CN102068945B - Reactive distillation device and method for separating and purifying methylal - Google Patents
Reactive distillation device and method for separating and purifying methylal Download PDFInfo
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- CN102068945B CN102068945B CN2010105893599A CN201010589359A CN102068945B CN 102068945 B CN102068945 B CN 102068945B CN 2010105893599 A CN2010105893599 A CN 2010105893599A CN 201010589359 A CN201010589359 A CN 201010589359A CN 102068945 B CN102068945 B CN 102068945B
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Abstract
The invention relates to a reactive distillation device and method for separating and purifying methylal. The device mainly comprises a reactor/agitator, a distillation column, a condenser, a reflux ratio controller, stainless steel fillers, a temperature gauge, a pressure gauge and a product collection and storage tank. The methylal is synthesized by subjecting the raw materials including methanol and formaldehyde to react and is separated and purified. After the methylal product is extracted, the distillation column is continuously used for separating and recovering the methanol and is used for the next cycle, thus improving the utilization ratio of the raw materials. The methanol is added to the reactor by one step. The problem that the product purity fails to meet the requirement due to azeotropy of the methanol and the methylal can be solved through the operation mode of feeding the formaldehyde from the top of the distillation column. The concentration of the formaldehyde in the residual liquid in the reactor conforms to the effluent standard. Through the operation mode of carrying out reaction and separation separately, the adverse effects of difficult control and difficult filling of catalysts caused by inconsistence of the reaction conditions and the separation conditions can be overcome and the operation difficulty of reactive distillation can be reduced, thus expanding the application range of reactive distillation.
Description
Technical field
The present invention relates to a kind of dimethoxym ethane that is used for and separate the reaction and rectification device and the method for purifying.Specifically be to be the raw material reaction synthesizing dimethoxym ethane and it is separated the novel intermittent formula reactive distillation mode of operation and the implementation method of purification with methyl alcohol, formaldehyde.After the extraction of dimethoxym ethane product finished, rectifying column continued on for the Separation and Recovery of methyl alcohol, supplies next to recycle, and has improved raw material availability.The disposable adding reactor of methyl alcohol, the mode of operation of rectifying column jacking formaldehyde can solve because methyl alcohol and dimethoxym ethane azeotropic cause product purity not reach the problem of requirement, concentration of formaldehyde allow compliance with emission standards in the reactor residual solution.Reaction separates that the mode of operation of carrying out can overcome because reaction and the inconsistent adverse effects of bringing such as restive, catalyst filling difficulty of separation condition with separating, thereby the operation easier that reduces reactive distillation enlarges its range of application.
Background technology
Reactive distillation is a kind of as special extract rectification; Be that course of reaction and distillation process are combined, and the coupling process that in same equipment (destilling tower), carries out, through the method for rectifying reactant and product are separated; To destroy the equilibrium relation of reversible reaction; Make reaction continue to carry out, thereby improve conversion ratio, the shortening reaction time of reversible reaction, improve the production capacity of selectivity and strengthening device to the direction that generates product; And utilize the heat of exothermic reaction to cut down the consumption of energy, reduce operating cost and investment.
According to the difference of reaction system and employing catalyst, reactive distillation can be divided into homogeneous reaction rectifying (comprising catalysis and uncatalyzed reaction rectifying) and heterogeneous catalytic reaction rectifying.Be mainly used in in the synthetic reaction of ether reaction, esterification, hydrolysis, addition reaction, dehydration, substitution reaction and polymer.
Traditional reactive distillation process is with in the disposable adding reactor of raw material; After question response finishes mixture added in the rectifying column in the lump and separate; Because the restriction of molecular balance; The content that gets into reactant in the mixture of rectifying column is still very high, causes to can not get purer product after the separation and need reclaim raw material, thereby has increased operating cost and cost of investment.
Improved reactive distillation process only utilize a tower just can realization response with separate two processes, whole tower is divided into three parts from top to bottom: rectifying section, conversion zone and stripping section.Raw material gets into reactive distillation column from the below and the top of conversion zone respectively, and in the abundant haptoreaction of conversion zone, product is in time separated with reactant, and raising conversion ratio and separative efficiency are mutually promoted in reaction with separating.
