CN101003465A - Method for preparing resorcinol by continuous hydrolyzing metaphenylene diamine - Google Patents
Method for preparing resorcinol by continuous hydrolyzing metaphenylene diamine Download PDFInfo
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- CN101003465A CN101003465A CN 200710019561 CN200710019561A CN101003465A CN 101003465 A CN101003465 A CN 101003465A CN 200710019561 CN200710019561 CN 200710019561 CN 200710019561 A CN200710019561 A CN 200710019561A CN 101003465 A CN101003465 A CN 101003465A
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- mphenylenediamine
- resorcinol
- metaphenylene diamine
- continuous hydrolyzing
- hydrolyzing
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Abstract
This invention discloses a method for preparing resorcinol by continuous hydrolysis of m-phenylene diamine. The hydrolysis reaction adopts at least one high-pressure hydrolysis kettle and at least one high-pressure collection kettle in series. The method comprises: (1) adding a certain volume of deionized water or distilled water into the high-pressure hydrolysis kettle, heating to a certain temperature, and keeping the temperature; (2) pumping m-phenylene diamine sulfate into a preheater, preheating, and pumping into the high-pressure hydrolysis kettle; (3) hydrolyzing continuously, collecting the product in the high-pressure collection kettle, cooling, and performing post-treatment. The method has such advantages as simple apparatus, clean process, and high efficiency.
Description
Technical field
The present invention relates to a kind of preparation technology of Organic Chemicals Resorcinol.
Background technology
Resorcinol is 1, and the 3-dihydroxy-benzene is used for industries such as rubber, plastics, medicine, agricultural chemicals, dyestuff mainly as organic intermediate.The tire manufacturing is used for cord thread soaker, use for synthetic rubber tacky resin, produces wood adhesive RS, RL, RERH etc., synthetic benzophenone ultraviolet absorbers UV-0, UV-531, UV-9 etc., organic intermediate meta-aminophenol etc.Can be used for preparing that a first tackiness agent and wood gluing plate also can be used for producing rubber and timber and stick with glue agent, are used for synthetic dyestuff intermediate meta-aminophenol with high performance adhesive etc. between tire fabric uses.
It is the sulfonated alkali fusion method of raw material that the route of the synthetic Resorcinol of industrialization at present mainly contains with benzene, be the oxidation style and the mphenylenediamine hydrolysis method of raw material with the m-Diisopropylbenzene, wherein, mphenylenediamine hydrolysis method raw material sources are extensive, technical process short, its shortcoming is to need higher temperature of reaction, pressure and acidic mediums, has increased the dangerous of technology and to the requirement of reactor material erosion resistance.
Before this a series of patent reports for solving the research that the material problem is done, for example United States Patent (USP) 3,462,497 have disclosed the technology that adopts the liner Monel metal in a kind of phosphoric acid or the sulfuric acid medium, United States Patent (USP) 3,862,245 what adopt is a kind of sulfuric acid medium, tantalum pipe reactor, the clear 52-153 of Japanese Patent, 919 adopt the material of hydrochloric acid medium, Ha Shi B alloy etc., and these technological processs are interrupter method production, and single complete equipment production capacity is very low, cause investing excessive, heavy industrialization is lacked competitiveness.
Along with the continuous expansion of Resorcinol consumption and the aggravation and the chemical process environmental requirement of market competition improve day by day; adopt the operational path production Resorcinol of clean environment firendly urgent all the more; domestic main employing is that the sulfonated alkali fusion method production process of raw material exists the insoluble technology barrier of environmental issue with benzene; and the mphenylenediamine hydrolysis method replaces sulfonated alkali fusion method and still has certain difficulty because interrupter method production is difficult to mass-producing.
Summary of the invention
The object of the invention is to invent a kind of mphenylenediamine hydrolysis production method that can effectively improve the Resorcinol yield.
The present invention mainly comprises hydrolysis reaction and aftertreatment, and characteristics are:
1) hydrolysis reaction:
Adopt at least one highly pressured hydrolysis reactor and at least one high pressure rewinding still, the highly pressured hydrolysis reactor is connected successively, and the rewinding still is connected on the discharge port of last hydrolytic reaction pot;
After in the highly pressured hydrolysis reactor, filling ionized water or distilled water, use the nitrogen replacement system, make in the system behind the no air, the highly pressured hydrolysis reactor is warmed up to 229～241 ℃, in the highly pressured hydrolysis reactor, be pressed into preheating temperature then continuously and be 220～250 ℃ mphenylenediamine sulfate liquor, carry out continuous hydrolyzing;
2) aftertreatment:
The hydrolyzed solution that high pressure rewinding still is collected cools to 30～40 ℃, uses organic solvent extraction, and the oil reservoir that extraction obtains washs with 3% sulfuric acid normal temperature, and the washing oil reservoir washes with water again, and with the oil reservoir negative pressure precipitation that obtains, redistillation obtains Resorcinol.
