared in the mixed reaction solution that described mphenylenediamine is formed at mphenylenediamine, an acidic catalyst, solid super acid catalyst and water is 5 ~ 15%; The weight ratio of described solid super acid catalyst shared by mixed reaction solution is 1 ~ 10%.
Preferred reactor heating and temperature control is at 190 DEG C ~ 270 DEG C, and pressure-controlling is at 1.8 ~ 2.3MPa, and the reaction times is 4 ~ 12 hours.
Preferred steps 3) in the solvent of extraction be one or more mixture in n-butyl acetate, ethyl acetate, propyl carbinol, isopropylcarbinol, ether, diisopropyl ether, glycol dimethyl ether or pimelinketone; Preferred steps 4) in the pressure of Resorcinol crude product underpressure distillation be 1.5 ~ 4Kpa.
Concrete reaction equation is as follows:
Beneficial effect:
The direct catalysis method of mphenylenediamine is adopted to produce Resorcinol, pollute few, discharge of wastewater is little, processing condition are easy to control, product yield is high, not only solves and perplexs the pollution problem that sulfonated alkali fusion method produces Resorcinol enterprise always, and effectively suppress the generation of side reaction, improve the yield of Resorcinol, reduce coke-like produce raw.Solid super-strong acid can recycling.
Sulfonated alkali fusion method produces Resorcinol, a large amount of strong acid (as sulfuric acid, hydrochloric acid), highly basic (as sodium hydroxide) is consumed in production process, produce a large amount of inorganic salt (as sodium sulfate, S-WAT) and waste liquid simultaneously, liquid waste disposal costly, also have larger waste water, environmentally friendly degree is low simultaneously.The waste water that this technique produces is few, greatly reduces the pollution to environment.
Accompanying drawing explanation
The process flow sheet of Fig. 1 mphenylenediamine hydrolysis method.
Embodiment
Embodiment 1:
In the 5L autoclave being furnished with stirring (electric heating coil heating), add 216.0g mphenylenediamine, 350.0g hydrochloric acid (concentration 30%), 2200g water, 27.94gSO
4 2-/ ZrO
2-TiO
2, feed temperature is no more than 80 DEG C, adds rear stirring 30min, makes mixing of materials even.After airtight, be heated to 200 DEG C, pressure is 1.8MPa, insulation reaction 10 hours, cools to room temperature 30 DEG C after reaction terminates; Take out reaction solution, filter, by 250.0g extracted with diethyl ether 4 times, steam solvent and obtain crude product 175.0g, content is 95.50%, and under 1.8KPa, obtain product 162.0g through distillation, content is 99.38%.
Embodiment 2:
In the 5L autoclave being furnished with stirring (electric heating coil heating), add 220.8g mphenylenediamine, 368.0g sulfuric acid (concentration 98%), 2600g water, 354.31gSO
4 2-/ ZrO
2-TiO
2, feed temperature is no more than 80 DEG C, adds rear stirring 30min, makes mixing of materials even.After airtight, be heated to 220 DEG C, pressure is 2.2MPa, insulation reaction 8 hours, cools to room temperature 30 DEG C after reaction terminates; Take out reaction solution, filter, with 400g extraction into ethyl acetate 4 times, steam solvent and obtain crude product 185.0g, content is 95.30%, and obtain product 178.0g at 2.0KPa through distillation, content is 99.40%.
Embodiment 3:
In the 5L autoclave being furnished with stirring (electric heating coil heating), add 426.0g mphenylenediamine, 240.0g hydrochloric acid (concentration 30%), 2600g water, 40.0gSO
4 2-/ TiO
2-SnO
2, feed temperature is no more than 80 DEG C, adds rear stirring 30min, makes mixing of materials even.After airtight, be heated to 200 DEG C, pressure is 2MPa, insulation reaction 4 hours, cools to room temperature 30 DEG C after reaction terminates; Take out reaction solution, filter, extract 4 times with 500g isopropylcarbinol, steam solvent and obtain crude product 295.0g, content is 95.25%, and obtain product 281.0g at 1.9KPa through distillation, content is 99.50%.
Embodiment 4:
In the 5L autoclave being furnished with stirring (electric heating coil heating), add 151.8g mphenylenediamine, 184.0g sulfuric acid (concentration 98%), 2600g water, 100.0gSO
4 2-/ Al
2o
3, feed temperature is no more than 80 DEG C, adds rear stirring 30min, makes mixing of materials even.After airtight, be heated to 270 DEG C, pressure is 1.9MPa, insulation reaction 5 hours, cools to room temperature 30 DEG C after reaction terminates; Take out reaction solution, filter, by 300g extracted with diethyl ether 4 times, steam solvent and obtain crude product 113.0g, content is 95.35%, and obtain product 95.0g at 2.3KPa through distillation, content is 99.45%.
