CN100494138C - Industrialized method for preparing resorcin - Google Patents
Industrialized method for preparing resorcin Download PDFInfo
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- CN100494138C CN100494138C CNB2005101171997A CN200510117199A CN100494138C CN 100494138 C CN100494138 C CN 100494138C CN B2005101171997 A CNB2005101171997 A CN B2005101171997A CN 200510117199 A CN200510117199 A CN 200510117199A CN 100494138 C CN100494138 C CN 100494138C
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Abstract
This invention relates to a method for preparing resorcinol. The method comprises: (1) adding sulfuric acid aqueous solution into m-phenylenediamine under stirring to obtain uniformly mixed raw materials; (2) adding the mixed raw materials into a reactor, sealing, heating, hydrolyzing to obtain resorcinol, and continuously heating till the hydrolysis reaction is complete; (3) terminating heating, and discharging pressure; (4) adding the mixed materials into an extraction apparatus, and extracting with an extractant; (5) rectifying the extract to remove the extractant and obtain resorcinol product. This invention has such advantages as high yield and little pollution.
Description
Technical field
The present invention relates to a kind of preparation method of Resorcinol.
Background technology
Resorcinol (claiming dihydroxy-benzene again) is important fine-chemical intermediate, and Application Areas mainly is a rubber industry, is used to produce rubber with tackifying resin, wood adhesive, UV light absorber etc., in fields such as medicine, agricultural chemicals and dyestuffs application is arranged also.Along with tire industry east, the world is moved and Chinese rubber goods industry fast development, China has now become the fastest country in global Resorcinol market growth.
At present, the main method of China's production Resorcinol is a sulfonated alkali fusion method.Sulfonated alkali fusion method technology is summarized as follows:
(1) sulfonation reaction takes place and generates Phenylsulfonic acid in liquid phenenyl in oleum, Phenylsulfonic acid further and oleum generation sulfonation reaction generate between benzene disulfonic acid;
(2) benzene disulfonic acid mixture and NaOH alkali fusion between generating generate Resorcinol sodium.
(3) in Resorcinol sodium, add the acid neutralization and make Resorcinol.
The shortcoming that this kind sulfonated alkali fusion method prepares Resorcinol is with producing a large amount of waste water in the acid and during the material behind the alkali fusion, according to related data, prepare in the whole technological process of Resorcinol at sulfonated alkali fusion method, 1 ton of Resorcinol of every production will produce about 60 tons of sewage, so a large amount of sewage not only endangers environment, and the processing cost of improvement sewage is higher; To prepare the yield of Resorcinol lower for sulfonated alkali fusion method in addition, only can reach 70%; So it is relatively poor that sulfonated alkali fusion method prepares the process economy of Resorcinol.
Summary of the invention
The purpose of this invention is to provide that a kind of manufacturing cost is lower, yield is higher and the environment protecting industrialized process for preparing of Resorcinol preferably.
Total technical conceive of the present invention is: mphenylenediamine, aqueous sulfuric acid are joined in the acid-resistant reactor, sealed reactor also heats mixing raw material and makes mphenylenediamine generation hydrolysis reaction and generate Resorcinol, material after then hydrolysis reaction being finished extracts, and again extraction phase solution rectification process is obtained the Resorcinol finished product.
The technical scheme that realizes the object of the invention is that the industrialized process for preparing of Resorcinol of the present invention has following steps: 1. under agitation add mphenylenediamine, the mixing raw material that obtains mixing in aqueous sulfuric acid; 2. the mixing raw material for preparing is added in the reactor, add the back sealed reactor, the raw material in the reactor heating makes mphenylenediamine generation hydrolysis reaction generate Resorcinol, continues heat tracing and finishes until hydrolysis reaction; 3. after hydrolysis reaction is finished, stop heating, the mixture in the reactor is carried out row pressure handle; 4. the mixture in the reactor is added in the extraction plant and carry out extraction treatment with extraction agent; 5. extraction phase solution being carried out rectification process separates extraction agent and obtains the Resorcinol product from extraction phase solution.