The Backpack type reactive distillation is a kind of novel catalytic distillation pattern; Main feature is in tower, to transfer to reaction outside the tower; Help the replacing of catalyst like this, can utilize fully again simultaneously that the reactive distillation conversion ratio is high, selectivity is good, energy consumption is low, product purity is high, series of advantages such as easy to operate and reduced investment.Abroad, the commercial Application of utilizing the Backpack type reactive distillation to produce dimethoxym ethane has been arranged, be applicable to the Large Scale and Continuous reactive distillation processes, but domestic this technology also useless.
Though constantly the technology of reactive distillation is improved; But still has himself limitation: reaction system is had relatively high expectations; Reaction must be carried out under identical temperature and pressure with separated; The volatility of target product and reactant can not be close, under rectification temperature, can cause the adverse effects such as increase of side reaction; Chemical reaction must be a liquid phase reactor, and used catalyst can not have with each component of reaction system and dissolves each other or interact in the catalytic distillation process, and raw material can not contain catalyst poison, in the reaction easily the petrochemical process of coking on catalyst should not use; Require catalyst that the higher active and long life-span must be arranged in the rectification temperature scope in addition, its type of feed also can produce very big influence to rectifying.
Summary of the invention
The object of the present invention is to provide a kind of reaction and rectification device and method that dimethoxym ethane separates purification that be used for, it is reaction and separates the novel intermittent formula reactive distillation mode of operation and the implementation method of purifying and being coupled.Reaction raw materials formaldehyde adds from rectifying tower top, in tower, forms the excessive state of formaldehyde, is beneficial to reaction and carries out to the positive reaction direction, and can destroy the azeotropic of methyl alcohol and dimethoxym ethane, reduces separating difficulty, improves the concentration of dimethoxym ethane in the product.Dimethoxym ethane loops back reactor with methyl alcohol, water at the bottom of the tower, improves the material benzenemethanol conversion ratio.Applicability of the present invention is strong, can improve the range of application of reactive distillation.
A kind of reaction and rectification device that is used for dimethoxym ethane separation purification provided by the invention mainly comprises: reactor and agitator, and rectifying column, condenser, reflux ratio controller, stainless steel helices, thermometer, pressure gauge, product is collected holding vessel.
Connected mode is following: be connected through feed-line (two strands of logistics pipelines) between the reactor that agitator is housed and the rectifying column, reactor provides gas feed to rectifying column, and liquid loops back reactor at the bottom of the rectifying column; Load θ (3 * 3) stainless steel helices in the rectifying column, cat head is provided with condenser, reflux ratio controller and product and collects holding vessel, and cooling medium is a water, is connected with temperature at the bottom of reactor, the rectifying Tata and takes into account pressure gauge.
Course of reaction of the present invention is employed in the mode that rectifying column carries out outward, and in the disposable whole adding agitated reactors of material benzenemethanol, formaldehyde adds from rectifying tower top, through getting into reactor at the bottom of the tower, has improved reaction rate and raw material availability; The rectifying separation process adopts the mode of tower spirit body charging, and liquid loops back reactor at the bottom of the tower simultaneously, selects suitable reflux ratio in the operation, and specific operation process and conventional rectification do not have obvious difference.
A kind of concrete operations step that is used for the method for dimethoxym ethane separation purification provided by the invention comprises:
(1) methyl alcohol joins in the reactor through the methyl alcohol feed-line is disposable, and the control reactor temperature is 20～70 ℃, pressure 0.08～0.12MPa;
(2) formaldehyde continues to add from rectifying tower top through the flow rate of formaldehyde feed-line with 5～20ml/min, goes out to get into reactor from tower bottom flow behind the whole tower of flowing through;
(3) the product dimethoxym ethane gets into rectifying column through the logistics feed-line with the form of gas at the bottom of tower; In the uphill process with overhead streams under formaldehyde contact; Destroy methyl alcohol and dimethoxym ethane azeotropism, it is 2～5 that reflux ratio is set, the separation purification process of beginning dimethoxym ethane;
(4) open valve, cat head extraction purity is 90～95% dimethoxym ethane, is collected into the overhead product storage tank, and liquid loops back reactor through the logistics feed-line at the bottom of the tower, and the control tower top temperature is at 40～42 ℃;
(5) (the formaldehyde addition was pressed reaction than decision by initial methanol feeding amount after the formaldehyde charging finished; The volume ratio of methyl alcohol and formaldehyde is about 2～4); Rectifying column gets into the Methanol Recovery stage, closes second valve and opens the 3rd valve simultaneously, and the control tower top temperature is at 63～66 ℃.Overhead product gets into the Methanol Recovery jar, gives over to next intermittent feeding;
(6) methanol concentration drops at 10%～15% o'clock in the reactor, stops this batch process, opens first valve residual solution in the reactor is discharged, and concentration of formaldehyde is lower than 0.1% in the residual solution, allow compliance with emission standards;
(7) intermittently operated is next time prepared in charging again.