Embodiment 5:
In the 5L autoclave being furnished with stirring (electric heating coil heating), add 450g mphenylenediamine, 110.0g sulfuric acid (concentration 98%), 2400g water, 50.0gSO
4 2-/ Fe
2o
3, feed temperature is no more than 80 DEG C, adds rear stirring 30min, makes mixing of materials even.After airtight, be heated to 230 DEG C, pressure is 2MPa, insulation reaction 7 hours, cools to room temperature 30 DEG C after reaction terminates; Take out reaction solution, filter, extract 4 times by 600g diisopropyl ether, steam solvent and obtain crude product 390g, content is 95.24%, and obtain product 372g at 3.8KPa through distillation, content is 99.38%.
Claims (4)
1. a technique for Resorcinol is produced in mphenylenediamine hydrolysis, and its concrete steps are as follows: 1) mphenylenediamine, an acidic catalyst, solid super acid catalyst and water are joined in proportion in highly pressured hydrolysis reactor, mix, obtain mixed reaction solution; Wherein said an acidic catalyst is at least the one in sulfuric acid, phosphoric acid or hydrochloric acid; Solid super acid catalyst is at least SO
4 2-/ TiO
2-La
2o
3, SO
4 2-/ Fe
2o
3, SO
4 2-/ Al
2o
3, SO
4 2-/ TiO
2-SnO
2, SO
4 2-/ ZrO
2-TiO
2, MoO
3/ TiO
2or SiO
2/ ZrO
2in one; The molar ratio of mphenylenediamine, an acidic catalyst is 1:(0.15 ~ 1.9); The weight ratio of described mphenylenediamine shared by mixed reaction solution is 5 ~ 15%; The weight ratio of described solid super acid catalyst shared by mixed reaction solution is 1 ~ 10%; 2) reactor heating, makes mphenylenediamine be hydrolyzed and obtains Resorcinol hydrolysis reaction liquid; 3) to hydrolysis reaction liquid after filtration, solvent extraction obtains Resorcinol crude product; 4) underpressure distillation of Resorcinol crude product is obtained Resorcinol finished product.
2. technique according to claim 1, is characterized in that: reactor heating and temperature control is at 190 DEG C ~ 270 DEG C, and pressure-controlling is at 1.8 ~ 2.3MPa, and the reaction times is 4 ~ 12 hours.
3. technique according to claim 1, is characterized in that: step 3) in the solvent of extraction be one or more mixture in n-butyl acetate, ethyl acetate, propyl carbinol, isopropylcarbinol, ether, diisopropyl ether, glycol dimethyl ether or pimelinketone.
4. technique according to claim 1, is characterized in that: step 4) in the pressure of Resorcinol crude product underpressure distillation be 1.5 ~ 4KPa.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104262109B (en) * | 2014-09-01 | 2016-09-28 | 湖南湘易康制药有限公司 | A kind of synthetic method of resorcinol |
| CN107262150B (en) * | 2017-06-06 | 2018-10-16 | 青岛科技大学 | A kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst |
| CN109422659B (en) * | 2017-08-23 | 2022-02-11 | 中国石油化工股份有限公司 | Method for preparing m-aminophenol by hydrolyzing m-phenylenediamine |
| CN109516924B (en) * | 2018-11-14 | 2021-10-29 | 南京工业大学 | Method for preparing m-aminophenol by catalyzing resorcinol |
| CN114163311A (en) * | 2020-09-11 | 2022-03-11 | 王兴路 | High-efficiency and clean production method of phenolic compound |
| CN114149306A (en) * | 2021-12-09 | 2022-03-08 | 青岛科技大学 | Synthesis process of resorcinol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830933A (en) * | 2006-04-12 | 2006-09-13 | 吴江市汇丰化工厂 | Process for preparing resorcinol |
| CN1927795A (en) * | 2006-06-13 | 2007-03-14 | 老河口市华润化工有限公司 | Method of preparing resorcin by hydrolyzing m-phenylenediamine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6023651B2 (en) * | 1976-06-29 | 1985-06-08 | 三井東圧化学株式会社 | Method for hydrolyzing paraphenylenediamine |
| JP2500117B2 (en) * | 1991-07-30 | 1996-05-29 | セントラル硝子株式会社 | Glass with a functional coating with a protective coating |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1830933A (en) * | 2006-04-12 | 2006-09-13 | 吴江市汇丰化工厂 | Process for preparing resorcinol |
| CN1927795A (en) * | 2006-06-13 | 2007-03-14 | 老河口市华润化工有限公司 | Method of preparing resorcin by hydrolyzing m-phenylenediamine |
Non-Patent Citations (1)
| Title |
|---|
| 间苯二酚的低污染合成工艺研究;田璇;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20080115(第1期);第31-32页 * |
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