In the industrialized process for preparing of above-mentioned Resorcinol, the reaction formula that mphenylenediamine generation hydrolysis reaction generates Resorcinol is:
Above-mentioned steps 1. in, the vitriolic weight percent concentration is 5% to 25% in the aqueous sulfuric acid, preferred 10% to 23%; The mol ratio of mphenylenediamine consumption and the contained sulfuric acid amount of aqueous sulfuric acid is 1: 1.5 to 1: 2.5, preferred 1: 1.8 to 1: 2.4.
Above-mentioned steps 2. in, material temperature is controlled at 200 ℃ to 280 ℃, preferred 230 ℃ to 255 ℃ in mphenylenediamine generation hydrolysis reaction generates in the hydrolysis reaction of Resorcinol reactor.Reactor be salable type have purge valve, thermometer and manometric tantalum, zirconium or a tantalum zirconium alloy reactor; Reactor heating is to use the heating of oil bath chuck.Described tantalum, zirconium or tantalum zirconium alloy reactor are meant that the inwall at reactor is to be made by tantalum, zirconium or tantalum zirconium alloy, and other and material touch the position and also made by corresponding tantalum, zirconium or tantalum zirconium alloy.
Above-mentioned steps 3. in, it is the purge valve of opening reactor that the row pressure that the mixture in the reactor is carried out is handled, and by the pipeline that links to each other with purge valve the high pressure gas in the reactor is drained in the atmosphere after the absorption agent absorption; Absorption agent can be selected water for use.It is to make the pressure in the reactor reduce to environmental stress that a kind of row pressure of preferably mixture in the reactor being carried out is handled; It is to make the pressure in the reactor reduce to 1.1～2 normal atmosphere that the another kind of row pressure of preferably mixture in the reactor being carried out is handled, like this when the mixture in the reactor is taken out, can utilize that the pressure of gas extrudes mixture in the reactor through pipeline, make things convenient for the transfer of mixture in the reactor.When absorption agent is water, when can preparing Resorcinol afterwards,, promptly can use by the absorption agent after row pressure is finished dealing with as a kind of raw material of preparation Resorcinol as the dilution water of preparation during aqueous sulfuric acid.
Above-mentioned steps 4. in, it is to make mixture and extraction agent adverse current carry out the continous way extraction treatment by extraction plant to obtain extraction phase solution and extracting phase solution that mixture is carried out extraction treatment; Described extraction plant is every sieve formula extraction tower; Described extraction agent is butylacetate or propyl carbinol; Described extraction phase solution mainly contains Resorcinol and extraction agent; The described surplus phase solution of quenching mainly contains monoammonium sulfate, sulfuric acid and water.
Above-mentioned steps 4. in, before the adding of the mixture in reactor extraction plant is carried out extraction treatment with extraction agent, can also carry out processed to mixture earlier, to reduce the water content of mixture, can in follow-up extracting operation, reduce the consumption of extraction agent like this.It is that mixture is carried out air distillation processing or underpressure distillation processing that mixture is carried out processed; When mixture being carried out air distillation and handle, be to be that environmental stress and temperature of charge are to carry out under 120 ℃ to the 160 ℃ conditions at pressure; When mixture being carried out underpressure distillation and handle, be to be that 550mmHg to 700mmHg and temperature of charge are to carry out under 90 ℃ to the 130 ℃ conditions at pressure.Because the mixture in the reactor is after handling through row pressure, still has higher temperature, generally can reach 130 ℃～160 ℃, so the method that a kind of concrete processed is taked is to utilize the high temperature of mixture self, mixture is sealed in the acid-resistant container, and bleeding makes the pressure in the acid-resistant container be reduced to 550mmHg～700mmHg, to reduce the boiling point of water, water vapor is overflowed, make the moisture in the mixture be easier to be evaporated.