Among the present invention, in the highly pressured hydrolysis reactor, add the ionized water or the distilled water of certain volume earlier, as bed material, the preset temperature that is rapidly heated then insulation.The mphenylenediamine vitriol raw material for preparing is squeezed into preheater with volume pump and is carried out raw material preheating, one-level highly pressured hydrolysis reactor is squeezed in raw material serialization through preheating, carry out continuous hydrolyzing reaction, high pressure rewinding still carries out the serialization extraction simultaneously, the extraction material post-processing operation of lowering the temperature.
The present invention is a kind of device intensification, operational path clean environment firendly, high efficiency of having realized, can effectively reduce investment, the continuous growth of meeting the market requirement amount.
Among the present invention,, need to use the nitrogen replacement hydrolysis device earlier, make no air in the system, and then in reactor, be pressed into the mphenylenediamine sulfate liquor because stock yard phenylenediamine and product Resorcinol are easily oxidized.
Among the present invention, for guaranteeing the enforcement of continuous process, earlier mphenylenediamine and sulfuric acid are formed homogeneous mphenylenediamine sulfate liquor, reduce the acidity of system, will be pressed in the reactor after the preheating of mphenylenediamine sulfate liquor again, if and directly in reactor, be pressed into mphenylenediamine and sulfuric acid respectively respectively, increased the quantity of preheater, the mphenylenediamine pre-heating system easily stops up, and the direct preheating of dilute sulphuric acid is acid strong, stronger to pipeline, equipment corrosion, shortened work-ing life.
The present invention has adopted above-mentioned kettle-type continuous flow process, has effectively improved the production capacity of FU volume, compares production capacity with interrupter method and improves 1～2 times, has reduced investment, makes this route realize that large-scale industrial production becomes possibility.The Resorcinol purity of producing by above-mentioned processing method can reach 99.5%, and yield is greater than 88%.
When hydrolysis reaction, transform fully in order to guarantee mphenylenediamine, control is pressed into the input speed of mphenylenediamine sulfate liquor, makes reaction time 2.5～4 hours.
For carrying out smoothly of continuous reaction, ionized water is inserted in beginning in the highly pressured hydrolysis still or distilled water to coefficient is 0.8, begins to be pressed into from first still the mphenylenediamine sulfate liquor of preheating then, carries out the continuous hydrolyzing reaction.
Among the present invention, during preparation mphenylenediamine vitriol, the mol ratio of mphenylenediamine, 98% sulfuric acid and water is 1: (1～3): (50～100) are preferably in 1: 2: 63.
The method of preparation mphenylenediamine vitriol is: be mixed with the dilute sulphuric acid that concentration is 12-15% with 98% sulfuric acid and water earlier, and then the adding mphenylenediamine stirs, make its whole dissolvings, 40～90 ℃ of preparation temperature, preferably be controlled at 60～70 ℃, cause the mphenylenediamine oxidation easily in the too high process for preparation of temperature.
Highly pressured hydrolysis reactor of the present invention and high pressure rewinding still can adopt the material of anti-15% vitriolic high temperature corrosion to make, available Monel metal or tantalum material or zirconium material.
The extraction organic solvent of reaction feed liquid is propyl carbinol or n-butyl acetate.
Embodiment
Embodiment one:
1, the preparation (every batch) of mphenylenediamine vitriol
Claim 1000g98% sulfuric acid slowly to be added drop-wise to the dilute sulphuric acid of preparation 15% in the 5533g deionized water, and then add mphenylenediamine 490g, stir that make its whole dissolvings, the preparation temperature is 60～70 ℃.Wherein, mphenylenediamine: sulfuric acid: water=1: 2: 63 (mol ratio).The mphenylenediamine vitriol 7023g for preparing is preheating to 229～231 ℃, stand-by.After every batch of material preparation finishes, repeat this process again, make the required material of raw material and hydrolysis supporting.
2, continuous hydrolyzing
Adopt the series connection of a plurality of autoclaves, the quantity of autoclave is by the volume of still and corresponding production capacity decision, and autoclave is made by Monel metal or tantalum material or zirconium material.
Be the autoclave with four 1 liter among the embodiment, wherein three is hydrolytic reaction pot, and one is the rewinding still, and three highly pressured hydrolysis reactors are connected successively, and the rewinding still is connected on the discharge port of last highly pressured hydrolysis reactor.Fill ionized water or distilled water 800ml respectively in three highly pressured hydrolysis reactors, coefficient is 0.8, connects the system that is made up of four autoclaves.Charge into nitrogen to first highly pressured hydrolysis reactor, with nitrogen replacement system 3 times, be rapidly heated 229～231 ℃, in preheater, hydrolytic reaction pot, be pressed into mphenylenediamine sulfate liquor continuously with high-pressure metering pump then through preheating, input speed 600ml/hr, reaction time is 4hr, carries out continuous reaction, the extraction of serialization simultaneously hydrolyzed solution.
