CN101735019B - Process for producing resorcinol by continuously hydrolyzing m-phenylenediamine - Google Patents

Process for producing resorcinol by continuously hydrolyzing m-phenylenediamine Download PDF

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CN101735019B
CN101735019B CN200910156657A CN200910156657A CN101735019B CN 101735019 B CN101735019 B CN 101735019B CN 200910156657 A CN200910156657 A CN 200910156657A CN 200910156657 A CN200910156657 A CN 200910156657A CN 101735019 B CN101735019 B CN 101735019B
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hydrolysis
mphenylenediamine
reaction
tower reactor
phenylenediamine
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CN101735019A (en
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何旭斌
王新武
陶建国
孟明
朱敬鑫
张桂香
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SHANGHAI HONGYUAN XINCHUANG MATERIAL TECHNOLOGY CO., LTD.
Zhejiang Hongsheng Chemical Research Limited
Zhejiang Longsheng Chemicals Co., Ltd.
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ZHEJIANG HONGSHENG CHEMICAL RESEARCH Ltd
ZHEJIANG LONGSHENG CHEMICALS CO Ltd
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Abstract

The invention discloses a process for producing resorcinol by continuously hydrolyzing m-phenylenediamine. The devices adopted by the process include a pipe mixer, a heat exchanger and a tower reactor, wherein baffle plates are distributed in the tower reactor from top down and the external wall of the tower reactor is provided with a heating pipe coil. The process comprises the following steps: 1, continuously preparing a hydrolysis raw material by using the pipe mixer to form homogeneous aqueous solution of m-phenylenediamine sulfate; 2, preheating the aqueous solution of m-phenylenediamine sulfate to 225 to 245 DEG C by the heat exchanger, continuously filling the aqueous solution of m-phenylenediamine sulfate to the tower reactor from the top part of the tower reactor, keeping the reaction and retention time of the reaction material in the tower reactor between 120 and 240 minutes, and performing continuous hydrolysis reaction; and 3, performing post-processing step of the hydrolysis reaction solution obtained by the hydrolysis reaction to obtain the resorcinol. The process has the characteristics of high equipment efficiency, short production period, high product yield, stable product quality and simple and convenient process control.

Description

The technology of producing resorcinol by continuously hydrolyzing m-phenylenediamine
(1) technical field
The present invention relates to a kind of technology of producing resorcinol by continuously hydrolyzing m-phenylenediamine.
(2) background technology
Resorcinol (Resorcinol) is commonly called as resorcinol; Have another name called 1; 3-dihydroxy-benzene etc.; Be a kind of important Organic Chemicals, be widely used in fields such as agricultural chemicals, dyestuff, coating, medicine, plastics, rubber, electronic chemical product, wherein be mainly used in the soaker used of preparation tyre cord, use for synthetic rubber tacky resin, wood gluing plate hight performance tackiness agent, synthetic benzophenone UV light absorber, Metha Amino Phenon etc.
It is the sulfonated alkali fusion method of raw material that the route of the synthetic Resorcinol of industriallization at present mainly contains with benzene, be the oxidation style and the mphenylenediamine hydrolysis method of raw material with the m-Diisopropylbenzene.Domestic main employing is the sulfonated alkali fusion method of raw material with benzene, owing to technology and equipment reason, has the technology barrier that is difficult to overcome aspect production cost and the environment protection treating improving.The mphenylenediamine hydrolysis process is because of raw material sources are convenient, technical process is short, good environmental protection presents good prospects for application, and corresponding, the HTHP of hydrolysis reaction and acidic medium operating mode have proposed higher requirement to the reactor material erosion resistance.
Can high yield in the aqueous media of mphenylenediamine in the presence of mineral acids such as sulfuric acid, phosphoric acid, hydrochloric acid, the one-step synthesis Resorcinol, organic solvent extraction is used in hydrolysis material cooling back, extract can obtain Resorcinol through rectifying.Because the characteristic of mphenylenediamine hydrolysis reaction; All there is the influence that is mutually related in conditions such as the proportioning of sulfuric acid, water and mphenylenediamine, temperature of reaction, reaction times to transformation efficiency, product yield; Around the reaction process and the equipment of the synthetic Resorcinol of mphenylenediamine hydrolysis, before this a series of bibliographical informations corresponding research:
US3462497 has disclosed a kind of in phosphoric acid or sulfuric acid medium, adopts the intermittent hydrolysis technology of carrying out in the airtight high pressure stirring tank of liner Monel metal, data presentation among the embodiment, and hydrolysis generates a large amount of arborescens products under the sulfuric acid medium.