Above-mentioned steps 5. in, the rectification process process that extraction phase solution is carried out comprise successively fore-running, slightly the section of heating up in a steamer and after the section of heating up in a steamer, wherein, fore-running rectifying goes out mainly to contain the front-end volatiles of water and extraction agent, slightly the section of heating up in a steamer rectifying goes out mainly to contain the thick cut of water and Resorcinol, after the section of heating up in a steamer rectifying go out mainly to contain the after cut of Resorcinol, and with after cut as the Resorcinol finished product; When the contained extraction agent of extraction phase solution is butylacetate, go out in the fore-running of front-end volatiles in rectifying, adding water in reboiler, to make the water and the ratio of extraction phase solution amount be 1: 4 to 1: 5, the rectifying tower internal pressure is an environmental stress, controlling reboiler temperature simultaneously is 100 ℃ to 150 ℃, tower top temperature is 90 ℃ to 135 ℃, and the color of these front-end volatiles is colourless; When the color of cut begins yellowing, carry out the slightly section of the heating up in a steamer operation that rectifying goes out thick cut, go out in the slightly section of heating up in a steamer of thick cut in rectifying, control rectifying tower internal pressure is 700mmHg to 750mmHg, reboiler temperature is 150 ℃ to 210 ℃, and tower top temperature is 135 ℃ to 190 ℃; When the color of cut begins to become when colourless from yellow, carry out rectifying go out after cut after the section of heating up in a steamer operation, rectifying go out after cut after in the section of heating up in a steamer, control rectifying tower internal pressure is 700mmHg to 750mmHg, reboiler temperature is 155 ℃ to 210 ℃, and tower top temperature is 135 ℃ to 190 ℃; When the contained extraction agent of extraction phase solution is propyl carbinol, go out in the fore-running of front-end volatiles in rectifying, in reboiler, add the ratio 1: 4 to 1: 5 that water makes water and extraction phase solution amount, the rectifying tower internal pressure is an environmental stress, controlling reboiler temperature simultaneously is 90 ℃ to 120 ℃, tower top temperature is 85 ℃ to 110 ℃, and the color of these front-end volatiles is colourless; When the color of cut begins yellowing, carry out the slightly section of the heating up in a steamer operation that rectifying goes out thick cut, go out in the slightly section of heating up in a steamer of thick cut in rectifying, control rectifying tower internal pressure is 700mmHg to 750mmHg, reboiler temperature is 155 ℃ to 210 ℃, and tower top temperature is 130 ℃ to 190 ℃; When the color of cut begins to become when colourless from yellow, carry out rectifying go out after cut after the section of heating up in a steamer operation, go out in the process of after cut in rectifying, control rectifying tower internal pressure is 700mmHg to 750mmHg, reboiler temperature is 155 ℃ to 210 ℃, and tower top temperature is 135 ℃ to 190 ℃.
In addition, can mainly be contained the aqueous phase solution of water after the smart distilled front-end volatiles that mainly contain water and extraction agent are handled through cooling, standing demix, separatory successively and mainly be contained the organic phase solution of extraction agent; When aqueous phase solution wherein carried out rectifying to extraction phase solution in can preparation Resorcinol process afterwards, water joined in the reboiler to recycle as a supplement; Organic phase solution wherein can be used as extraction agent and recycles.Contain water and Resorcinol in the thick cut, thereby the content of Resorcinol is lower, generally not with thick cut as the Resorcinol sale of finished goods, but when next rectifying, it is added and carry out rectifying once more in reboiler to reclaim Resorcinol wherein.
Above-mentioned steps 5. in, before extraction phase solution is carried out rectification process, the aqueous solution that can also add earlier solid-state sodium hydroxide, solid-state yellow soda ash, aqueous sodium hydroxide solution or yellow soda ash in extraction phase solution is 3～5 until its pH value, like this in follow-up rectification process, at first can reduce of the corrosion of extraction phase solution, secondly can improve the coloured light degree of the Resorcinol finished product of final acquisition rectifying device.