The present invention has adopted the mode of operation of outside the rectifying separation tower, reacting.Each batch process is reflected at rectifying column and carries out outward, and wherein material benzenemethanol once adds from reactor; Formaldehyde adds with certain speed from rectifying tower top, and the product dimethoxym ethane gets into rectifying column with gas form at the bottom of tower, realizes separating; Cat head extraction product, solution loops back reactor at the bottom of the tower.After finishing the formaldehyde charging, the extraction of dimethoxym ethane product finishes, and rectifying column continues to separate purification methyl alcohol, supplies next to recycle, thereby has improved raw material availability.The mode of operation that cat head advances formaldehyde can solve because methyl alcohol and dimethoxym ethane azeotropic cause product purity not reach the problem of requirement; Reactor residual solution concentration of formaldehyde allow compliance with emission standards; Reaction separates that the mode of operation of carrying out can overcome because reaction and the inconsistent adverse effects of bringing such as restive, catalyst filling difficulty of separation condition with separating, thereby the operation easier that reduces reactive distillation enlarges its range of application.
In a word; The present invention has broken through the limitation that existing reactive distillation requirement reaction and rectifying are carried out in same tower, reaction raw materials formaldehyde adds from rectifying tower top, in tower, forms the excessive state of formaldehyde; Being beneficial to reaction carries out to the positive reaction direction; And can destroy the azeotropic of methyl alcohol and dimethoxym ethane, reduce separating difficulty, improve the concentration of dimethoxym ethane in the product.Dimethoxym ethane loops back reactor with methyl alcohol, water at the bottom of the tower, improves the material benzenemethanol conversion ratio.Applicability of the present invention is strong, can improve the range of application of reactive distillation.The present invention can be under the prerequisite that guarantees higher reaction yield and product purity, cuts down the consumption of energy and controls difficulty, saves equipment investment and operating cost, brings considerable economic well-being of workers and staff.
Description of drawings
Fig. 1 is the Experimental equipment of this specification.
Fig. 2 is a dimethoxym ethane extraction stage cat head dimethoxym ethane mass fraction change curve in time.
Fig. 3 is a Methanol Recovery stage cat head methanol quality mark change curve in time.
The specific embodiment
In conjunction with in the accompanying drawing the present invention being elaborated.
As shown in the figure, the 1-methanol feeding; The charging of 2-formaldehyde; The 3-reactor; The 4-condenser; 5-dimethoxym ethane feed-line; Withdrawing fluid at the bottom of the 6-tower; The 7-rectifying column; First valve, 8, the second valves, 9, the three valves 10 are the pipe-line control valve door; The 11-reflux pump.Load θ (3 * 3) stainless steel helices in the rectifying column, theoretical cam curve is about 30～40.
The device parameter that adopts in the experiment: reactor and agitating device (D2025W electric mixer), rectifying column (glass tower, tower height 3000mm; Tower diameter 30mm; Theoretical cam curve is about 30～40), condenser, reflux ratio controller (XMTD-908 type); Temperature, pressure measxurement (U manages differential manometer) device, product is collected holding vessel (glass tank volume 1000ml).Product is formed employing gas chromatograph (the Shandong SP6802 of southern Shandong chemical industry Co., Ltd type) and is carried out determination and analysis.
Connected mode of each device is following: through 5,6 connections of two strands of logistics pipelines, reactor provides gas feed 5 to rectifying column between the reactor 3 that agitating device is housed and the rectifying column 7, and liquid 6 loops back reactor at the bottom of the rectifying column; Load θ (3 * 3) stainless steel helices in the rectifying column, cat head is provided with condenser 4, reflux ratio controller and product and collects holding vessel 12,13, and cooling medium is a water, is connected with temperature and device for pressure measurement at the bottom of reactor, the rectifying Tata.