The hydrolysis process that US3862245 introduces, mphenylenediamine is 1: 1.6~1.8 with adding the preferred mol ratio of vitriolic, 220~230 ℃ of temperature of reaction, reaction times 1.5~6h is reflected in the tantalum pipe reactor of oil bath heating and carries out continuously, and yield reaches 67.5%.This technology exists per pass conversion and the lower problem of hydrolysis yield.The same JP74-143979 that adopts tubular reactor to study, tubing is used the tantalum manufacturing, sulfuric acid and mphenylenediamine mol ratio 1.6: 1,220 ℃ of temperature of reaction, residence time 3h, product yield only reach 67.5%.
The sulfuric acid and the mphenylenediamine mol ratio of US6531637 research are 1.6~2.1, and the mol ratio of water and mphenylenediamine is 50~120: 1,200~250 ℃ of temperature of reaction, preferred reaction time 2~10h.Hydrolysis reaction process by zirconium and zirconium alloy or the reaction kettle of the belt stirrer of liner zirconium and zirconium alloy in carry out, reaction process continues to stir.The embodiment data presentation; Under the certain material proportion and temperature of reaction; The one way hydrolysis prolongation residence time can be improved yield; Further improve sulfuric acid proportioning and temperature of reaction and help improving reaction yield and reduce the reaction times, but can increase the risk that resinous generates yet, yield does not improve.
It is the technology of the reaction kettle discontinuous hydrolysis production Resorcinol of tantalum, zirconium or tantalum alloy, zirconium alloy at inwall that CN200510117199B has introduced a kind of; Reaction kettle can not established whipping appts; The sulfate solution of the mphenylenediamine of preparation consumption adds reaction kettle, adds thermal material and insulation through the heating unit that carries with oil bath.Hydrolysis material mphenylenediamine and vitriolic proportioning are 1: 1.8~2.4,230~255 ℃ of temperature of reaction, reaction time 3~8h; The embodiment data presentation adopts the reaction example yield level of high temperature, short residence time(SRT) obviously on the low side.
For the yield that improves Resorcinol reduces the reaction times; Patent US6531637 proposes that also the material of an one-step hydrolysis is shifted out the Resorcinol continued through cooling, extraction and carries out the reaction of two one-step hydrolysis, and the hydrolysis yield can significantly improve, but obviously; Experienced the intermittent process of cooling, intensification in the middle of two one-step hydrolysis; And second the one-step hydrolysis reacting material concentration lower, two one-step hydrolysis material heating and cooling energy consumptions are high, plant efficiency is low, more do not possess economy.
The equipment that Resorcinol is produced in the mphenylenediamine hydrolysis generally adopts nonferrous materials manufacturings such as zirconium, tantalum, and the relevant device cost is higher.Because tubular reactor is owing to be difficult to provide longer reaction time, reaction yield is difficult to reach the ideal effect.Hydrolysis process for above-mentioned employing reaction kettle; Because there is certain coefficient in reaction kettle; The input and output material of intermittent hydrolysis flow process, material heating and cooling non-cutting times is long etc., and production efficiency of equipment is low, the reaction volume that the batch reactor requirements of process is bigger; Single complete equipment production capacity is very low, causes investing excessive.The heating and cooling of intermittent process material periodically hocket in addition, and energy can't rationally be utilized, and energy consumption is bigger, consider from technology macroeconomic property, and heavy industrialization is lacked competitiveness.Tank reactor is because temperature of reaction and pressure are high, reaction medium is to the particular requirement of stirring rake solidity to corrosion and sealing property in addition, and it is more to increase whisking appliance investment increase.