The present invention has beneficial effect: in (1) method of the present invention when carrying out row pressure, when the high pressure gas in the reactor are adopted composition be the absorption agent of water absorb, when being expelled in the atmosphere then, when absorption agent can prepare Resorcinol afterwards as the dilution water of preparation during aqueous sulfuric acid, promptly can recycle, need not discharging, avoid contaminate environment.(2) in the inventive method, before the mixture in the reactor is added extraction plant,, can carry out processed to mixture earlier, to reduce the water content in the mixture because the moisture in the mixture is too many; Can in the extracting operation of back, reduce the consumption of extraction agent such as butylacetate like this, can also in follow-up distillation operation, reduce energy consumption, reduce to produce and give birth to this.When mixture is carried out processed, can carry out air distillation processing or underpressure distillation processing to mixture.As the dilution water of preparation during sulphuric acid soln, promptly can recycle when the water that distills out prepares Resorcinol afterwards, need not discharging, avoid contaminate environment.In addition, when the mixture in the reactor is carried out processed, because the mixture in the reactor is after handling through row pressure, still has higher temperature, generally can 130 ℃～160 ℃, carry out underpressure distillation so can utilize the high temperature of mixture self and handle its water content of reduction, being about to mixture is sealed in the acid-resistant container, bleed and make the pressure in the acid-resistant container be reduced to 700mmHg～750mmHg, to reduce the boiling point of water, water vapor is overflowed, can make full use of the process characteristic of manufacture method of the present invention like this, economize on resources and reduce production costs.(3) in the traditional preparation of industrialization Chemicals method, when the hydrolysis of organic matter reaction is carried out, generally all to apply stirring action, this will make the complex structure of reactor and manufacturing cost higher, but the present inventor finds by practice, manufacture method of the present invention all has reaction product and better conversion rate preferably stirring and do not have under the agitation condition, so overcome this prejudice traditionally in the methods of the invention, promptly do not apply stirring action in the methods of the invention the hydrolysis reaction, operation is simple and feasible to make the inventive method, owing to need not whipping appts is set, reduced the cost of making reactor simultaneously in reactor.(4) the extracting phase solution that mainly contains monoammonium sulfate, sulfuric acid and water that obtains after extraction treatment in the inventive method also can fully utilize, organic impurity because of sulfur acid ammonium and minute quantity in the extracting phase solution, after neutralization, evaporation concentration, filtration, can make ammonium sulfate, promptly can be used as the chemical fertilizer sale after again it being made with extra care raising purity, thereby realized the comprehensive utilization of resource, need not extracting phase solution is discharged, avoid contaminate environment also can reduce production costs.(5) mixture to obtaining behind the hydrolysis reaction in the inventive method carries out in the extraction treatment operation, both can take the intermittent type extraction treatment, also can take the continous way extraction treatment, but the inventive method preferably adopts the continous way extraction treatment, at first because the treatment capacity of continous way extraction is big, be suitable for large-scale industrial production, secondly because the contriver find in practice: identical down in other condition, the content of Resorcinol content of Resorcinol in the resulting extracting phase solution after the intermittent type extraction treatment in the resulting extracting phase solution after the continous way extraction treatment; In addition, if reach same effect of extracting, even the close words of content of Resorcinol in the resulting extracting phase solution after continous way extraction treatment and the intermittent type extraction treatment, the quality of the required extraction agent of intermittent type extraction treatment is about 4 times of quality of the required extraction agent of continous way extraction treatment, related data when table 1 carries out continous way extraction treatment and intermittent type extraction treatment for the contriver can be clear that by the data in the table 1 the continous way extraction treatment is more abundant, more thorough than intermittent type extraction treatment.(6) method of the present invention is a kind of industrialized process for preparing, this method can obtain high-quality Resorcinol finished product, the average yield of Resorcinol can reach 85.88%, the purity of Resorcinol can reach 99.9%, simultaneously can realize in the whole technological process water being carried out recycle, do not produce processing wastewater, promptly realize the zero release of waste water, so the inventive method is the manufacture method of the Resorcinol of an environmental protection.
Table 1
Embodiment
(embodiment 1)
The industrialized process for preparing of the Resorcinol of present embodiment has following steps:
1. be to add the 70kg mphenylenediamine in 5% the 2540kg aqueous sulfuric acid to weight percent concentration under agitation, making the mol ratio (press pure substance and calculate, descend with) of mphenylenediamine consumption and sulfuric acid consumption is 1: 2.0, thus the mixing raw material that obtains mixing;
2. the mixing raw material for preparing is added in the zirconium reactor that has purge valve, thermometer and tensimeter and can seal, mixing raw material adds the back sealed reactor, then with the type of heating of oil bath the mixing raw material in the reactor is heated to 240 ℃ and make mphenylenediamine generation hydrolysis reaction generate Resorcinol, lasting heat tracing 8 hours is to finish hydrolysis reaction;
3. after hydrolysis reaction is finished, stop heating, mixture in the reactor is carried out row pressure to be handled, promptly open the purge valve of reactor, by the pipeline that links to each other with purge valve the high pressure gas in the reactor are drained in the atmosphere after water absorbs by tank, the pressure in reactor is reduced to environmental stress; After handling, row pressure obtains the mixture of 2230kg.