Concrete operating procedure comprises:
(1) 1500ml methyl alcohol is through methyl alcohol feed-line 1 disposable joining in the reactor, and the control reactor temperature is 20～70 ℃, pressure 0.08～0.12MPa;
(2) formaldehyde continues to add from rectifying tower top through the flow rate of formaldehyde feed-line 2 with 5～20ml/min, goes out to get into reactor from tower bottom flow behind the whole tower of flowing through;
(3) the product dimethoxym ethane gets into rectifying column through mass transport pipeline 5 with the form of gas at the bottom of tower; In the uphill process with overhead streams under formaldehyde contact; Destroy methyl alcohol and dimethoxym ethane azeotropism, it is 2～5 that reflux ratio is set, the separation purification process of beginning dimethoxym ethane;
(4) open valve 9, cat head extraction purity is 90～95% dimethoxym ethane, is collected into overhead product storage tank 12, and liquid loops back reactor through logistics feed-line 6 at the bottom of the tower, and control cat head temperature maintenance is at 40～42 ℃;
(5) the formaldehyde charging finishes back (the formaldehyde addition by the decision of reaction ratio, is about 500ml by initial methanol feeding amount in this experiment), and rectifying column gets into the Methanol Recovery stage, and valve-off 9 is opened valve 10 simultaneously, and the control tower top temperature is at 63～66 ℃.Overhead product gets into Methanol Recovery jar 13, gives over to next intermittent feeding;
(6) methanol concentration drops at 10%～15% o'clock in the reactor, stops this batch process, opens valve 8 residual solution in the reactor is discharged, and concentration of formaldehyde is lower than 0.1% in the residual solution, allow compliance with emission standards;
(7) intermittently operated is next time prepared in charging again.
The product composition adopts gas chromatograph to analyze, and analysis condition is following:
Capillary chromatographic column: column length 30m, internal diameter 0.32um, external diameter 0.5um;
Combustion gas: hydrogen; Combustion-supporting gas: air; Carrier gas: nitrogen;
Gasification temperature: 150 ℃; Column temperature: 100 ℃; Detected temperatures: 150 ℃.
Result and discussion
(1) be reflected at rectifying column and carry out outer intermittence, the filling of catalyst and dismounting are than being easier to, making things convenient for; Formaldehyde is from the cat head charging, and circulating fluid improves utilization ratio of raw materials at the bottom of the tower; Concentration of formaldehyde satisfies discharge standard in the interior residual solution of reaction end post-reactor;
(2) rectifying column only needs 30 blocks of column plates, does not need traditional conversion zone in the tower, accomplishes product and separates the recovery of purification continued as methyl alcohol, reduces the investment goods expense and also can cut down the consumption of energy;
(3) formaldehyde destroys the azeotropic of methyl alcohol and dimethoxym ethane from the cat head charging, and the purity of overhead product dimethoxym ethane can reach more than 96%, and the continuous extraction product of cat head dimethoxym ethane promotes that reaction forward moves, and has improved reaction rate, and the utilization rate of formaldehyde is near 100%; After reaction finished, rectifying column was used to separate purification methyl alcohol, and the methyl alcohol yield can reach 97～98%; Dimethoxym ethane product extraction stage cat head dimethoxym ethane mass fraction in time change curve and Methanol Recovery stage cat head methyl alcohol change curve is respectively as shown in Figures 2 and 3 in time;
(4) adopt this mode of operation, the mutual restriction property of course of reaction and separation process is very little, is easy to control; The adaptable reaction type of reactive distillation is expanded, the also corresponding reduction of operation easier.