For improving Resorcinol yield and production efficiency of equipment; CN200710019561B has proposed a kind of method of preparing resorcinol by continuous hydrolyzing metaphenylene diamine; This patent adopts the placed in-line hydrolysis process of many stills; Adopt three hydrolysis kettles, a rewinding still among the embodiment, the highly pressured hydrolysis still is processed by Monel metal or tantalum material or zirconium material.Reaction mass mphenylenediamine sulfate liquor is intermittently batching, adding continuously in batches; Reaction product is taken out continuously, has avoided batch reactor loading and unloading material supervisor, has improved the utilization coefficient of equipment; Compare production capacity with interrupter method and improve 1~2 times, reduced facility investment relatively.But obviously; There is serious backmixing in material in the still formula hydrolysis reactor: during the tank reactor operate continuously, and the material diffusion of moving from top to bottom, a raw material and the interior mixing of materials of pot that the concentration of adding is higher; The natural convection that the severe difference of one side different components causes all can produce backmixing; On the other hand, because the liquid-flow form is different in the reaction kettle, if do not dispose stirring rake, mixing of materials and inhomogeneous in the still, partial material residence time in reaction kettle is longer.Although adopt a plurality of reactor serial operations; The degree that has suppressed backmixing relatively; But the transformation efficiency of per unit reactor volume reactant is this minimum in flow reactor shortcoming still can't be avoided; Therefore, be inevitable in order to obtain the bigger reactor drum of high conversion employing or to increase reactor drum progression.Still reaction is owing to exist the material back-mixing, and partial material residence time in reaction kettle is very long, and overreaction causes the amount of side reaction product to increase.In addition; Still formula rhythmic reaction is not with under the condition of stirring at reactor drum; Rely on the heating of outer wall coil pipe will cause material in reactor to have bigger thermograde, unfavorable to the control of hydrolysis reaction processing condition (mainly being temperature), cause the side reaction aggravation near the too high temperature of still inwall.
The preparation of mphenylenediamine hydrolysis material also is the important step of this device.Because mphenylenediamine hydrolyzed solution storing material process is very easily decomposed, and influences the yield and the quality of follow-up hydrolysis prods.The technology of at present having reported all adopts the mechanical agitation type mixing tank intermittently to prepare the technology of mphenylenediamine sulfate solution, adopts stirring tank to divide two step configuration dilute sulphuric acid and mphenylenediamine sulfate solutions like CN200710019561B.There is the mixing region ununiformity in the mechanical agitation type mixing tank, and is even in order to make two kinds or various liquid material thorough mixing in the shortest time, must strengthen mixture strength, and mixture strength increases and certainly will cause outside input energy consumption too high.Intermittently batching is used for ensureing subsequent handling, need dispose the dosing unit and the storage vessel of two cover dosing units or a cover comparatively large vol simultaneously, and this all can cause the hydrolysis material storage time long, and raw material decomposes to be increased, and has reduced reaction yield and quality product.
(3) summary of the invention
The objective of the invention is to effectively to improve the mphenylenediamine hydrolysis and produce the production efficiency of Resorcinol, provide that a kind of plant efficiency is high, with short production cycle, product yield is high, the technology of constant product quality, mphenylenediamine continuous hydrolyzing production Resorcinol that technology controlling and process is easy.
For realizing the foregoing invention purpose, the present invention adopts following technical scheme:
A kind of technology of producing resorcinol by continuously hydrolyzing m-phenylenediamine; The device of said process using comprises in order to the line mixer of preparation mphenylenediamine hydrolysis material, in order to interchanger and the tower reactor in order to be hydrolyzed and to react with the mixing raw material heating; The outlet of said line mixer is communicated with the material inlet of said interchanger; The material outlet of said interchanger is communicated with the hydrolysis material import of said tower reactor; Arrange traverse baffle in the said tower reactor from top to bottom, the outer wall of said tower reactor has heating coil; Said technology comprises the steps:
1. prepare hydrolysis material mphenylenediamine vitriol continuously through line mixer, form the aqueous solution of uniform mphenylenediamine vitriol;
After the aqueous solution of the mphenylenediamine vitriol that 2. prepares is preheating to 225~245 ℃ through interchanger earlier; Join the tower reactor continuously from the tower reactor top; The reaction time of control reaction mass in tower reactor is 120-240min; Carry out the continuous hydrolyzing reaction, the tower reactor bottom is extraction hydrolysis reaction solution continuously; The heating coil control hydrolysis temperature of passing through control tower reactor outer wall in the hydrolysis reaction is at 225~245 ℃;
3. hydrolysis reaction gained hydrolysis reaction liquid obtains the Resorcinol product through postprocessing working procedures.