4. then mixture is carried out extraction treatment, make mixture and extraction agent adverse current obtain extraction phase solution and extracting phase solution by carrying out the continous way extraction treatment every sieve formula extraction tower; Even mixture flows through from the top down every sieve formula extraction tower, extraction agent flows through from bottom to top every sieve formula extraction tower, mixture and extraction agent are behind thorough mixing in sieve formula extraction tower, the extraction phase solution that is mainly contained Resorcinol and extraction agent in top outlet every sieve formula extraction tower, the extracting phase solution that is mainly contained monoammonium sulfate, sulfuric acid and water at lower part outlet every sieve formula extraction tower, used extraction agent is a butylacetate in the present embodiment, the quality of used butylacetate is 480kg, and gained extraction phase solution is 605kg after the extraction treatment;
5. the rectification process process that extraction phase solution is carried out comprise successively fore-running, slightly the section of heating up in a steamer and after the section of heating up in a steamer, wherein, fore-running rectifying goes out mainly to contain the front-end volatiles of water and extraction agent, slightly the section of heating up in a steamer rectifying goes out mainly to contain the thick cut of water and Resorcinol, after the section of heating up in a steamer rectifying go out mainly to contain the after cut of Resorcinol, and with after cut as the Resorcinol finished product.Because water and butylacetate can form azeotrope, and azeotropic point is lower, so go out in the fore-running of front-end volatiles in rectifying, in reboiler, add water, make the ratio 1: 4.5 of water and extraction phase solution amount, to guarantee that the moisture content in the reboiler enough makes water and butylacetate steam with azeotrope, thereby the energy consumption in the reduction rectifying, controlling the rectifying tower internal pressure simultaneously is environmental stress, reboiler temperature is 100 ℃ to 150 ℃, tower top temperature is 90 ℃ to 135 ℃, and this moment, the color of cut was colourless; When the color of cut when becoming yellow, begins the slightly operation of the section of heating up in a steamer from colourless, control rectifying tower internal pressure is 700mmHg to 750mmHg, and reboiler temperature is 155 ℃ to 210 ℃, and tower top temperature is 130 ℃ to 190 ℃; When the color of cut when yellow becomes colorless once more, the operation of the section of heating up in a steamer after beginning to carry out, control rectifying tower internal pressure is 700mmHg to 750mmHg, reboiler temperature is 155 ℃ to 210 ℃, tower top temperature is 135 ℃ to 190 ℃; As the Resorcinol finished product, the weight percent content of the Resorcinol in this after cut is 98.71% with after cut.Related data sees Table 2 in the present embodiment.
In addition, mainly contained the aqueous phase solution of water after the front-end volatiles that smart distilled mainly contains water and extraction agent in the present embodiment are handled through cooling, standing demix, separatory successively and mainly contained the organic phase solution of extraction agent; When aqueous phase solution wherein carried out rectifying to extraction phase solution in can preparation Resorcinol process afterwards, water joined in the reboiler to recycle as a supplement; Organic phase solution wherein can be used as extraction agent and recycles, and the extraction agent that is recovered in the present embodiment is that the quality of organic phase solution is 950kg.
(embodiment 2 to embodiment 5)
All the other are substantially the same manner as Example 1, and difference is: proportioning raw materials and processing parameter among each embodiment are different, and the related data among each embodiment sees Table 2.
Table 2
(embodiment 6)
All the other are substantially the same manner as Example 1, and difference is: used extraction plant adopts packed extraction tower in the present embodiment; Used extraction agent is a propyl carbinol, and the processing parameter in each processing step is slightly different in addition.Related data in the present embodiment sees Table 3.
(embodiment 7 to embodiment 10)
All the other are substantially the same manner as Example 6, and difference is: proportioning raw materials and processing parameter among each embodiment are different, and related data detailed among each embodiment sees Table 3.