3, aftertreatment
When rewinding still continuous acquisition to hydrolyzed solution when reaching the 7000g left and right sides, the beginning post-processing operation, at first hydrolyzed solution is cooled to 30～40 ℃, divide 4～6 extractions with 3500g propyl carbinol or n-butyl acetate extraction, the oil reservoir 4000g that extraction obtains, with 3% sulfuric acid 500g normal temperature washing oil reservoir, washing back oil reservoir is used the 500g water washing more then.Oil reservoir negative pressure (200mmHg) precipitation that obtains, when temperature to 160 ℃, precipitation finishes, and distills under the vacuum condition of 10mmHg at last, promptly obtains purity and be 99.5% Resorcinol 449g, and yield is 90%.
Embodiment two:
1, the preparation (every batch) of mphenylenediamine vitriol
Claim 1000g98% sulfuric acid slowly to be added drop-wise to the dilute sulphuric acid of preparation 12% in the 7167g deionized water, and then add mphenylenediamine 490g, stir that make its whole dissolvings, the preparation temperature is 60～70 ℃.Wherein, mphenylenediamine: sulfuric acid: water=1: 2: 80 (mol ratio).The mphenylenediamine vitriol 8657g for preparing is preheating to 229～231 ℃, stand-by.After every batch of material preparation finishes, repeat this process again, make the required material of raw material and hydrolysis supporting.
2, continuous hydrolyzing
Adopt the hydrolysis reaction equipment identical with example one.
Fill ionized water or distilled water 800ml respectively in three highly pressured hydrolysis reactors, coefficient is 0.8, connects the system that is made up of four autoclaves.
Charge into nitrogen to first highly pressured hydrolysis reactor, use the nitrogen replacement system, make after no air exists in the system, be rapidly heated 229～231 ℃, be 229～231 ℃ mphenylenediamine sulfate liquor with being pressed into continuously in first hydrolytic reaction pot of pressure measurement pump then through preheating temperature, input speed is 600ml/hr, and reaction time is 4hr, carries out continuous reaction, the extraction of serialization simultaneously hydrolyzed solution.
3, aftertreatment
Method is with embodiment one.Finally obtain purity and be 99.5% Resorcinol, yield is 91.5%.
Embodiment three:
1, the preparation of mphenylenediamine vitriol
Method is with embodiment one.
2, continuous hydrolyzing
Adopt the hydrolysis reaction equipment identical with example one.
In three highly pressured hydrolysis reactors, fill ionized water or distilled water respectively, connect the system that forms by four autoclaves.
Charge into nitrogen to first highly pressured hydrolysis reactor, use the nitrogen replacement system, make after no air exists in the system, be rapidly heated 239～241 ℃, be 229～241 ℃ mphenylenediamine sulfate liquor with being pressed in first hydrolytic reaction pot of pressure measurement pump continuously then through preheating temperature, input speed is 960ml/hr, and reaction time is 2.5hr, carries out continuous reaction, the extraction of serialization simultaneously hydrolyzed solution.
3, aftertreatment
Method is with embodiment one.
Finally obtaining purity is 99.5% Resorcinol, yield 88.5%.
Sum up:
1, serialization preparing resorcin by hydrolyzing m-phenylenediamine of the present invention has effectively improved production capacity, compares production capacity with interrupter method and improves 1～2 times, can effectively reduce investment, and continuous growth that can the meeting the market requirement amount makes this route have more competitiveness.
2, serialization preparing resorcin by hydrolyzing m-phenylenediamine makes device intensify more, meets the demand for development that new industrialization is produced.
Claims (10)
1, a kind of method of preparing resorcinol by continuous hydrolyzing metaphenylene diamine comprises hydrolysis reaction and aftertreatment, it is characterized in that:
1) hydrolysis reaction:
Adopt at least one highly pressured hydrolysis reactor and at least one high pressure rewinding still, the highly pressured hydrolysis reactor is connected successively, and the rewinding still is connected on the discharge port of last hydrolytic reaction pot;
After in the highly pressured hydrolysis reactor, filling ionized water or distilled water, use the nitrogen replacement system, make in the system behind the no air, the highly pressured hydrolysis reactor is warmed up to 229～241 ℃, in the highly pressured hydrolysis reactor, be pressed into preheating temperature then continuously and be 220～250 ℃ mphenylenediamine sulfate liquor, carry out continuous hydrolyzing;
2) aftertreatment:
The hydrolyzed solution that high pressure rewinding still is collected cools to 30～40 ℃, uses organic solvent extraction, and the oil reservoir that extraction obtains washs with 3% sulfuric acid normal temperature, and the washing oil reservoir washes with water again, and with the oil reservoir negative pressure precipitation that obtains, redistillation obtains Resorcinol.