Specify in the face of above-mentioned process step down:
1. step of the present invention uses the line mixer material that is mixed; There is not moving parts in the line mixer; Dependence is assembled in mixing head internal resistance fluid element, like the mixed cell that flight, petal, waved plate, grizzly bar etc. constitute, produces shunting when making flow pass through mixed cell, intersects and mix and reverse eddy flow etc.; Disperse separately to be mixed with each other when two strands of liquid are flowed in mixer tube with certain flow velocity simultaneously, mixing of materials is abundant.The metering of convey materials is optional is perhaps selecting common topping-up pump, under meter and regulating valve for use with the metering topping-up pump; Realize that simultaneously the continuous supercharging of material is carried and the function of metering; When wherein selecting common topping-up pump, under meter and regulating valve for use, under meter and regulating valve can be arranged on before the common topping-up pump or common topping-up pump after.
Further; The preparation process of the preferred said hydrolysis material mphenylenediamine vitriol of the present invention adopts the continuous blended mode of two-stage pipeline: said line mixer is the compact cascade type mixing tank; Said compact cascade type mixing tank comprises one-level mixing tank and secondary mixing tank; The outlet of said one-level mixing tank connects the inlet of said secondary mixing tank; Deionized water or zero(ppm) water, 98% sulfuric acid, fused mphenylenediamine are used pump delivery respectively; Through the one-level mixing tank 98% sulfuric acid and deionized water or zero(ppm) water are mixed with 8~22% dilute sulphuric acid, then 8~22% dilute sulphuric acid are mixed through the secondary mixing tank with the fused mphenylenediamine, form the aqueous solution of uniform mphenylenediamine vitriol.
The mol ratio of mphenylenediamine described in the present invention and sulfuric acid, water is 1: 1.6~2.5: 50~100, and the mol ratio of preferred said mphenylenediamine and sulfuric acid, water is 1: 1.8~2.2: 60~90.
Step of the present invention technology 1. has significant advantage: continous batching, and be employed in spool road mixing tank and can accomplish effective mixing moment, the hydrolyzed solution material is promptly joined and is promptly got into hydrolysis reaction, solves the decomposition spoilage problems of still formula batching material storage process; Mass-transfer efficiency is very high, and pressure drop and energy expenditure are very low, energy saving, minimizing investment; It is very little to mix distance and installing space, through controlling the flow of all components abreast, very big storage area need be provided, and need not to use special-purpose mixing equipment, has avoided the defective of traditional steel basin etc.; Do not have moving parts, do not have wearing and tearing, almost do not have maintenance cost, for production brings very big benefit.
Interchanger according to the invention is a tube and shell heat exchanger, and heating medium adopts thermal oil.Certainly, also can select the interchanger of other types, need only the temperature that mixing raw material is heated to setting.
Among the present invention, hydrolysis reactor is made up of a tower reactor, and the length of the traverse baffle of said tower reactor is littler than the inner chamber width of said tower reactor, and adjacent traverse baffle up and down is installed in the both sides of tower reactor respectively.
Step of the present invention 2. in, the hydrolysis material is added by the tower upper inlet, the bottom discharge port flows out.During initial the driving, add deionized water or zero(ppm) water in tower reactor and the ripe still earlier, use the nitrogen replacement system; Heat to 225~245 ℃ by the outer wall heating coil; The material that adds preheating then continuously, input speed is controlled according to the proportioning of mphenylenediamine and sulfuric acid/water, the rational reaction time that temperature of reaction is confirmed, guarantees reaction times 120-210min; Carry out the continuous hydrolyzing reaction, the extraction of serialization simultaneously hydrolysis material.
The hydrolysis reaction output of column depends on the useful volume of tower, and along with device capability improves, volume strengthens; The length lengthening in order to reduce the material back-mixing, evenly flows the interior material of tower; The hydrolysis reaction tower of design larger ratio of height to diameter; But because the restriction of factors such as cost and manufacturing installation can be adopted the tower of being with traverse baffle, aspect ratio can suitably reduce.A plurality of traverse baffles are set in the tower, are divided into several cells to whole tower, eliminate back mixing.Described hydrolysis tower aspect ratio 3~10, baffle(s) spacing are 1/3~3/4 of diameter.In order to guarantee that the mphenylenediamine hydrolysis reaction transforms fully, the amount of each material of control preparation mphenylenediamine sulfate solution is to regulate the speed that the material in the reactor drum is separated in water inlet, control reaction time 120~240min.