Table 3
(embodiment 11)
All the other are substantially the same manner as Example 1, and difference is: above-mentioned steps 4. in, the mixture in the reactor being added before extraction plant carries out extraction treatment with extraction agent, earlier mixture is carried out processed, to reduce the water content of mixture.It is that mixture is added in the still kettle that mixture is carried out processed, pressure is that environmental stress and temperature of charge are under 100 ℃ to the 130 ℃ conditions, mixture is carried out air distillation to be handled, be the most of moisture that steams in the mixture in the present embodiment, also can steam the whole moisture in the mixture in other embodiments, to reduce the consumption of extraction agent in the follow-up extraction treatment, reduce production costs.Related data in the present embodiment sees Table 4.
(embodiment 12 to embodiment 13)
All the other are substantially the same manner as Example 11, and difference is: proportioning raw materials and processing parameter among each embodiment are different, and related data detailed among each embodiment sees Table 4.
(embodiment 14 to embodiment 15)
All the other are substantially the same manner as Example 11, and difference is: used extraction agent is a propyl carbinol among each embodiment, and related data detailed among each embodiment sees Table 4.
Table 4
(embodiment 16)
All the other are substantially the same manner as Example 1, difference is: step 4. in, before the adding of the mixture in reactor extraction plant is carried out extraction treatment with extraction agent, earlier mixture is carried out the underpressure distillation processed, to reduce the water content of mixture.It is that mixture is added in the still kettle that mixture is carried out processed, pressure is that 550mmHg～700mmHg and temperature of charge are under 95 ℃～120 ℃ conditions, mixture is carried out underpressure distillation to be handled, steam most of moisture or whole moisture in the mixture, to reduce the consumption of extraction agent in the follow-up extraction treatment, reduce production costs.
Proportioning raw materials and processing parameter among each embodiment are different, and the related data among each embodiment sees Table 5.
(embodiment 17 to embodiment 18)
All the other are substantially the same manner as Example 16, and difference is: proportioning raw materials and processing parameter among each embodiment are different, and related data detailed among each embodiment sees Table 5.
(embodiment 19 to embodiment 20)
All the other are substantially the same manner as Example 16, and difference is: used extraction agent is a propyl carbinol among each embodiment, and related data detailed among each embodiment sees Table 5.
Table 5
(embodiment 21)
All the other are substantially the same manner as Example 16, and difference is: step 5. in, before extraction phase solution was carried out rectification process, earlier adding solid-state sodium hydroxide in extraction phase solution was 4 until its pH value, then carries out rectification process again.The related data of present embodiment sees Table 6.
(embodiment 22 to embodiment 25)
All the other are substantially the same manner as Example 21, and difference is: adding solid-state yellow soda ash in extraction phase solution is 4 until its pH value.The related data of each embodiment sees Table 6.
Table 6
(embodiment 26 to embodiment 30)
All the other are substantially the same manner as Example 21, and difference is: raw material among each embodiment and the processing parameter in the processing step are slightly different.Related data among each embodiment sees Table 7.
Table 7
Obviously, the above embodiment of the present invention only is for example of the present invention clearly is described, and is not to be qualification to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give exhaustive to all embodiments.And these belong to conspicuous variation or the change that spirit of the present invention extended out and still are among protection scope of the present invention.
Claims (13)
1, a kind of industrialized process for preparing of Resorcinol has following steps: 1. under agitation add mphenylenediamine, the mixing raw material that obtains mixing in aqueous sulfuric acid; 2. under the condition of stirring mixing raw material for preparing not being added in the reactor, add the back sealed reactor, the raw material in the reactor heating makes mphenylenediamine generation hydrolysis reaction generate Resorcinol, continues heat tracing and finishes until hydrolysis reaction; 3. after hydrolysis reaction is finished, stop heating, the mixture in the reactor is carried out row pressure handle; 4. the mixture in the reactor is added in the extraction plant and carry out extraction treatment with extraction agent; 5. in extraction phase solution, add solid-state sodium hydroxide, solid-state yellow soda ash, aqueous sodium hydroxide solution or aqueous sodium carbonate is 3～5 until its pH value, extraction phase solution is carried out rectification process extraction agent is separated from extraction phase solution and is obtained the Resorcinol product.