Claims (2)
1. one kind is used for the method that dimethoxym ethane separates purification, and its reaction and rectification device mainly comprises: reactor and agitator, and rectifying column, condenser, reflux ratio controller, stainless steel helices, thermometer, pressure gauge, product is collected holding vessel; Be connected through feed-line between the reactor that agitator is housed and the rectifying column, reactor provides gas feed to rectifying column, and liquid loops back reactor at the bottom of the rectifying column; Load θ (3 * 3) stainless steel helices in the rectifying column, cat head is provided with condenser, reflux ratio controller and product and collects holding vessel, and cooling medium is a water, is connected with temperature at the bottom of reactor, the rectifying Tata and takes into account pressure gauge; It is characterized in that the step that it comprises:
(1) methyl alcohol joins in the reactor through the methyl alcohol feed-line is disposable, and the control reactor temperature is 20～70 ℃, pressure 0.08～0.12MPa;
(2) formaldehyde continues to add from rectifying tower top through the flow rate of formaldehyde feed-line with 5～20ml/min, goes out to get into reactor from tower bottom flow behind the whole tower of flowing through;
(3) the product dimethoxym ethane gets into rectifying column through the logistics feed-line with the form of gas at the bottom of tower; In the uphill process with overhead streams under formaldehyde contact; Destroy methyl alcohol and dimethoxym ethane azeotropism, it is 2～5 that reflux ratio is set, the separation purification process of beginning dimethoxym ethane;
(4) open valve, cat head extraction purity is 90～95% dimethoxym ethane, is collected into the overhead product storage tank, and liquid loops back reactor through the logistics feed-line at the bottom of the tower, and the control tower top temperature is at 40～42 ℃;
(5) after the formaldehyde charging finished, rectifying column got into the Methanol Recovery stage, closed second valve and opened the 3rd valve simultaneously, and the control tower top temperature is at 63～66 ℃, and overhead product gets into the Methanol Recovery jar, gives over to next intermittent feeding;
(6) methanol concentration drops at 10%～15% o'clock in the reactor, stops this batch process, opens first valve residual solution in the reactor is discharged, and concentration of formaldehyde is lower than 0.1% in the residual solution, allow compliance with emission standards;
(7) intermittently operated is next time prepared in charging again.
2. according to the described method of claim 1, the volume ratio that it is characterized in that described methyl alcohol and formaldehyde is 2～4.
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| CN2010105893599A CN102068945B (en) | 2010-12-15 | 2010-12-15 | Reactive distillation device and method for separating and purifying methylal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102423539B (en) * | 2011-09-05 | 2013-12-11 | 天津大学 | Energy-saving technology of catalytic reaction distillation process and device thereof |
| CN103908898A (en) * | 2013-01-07 | 2014-07-09 | 吕晓龙 | Composite hollow fiber film and making method thereof |
| CN107986947A (en) * | 2017-12-28 | 2018-05-04 | 四川鑫达新能源科技有限公司 | A kind of dimethoxym ethane heat integration synthesis system and preparation method |
| CN108424358B (en) * | 2018-05-22 | 2023-12-26 | 凯瑞环保科技股份有限公司 | Device and method for producing high-purity methylal by utilizing catalytic distillation coupling technology |
| CN113041636A (en) * | 2019-12-27 | 2021-06-29 | 浙江省化工研究院有限公司 | Continuous bromination addition reaction rectification process and device |
| CN111747828B (en) * | 2020-07-23 | 2023-05-26 | 浙江皇马科技股份有限公司 | Preparation method and system of ethylene glycol monopropyl ether |
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|---|---|---|---|---|
| US6713656B2 (en) * | 2001-10-05 | 2004-03-30 | Basf Aktiengesellschaft | Preparation of diacetals of glyoxal |
| CN1807378A (en) * | 2006-01-26 | 2006-07-26 | 南京师范大学 | Method for preparing methylal using combined continuous distillation and liquid-liquid extraction |
| CN101786946A (en) * | 2010-04-01 | 2010-07-28 | 江苏恒茂机械制造有限公司 | Methylal preparation device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19617210A1 (en) * | 1996-04-30 | 1997-11-06 | Basf Ag | Partition wall column for the continuous separation of multi-component mixtures by distillation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6713656B2 (en) * | 2001-10-05 | 2004-03-30 | Basf Aktiengesellschaft | Preparation of diacetals of glyoxal |
| CN1807378A (en) * | 2006-01-26 | 2006-07-26 | 南京师范大学 | Method for preparing methylal using combined continuous distillation and liquid-liquid extraction |
| CN101786946A (en) * | 2010-04-01 | 2010-07-28 | 江苏恒茂机械制造有限公司 | Methylal preparation device |
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