Among the present invention; The contact interface of the contact interface of said tower reactor and reaction mass and said interchanger and hydrolysis material all need adopt corresponding high temperature resistant dilute sulphuric acid (8~20%) corrosive material, and concrete available material comprises metal tantalum, zirconium or its alloy.
Postprocessing working procedures of the present invention can adopt conventional operation, comprise the steps: that hydrolysis reaction liquid is cooled to room temperature after, extract with organic solvent, the washing, desolventizing, rectifying makes the Resorcinol product.Preferred propyl carbinol of described organic solvent or N-BUTYL ACETATE.
Among the present invention; Because it is oxidized that stock yard phenylenediamine and product Resorcinol are prone to; Production system integral body comprises that mphenylenediamine sulfate solution configuration-system, preheater device, hydrolysis device and pipeline etc. all need use nitrogen replacement in advance; Make no air in the system, begin to add the mphenylenediamine material then.
The present invention is a kind of continuous, efficient, stable production process for resorcinol; Device intensification degree is high; Effectively reduce plant investment, strengthened the competitive power of mphenylenediamine hydrolysis production Resorcinol process scale operation, its main advantage is mainly reflected in following several respects:
1. adopt line-blending, continous batching, can accomplish effective mixing moment, the hydrolyzed solution material is promptly joined and is promptly got into hydrolysis reaction, solves the decomposition spoilage problems of still formula batching material storage process; In whole mixing process, the composition of very fast definite mixture, and make on its numerical value that remains on any adjustment in advance; Like this, not only increased operational handiness, through the flow of parallel control mixture; The concentration of fluid on whole cross section is continuously and equilibrated; Not only be easy to accomplish to mix, reduce energy consumption, and can effectively control device.
2. successive hydrolysis reaction technology is stable.Through traverse baffle is set, it is long-pending to reduce flow channel cross, material along column plate radially flow velocity improve relatively, improve local material replacement result, more help material and in hydrolysis tower, evenly flow, reduce back-mixing, avoid overreaction; The material reaction temperature relies on the preheating temperature of preheater material to control, and hydrolysis tower indirect heating coil pipe only plays insulation effect, and tower wall and center have a narrow range of temperature, and uniformity of temperature profile in the tower more helps accurate, the stable control of temperature of reaction.Above-mentioned measure all helps reducing side reaction and takes place, and improves reaction yield and quality product;
3. the reduction of material back-mixing has effectively improved the unit space reaction efficiency of hydrolysis device, reduces reaction time, improves the production capacity of unit volume.Through above-mentioned process method, Resorcinol hydrolysis yield is compared production capacity and is improved 2~3 times more than 90% with interrupter method, and hydrolysis reactor unit space reaction efficiency has reduced investment than adopting series connection still formula hydrolysis process reactor drum to improve more than 20%.
(4) description of drawings
Fig. 1 is the process flow sheet that the mphenylenediamine continuous hydrolysis prepares Resorcinol.
Fig. 2 is the structural representation of line mixer, wherein, and 1 import of a-material, 2 imports of b-material, the outlet of c-mixture.
Fig. 3 is the structural representation of tower hydrolysis reactor, wherein, and a-hydrolysis material import b-hydrolysis material outlet c-drain d-relief valve connection e-heating coil.
(5) embodiment
Through accompanying drawing and specific embodiment technical scheme of the present invention is further specified below, but protection scope of the present invention is not limited thereto:
With reference to Fig. 1~Fig. 3; A kind of mphenylenediamine continuous hydrolysis prepares the device of Resorcinol; Comprise the line mixer 1 in order to preparation mphenylenediamine hydrolysis material, interchanger 2 and tower reactor 3 in order to be hydrolyzed and to react in order to mixing raw material is heated; The outlet of said line mixer 1 is communicated with the material inlet of said interchanger 2; The material outlet of said interchanger 2 is communicated with the hydrolysis material import of said tower reactor 3, arranges traverse baffle 4 from top to bottom in the said tower reactor 3, and the outer wall of said tower reactor 3 has heating coil.
Said device also comprises metering topping-up pump 5, with the said metering topping-up pump 5 of installation on the pipeline that the import of said line mixer is connected.
Said device also comprises topping-up pump 5, and under meter and variable valve is installed on the pipeline that the import of said line mixer is connected.