2, according to the industrialized process for preparing of the described Resorcinol of claim 1, it is characterized in that: step 1. in, the weight percent concentration of aqueous sulfuric acid is 5% to 25%, and the mol ratio of mphenylenediamine consumption and the contained sulfuric acid amount of aqueous sulfuric acid is 1: 1.5 to 1: 2.5.
3, according to the industrialized process for preparing of the described Resorcinol of claim 2, it is characterized in that: step 1. in, the weight percent concentration of aqueous sulfuric acid is 10% to 23%; The mol ratio of mphenylenediamine consumption and the contained sulfuric acid amount of aqueous sulfuric acid is 1: 1.8 to 1: 2.4.
4, according to the industrialized process for preparing of the described Resorcinol of claim 1, it is characterized in that: step 2. in, material temperature is controlled at 200 ℃ to 280 ℃ in mphenylenediamine generation hydrolysis reaction generates in the hydrolysis reaction of Resorcinol reactor.
5, according to the industrialized process for preparing of the described Resorcinol of claim 4, it is characterized in that: step 2. in, material temperature is controlled at 230 ℃ to 255 ℃ in mphenylenediamine generation hydrolysis reaction generates in the hydrolysis reaction of Resorcinol reactor.
6, according to the industrialized process for preparing of the described Resorcinol of claim 1, it is characterized in that: step 2. in, reactor be salable type have purge valve, thermometer and manometric tantalum, zirconium or a tantalum zirconium alloy reactor; Reactor heating is to use the heating of oil bath chuck.
7, according to the industrialized process for preparing of the described Resorcinol of claim 1, it is characterized in that: step 3. in, the row pressure processing that mixture in the reactor is carried out is a purge valve of opening reactor, by the pipeline that links to each other with purge valve the high pressure gas in the reactor is drained in the atmosphere after absorption agent absorbs.
8, according to the industrialized process for preparing of the described Resorcinol of claim 7, it is characterized in that: it is to make the pressure in the reactor reduce to environmental stress that the mixture in the reactor is carried out the row pressure processing, perhaps makes the pressure in the reactor reduce to 1.1～2 normal atmosphere; Absorption agent is a water; As the dilution water of preparation during aqueous sulfuric acid, promptly a kind of raw material as the preparation Resorcinol used when the absorption agent after row pressure is finished dealing with prepared Resorcinol afterwards.
9, according to the industrialized process for preparing of the described Resorcinol of claim 1, it is characterized in that: step 4. in, it is to make mixture and extraction agent adverse current carry out the continous way extraction treatment by extraction plant to obtain extraction phase solution and extracting phase solution that mixture is carried out extraction treatment; Described extraction plant is every sieve formula extraction tower; Described extraction agent is butylacetate or propyl carbinol; Described extraction phase solution mainly contains Resorcinol and extraction agent; The described surplus phase solution of quenching mainly contains monoammonium sulfate, sulfuric acid and water.
10, according to the industrialized process for preparing of the described Resorcinol of claim 9, it is characterized in that: step 4. in, before the adding of the mixture in reactor extraction plant is carried out extraction treatment with extraction agent, earlier mixture is carried out processed, to reduce the water content of mixture.
11, according to the industrialized process for preparing of the described Resorcinol of claim 10, it is characterized in that: step 4. in, it is mixture to be carried out air distillation processing or underpressure distillation handle that mixture is carried out processed; When mixture being carried out air distillation and handle, be to be that environmental stress and temperature of charge are to carry out under 120 ℃ to the 160 ℃ conditions at pressure; When mixture being carried out underpressure distillation and handle, be to be that 550mmHg to 700mmHg and temperature of charge are to carry out under 90 ℃ to the 130 ℃ conditions at pressure.