2, according to the method for the described preparing resorcinol by continuous hydrolyzing metaphenylene diamine of claim 1, it is characterized in that controlling the input speed that is pressed into the mphenylenediamine sulfate liquor, made reaction time 2.5～4 hours.
3,, it is characterized in that the mphenylenediamine sulfate liquor preheating temperature that will be pressed into is 229～241 ℃ according to the method for the described preparing resorcinol by continuous hydrolyzing metaphenylene diamine of claim 1.
4, according to the method for the described preparing resorcinol by continuous hydrolyzing metaphenylene diamine of claim 1, the coefficient that it is characterized in that in the highly pressured hydrolysis reactor filling ionized water or distilled water is 0.8.
5, according to the method for the described preparing resorcinol by continuous hydrolyzing metaphenylene diamine of claim 1, when it is characterized in that preparing mphenylenediamine vitriol, the mol ratio of mphenylenediamine, 98% sulfuric acid and water is 1: (1～3): (50～100).
6, according to the method for the described preparing resorcinol by continuous hydrolyzing metaphenylene diamine of claim 1, the mol ratio that it is characterized in that mphenylenediamine, 98% sulfuric acid and water is 1: 2: 63.
7, according to the method for claim 5 or 6 described preparing resorcinol by continuous hydrolyzing metaphenylene diamine, the process for preparation that it is characterized in that mphenylenediamine vitriol is: be mixed with the dilute sulphuric acid that concentration is 12-15% with 98% sulfuric acid and water earlier, and then the adding mphenylenediamine stirs, make its whole dissolvings, 40～90 ℃ of preparation temperature.
8, according to the method for the described preparing resorcinol by continuous hydrolyzing metaphenylene diamine of claim 7, it is characterized in that preparing temperature is 60～70 ℃.
9,, it is characterized in that highly pressured hydrolysis reactor and high pressure rewinding still material adopt Monel metal or tantalum material or zirconium material to make according to the method for the described preparing resorcinol by continuous hydrolyzing metaphenylene diamine of claim 1.
10, according to the method for the described preparing resorcinol by continuous hydrolyzing metaphenylene diamine of claim 1, the extraction organic solvent that it is characterized in that reacting feed liquid is propyl carbinol or n-butyl acetate.
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| CNB2007100195616A CN100494139C (en) | 2007-01-09 | 2007-01-09 | Method for preparing resorcinol by continuously hydrolyzing metaphenylene diamine |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735019A (en) * | 2009-12-31 | 2010-06-16 | 浙江龙盛化工研究有限公司 | Process for producing resorcinol by continuously hydrolyzing m-phenylenediamine |
| CN102276423A (en) * | 2011-06-28 | 2011-12-14 | 江苏科圣化工机械有限公司 | Method for producing hydroquinone by direct hydrolysis of p-phenylenediamine |
| CN102911018A (en) * | 2011-08-04 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for separating phenol-containing organic substances from m-phenylenediamine acidic hydrolysate |
| CN113387812A (en) * | 2020-03-12 | 2021-09-14 | 深圳有为技术控股集团有限公司 | Process for preparing (hetero) aromatic polyamines |
-
2007
- 2007-01-09 CN CNB2007100195616A patent/CN100494139C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735019A (en) * | 2009-12-31 | 2010-06-16 | 浙江龙盛化工研究有限公司 | Process for producing resorcinol by continuously hydrolyzing m-phenylenediamine |
| CN101735019B (en) * | 2009-12-31 | 2012-09-26 | 浙江龙盛化工研究有限公司 | Process for producing resorcinol by continuously hydrolyzing m-phenylenediamine |
| CN102276423A (en) * | 2011-06-28 | 2011-12-14 | 江苏科圣化工机械有限公司 | Method for producing hydroquinone by direct hydrolysis of p-phenylenediamine |
| CN102911018A (en) * | 2011-08-04 | 2013-02-06 | 浙江龙盛化工研究有限公司 | Method for separating phenol-containing organic substances from m-phenylenediamine acidic hydrolysate |
| CN102911018B (en) * | 2011-08-04 | 2015-05-20 | 浙江龙盛化工研究有限公司 | Method for separating phenol-containing organic substances from m-phenylenediamine acidic hydrolysate |
| CN113387812A (en) * | 2020-03-12 | 2021-09-14 | 深圳有为技术控股集团有限公司 | Process for preparing (hetero) aromatic polyamines |
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