Mphenylenediamine sulfate solution process for preparation of the present invention adopts the metering topping-up pump to carry or common topping-up pump+flow metering+valve control.
Said interchanger 2 is a tube and shell heat exchanger, and heating medium adopts thermal oil or steam.Certainly, also can select the interchanger of other types.
The length of said traverse baffle 4 is littler than the inner chamber width of said tower reactor, and adjacent traverse baffle up and down is installed in the both sides of tower reactor respectively.
Comprise mixed cell 5 in the said line mixer; Mixed cell 5 is flight, petal, waved plate or grizzly bar; Have choked flow, mixing effect; Produce when making flow pass through mixed cell shunting, intersection mixing and reverse eddy flow etc., two strands of liquid disperse to be mixed with each other the material thorough mixing when flowing in mixer tube with certain flow velocity simultaneously separately.
Said line mixer 1 is the compact cascade type mixing tank, and said compact cascade type mixing tank comprises one-level mixing tank and secondary mixing tank, and the outlet of said one-level mixing tank connects the inlet of said secondary mixing tank.
With reference to accompanying drawing 1, the one-level mixing tank has two imports, and one of which is the import of water, and it two is 98% vitriolic import, and the secondary mixing tank also has two imports, and one of which is communicated with the one-level mixer outlet, and it two is the import of mphenylenediamine; On the pipeline of the import of water, 98% sulfuric acid and three kinds of raw materials of mphenylenediamine, can simultaneously the positive battery metering pump be set directly, common topping-up pump+flow metering+valve control perhaps is set simultaneously; Certainly, also can select on the pipeline of import of a certain or two kinds of raw materials the positive battery metering pump to be set, common topping-up pump+flow metering+valve control is set on the pipeline of the import of raw material in addition.
Embodiment 1
Hydrolysis reaction and feed proportioning system are with air in the nitrogen replacement system and device.
Carry 98% sulfuric acid, fused mphenylenediamine and de-mineralized water (or zero(ppm) water) continuously with topping-up pump respectively through metering; Wherein, 98% sulfuric acid and water are through the dilute sulphuric acid of one-level line mixer preparation 12%; Dilute sulphuric acid and mphenylenediamine are through secondary line mixer preparation mphenylenediamine sulfate liquor, and the flow of mphenylenediamine, 98% sulfuric acid, water is respectively 0.77kg/min, 2.075kg/min, 10.21kg/min, and the mol ratio of confirming mphenylenediamine, sulfuric acid, water is 1: 2.0: 60.
2m is adopted in hydrolysis 3Tower reactor, aspect ratio 4.2, in establish five traverse baffles.With the mphenylenediamine sulfate solution of the mphenylenediamine of metering after the supercharging, sulfuric acid, water preparation after being warmed up to 237 ℃ through interchanger; Be pressed into the cat head opening for feed of tower reactor continuously; Inlet amount 13.05kg/min; Keeping 237 ℃ of tower reactor temperature of reaction, reaction time is 160min, carries out the continuous hydrolysis reaction.Simultaneously, serialization extraction hydrolysis reaction solution at the bottom of the tower.
Hydrolysis reaction liquid cool to room temperature is collected the hydrolysis reaction liquid 10kg of extraction, divides 3~5 extractions with the 6kg propyl carbinol; The organic phase 7.74g that extraction obtains uses the 1kg water washing, and the organic phase distillation that obtains removes solvent; Precipitation finishes; Rectification under vacuum under the vacuum condition of 20mmHg then promptly obtains purity and is 99.6% Resorcinol 1.48kg, and yield is 91.4%.
Embodiment 2
According to embodiment 1 described method, different is: the mol ratio of mphenylenediamine, sulfuric acid, water is 1: 1.8: 80,242 ℃ of hydrolysising reacting temperatures, hydrolysis reaction residence time 135min.Product purity 99.4%, yield 90.0%.
Embodiment 3
According to embodiment 1 described method, different is: the mol ratio of mphenylenediamine, sulfuric acid, water is 1: 2: 100,230 ℃ of hydrolysising reacting temperatures, hydrolysis reaction residence time 200min.Product purity 99.5%, yield 91.2%.