12, according to the industrialized process for preparing of the described Resorcinol of claim 10, it is characterized in that: step 5. in, the rectification process process that extraction phase solution is carried out comprise successively fore-running, slightly the section of heating up in a steamer and after the section of heating up in a steamer, wherein, fore-running rectifying goes out mainly to contain the front-end volatiles of water and extraction agent, slightly the section of heating up in a steamer rectifying goes out mainly to contain the thick cut of water and Resorcinol, after the section of heating up in a steamer rectifying go out mainly to contain the after cut of Resorcinol, and with after cut as the Resorcinol finished product; When the contained extraction agent of extraction phase solution is butylacetate, go out in the fore-running of front-end volatiles in rectifying, adding water in reboiler, to make the water and the ratio of extraction phase solution amount be 1: 4 to 1: 5, the rectifying tower internal pressure is an environmental stress, controlling reboiler temperature simultaneously is 100 ℃ to 150 ℃, tower top temperature is 90 ℃ to 135 ℃, and the color of these front-end volatiles is colourless; When the color of cut begins yellowing, carry out the slightly section of the heating up in a steamer operation that rectifying goes out thick cut, go out in the slightly section of heating up in a steamer of thick cut in rectifying, control rectifying tower internal pressure is 700mmHg to 750mmHg, reboiler temperature is 150 ℃ to 210 ℃, and tower top temperature is 135 ℃ to 190 ℃; When the color of cut begins to become when colourless from yellow, carry out rectifying go out after cut after the section of heating up in a steamer operation, rectifying go out after cut after in the section of heating up in a steamer, control rectifying tower internal pressure is 700mmHg to 750mmHg, reboiler temperature is 155 ℃ to 210 ℃, and tower top temperature is 135 ℃ to 190 ℃; When the contained extraction agent of extraction phase solution is propyl carbinol, go out in the fore-running of front-end volatiles in rectifying, adding water in reboiler, to make the water and the ratio of extraction phase solution amount be 1: 4 to 1: 5, the rectifying tower internal pressure is an environmental stress, controlling reboiler temperature simultaneously is 90 ℃ to 120 ℃, tower top temperature is 85 ℃ to 110 ℃, and the color of these front-end volatiles is colourless; When the color of cut begins yellowing, carry out the slightly section of the heating up in a steamer operation that rectifying goes out thick cut, go out in the slightly section of heating up in a steamer of thick cut in rectifying, control rectifying tower internal pressure is 700mmHg to 750mmHg, reboiler temperature is 155 ℃ to 210 ℃, and tower top temperature is 130 ℃ to 190 ℃; When the color of cut begins to become when colourless from yellow, carry out rectifying go out after cut after the section of heating up in a steamer operation, go out in the process of after cut in rectifying, control rectifying tower internal pressure is 700mmHg to 750mmHg, reboiler temperature is 155 ℃ to 210 ℃, and tower top temperature is 135 ℃ to 190 ℃.
13, according to the industrialized process for preparing of the described Resorcinol of claim 12, it is characterized in that: can mainly be contained the aqueous phase solution of water after the front-end volatiles that smart distilled mainly contains water and extraction agent are handled through cooling, standing demix, separatory successively and mainly contain the organic phase solution of extraction agent; When in the preparation Resorcinol process afterwards of aqueous phase solution wherein extraction phase solution being carried out rectifying, water joins in the reboiler to recycle as a supplement; Organic phase solution wherein as extraction agent to recycle.
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| 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 |
| CN103466873B (en) * | 2013-09-30 | 2015-09-02 | 河南龙成煤高效技术应用有限公司 | A kind of process is containing the method for high-concentration phenol, ammonia sewage |
| CN105820056B (en) * | 2016-05-17 | 2018-07-17 | 湖北可赛化工有限公司 | A kind of synthetic method and production system of 4,4 '-dimethyl diphenylamines |
| CN111217677A (en) * | 2020-02-26 | 2020-06-02 | 山东创蓝垚石环保技术有限公司 | Method for producing resorcinol by material recycling and pressurized alkali fusion |
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| Title |
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| .精细化工中间体，第32卷第（5）期. 2002 |
| 间苯二酚的生产技术现状. 常玉等 |
| 间苯二酚的生产技术现状. 常玉等；.精细化工中间体，第32卷第（5）期. 2002 * |
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Assignee: Changzhou Chungang Chemical Industry Co., Ltd. Assignor: Changhong Chemical Tech Development Co., Ltd., Changzhou City Contract record no.: 2011320000949 Denomination of invention: Industrialized method for preparing resorcin Granted publication date: 20090603 License type: Exclusive License Open date: 20070509 Record date: 20110708 |
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