Embodiment 4
According to embodiment 1 described method, different is: the mol ratio of mphenylenediamine, sulfuric acid, water is 1: 2: 100,226 ℃ of hydrolysising reacting temperatures, hydrolysis reaction residence time 235min.Product purity 99.7%, yield 92.1%.

Claims (9)

1. the technology of a producing resorcinol by continuously hydrolyzing m-phenylenediamine; The device that it is characterized in that said process using comprises line mixer, interchanger and the tower reactor in order to be hydrolyzed and to react in order to mixing raw material is heated in order to the preparation hydrolysis material; The outlet of said line mixer is communicated with the material inlet of said interchanger; The material outlet of said interchanger is communicated with the hydrolysis material import of said tower reactor; Arrange traverse baffle in the said tower reactor from top to bottom, the outer wall of said tower reactor has heating coil; Said technology comprises the steps:
1. be raw material with the vitriol oil, deionized water or zero(ppm) water and fused mphenylenediamine, prepare hydrolysis material continuously, form the aqueous solution of uniform mphenylenediamine vitriol through line mixer;
After the aqueous solution of the mphenylenediamine vitriol that 2. prepares is preheating to 225~245 ℃ through interchanger earlier; Join the tower reactor continuously from the tower reactor top; The reaction time of control reaction mass in tower reactor is 120-240min; Carry out the continuous hydrolyzing reaction, the tower reactor bottom is extraction hydrolysis reaction solution continuously; Heating coil control hydrolysis temperature through the tower reactor outer wall in the hydrolysis reaction is 225~245 ℃;
3. hydrolysis reaction gained hydrolysis reaction liquid obtains the Resorcinol product through postprocessing working procedures.
2. the technology of producing resorcinol by continuously hydrolyzing m-phenylenediamine as claimed in claim 1; The preparation process that it is characterized in that said hydrolysis material mphenylenediamine vitriol adopts the continuous blended mode of two-stage pipeline: said line mixer is the compact cascade type mixing tank; Said compact cascade type mixing tank comprises one-level mixing tank and secondary mixing tank; The outlet of said one-level mixing tank connects the inlet of said secondary mixing tank; Deionized water or zero(ppm) water, 98% sulfuric acid, fused mphenylenediamine are used pump delivery respectively; Through the one-level mixing tank 98% sulfuric acid and deionized water or zero(ppm) water are mixed with 8~22% dilute sulphuric acid, then 8~22% dilute sulphuric acid are mixed through the secondary mixing tank with the fused mphenylenediamine, form the aqueous solution of uniform mphenylenediamine vitriol.
3. according to claim 1 or claim 2 the technology of producing resorcinol by continuously hydrolyzing m-phenylenediamine is characterized in that said three kinds of raw materials use the metering topping-up pump or use common topping-up pump, under meter and regulating valve to measure and carry before mixing.
4. according to claim 1 or claim 2 the technology of producing resorcinol by continuously hydrolyzing m-phenylenediamine, the mol ratio that it is characterized in that said mphenylenediamine and sulfuric acid, water is 1: 1.6~2.5: 50~100.
5. the technology of producing resorcinol by continuously hydrolyzing m-phenylenediamine as claimed in claim 4, the mol ratio that it is characterized in that said mphenylenediamine and sulfuric acid, water is 1: 1.8~2.2: 60~90.
6. according to claim 1 or claim 2 the technology of producing resorcinol by continuously hydrolyzing m-phenylenediamine; The length that it is characterized in that said traverse baffle is littler than the inner chamber width of said tower hydrolysis reactor, and adjacent traverse baffle up and down is installed in the both sides of tower hydrolysis reactor respectively.
7. according to claim 1 or claim 2 the technology of producing resorcinol by continuously hydrolyzing m-phenylenediamine is characterized in that the contact interface of said tower reactor and reaction mass and the contact interface of said interchanger and hydrolysis material adopt one of following material separately: metal tantalum, zirconium or its alloy.
8. according to claim 1 or claim 2 the technology of producing resorcinol by continuously hydrolyzing m-phenylenediamine; After it is characterized in that described postprocessing working procedures comprises the steps: that the hydrolysis material is cooled to room temperature, extract washing with organic solvent; Desolventizing, rectifying make the Resorcinol product.
9. the technology of producing resorcinol by continuously hydrolyzing m-phenylenediamine as claimed in claim 8 is characterized in that described organic solvent is propyl carbinol or N-BUTYL ACETATE.
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