CN202376971U - Tubular continuous esterification reaction device for synthesizing dicarboxylic ester - Google Patents
Tubular continuous esterification reaction device for synthesizing dicarboxylic ester Download PDFInfo
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- CN202376971U CN202376971U CN2011205034468U CN201120503446U CN202376971U CN 202376971 U CN202376971 U CN 202376971U CN 2011205034468 U CN2011205034468 U CN 2011205034468U CN 201120503446 U CN201120503446 U CN 201120503446U CN 202376971 U CN202376971 U CN 202376971U
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- 238000005886 esterification reaction Methods 0.000 title claims abstract description 25
- 150000002148 esters Chemical class 0.000 title claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 238000010992 reflux Methods 0.000 claims abstract description 20
- 238000003860 storage Methods 0.000 claims abstract description 11
- 230000032050 esterification Effects 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 14
- 238000011049 filling Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 150000001735 carboxylic acids Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005485 electric heating Methods 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 208000012826 adjustment disease Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The tubular continuous esterification reaction device for synthesizing the dicarboxylic ester is applied to the preparation of the continuous esterification reaction for synthesizing the dicarboxylic ester by using the C1-C4 low-carbon alcohol. The tower kettle is connected with the outlet of the tubular reactor, the outlet of the tubular reactor is connected with the lower outlet of the reflux tower, and the upper outlet of the reflux tower is connected with the inlet of the tower head; the tower head outlet is connected with the first condenser; the reflux device is connected with the outlet of the first condenser, and the outlet of the reflux device is connected with the inlet of the waste alcohol receiving tank; the outlet of the dicarboxylic acid raw material tank is connected with the inlet of a first feeding pump, the outlet of the first feeding pump is connected with a first preheater, the outlet of the low-carbon alcohol raw material tank is connected with the inlet of a second feeding pump, the outlet of the second feeding pump is connected with a second preheater, the outlet of the bottom of the tower kettle is connected with the inlet of a second condenser, and the outlet of the second condenser is connected with a product storage tank. The effect is as follows: the reflux of the reflux tower reduces the loss of the target product dicarboxylic ester and improves the product yield. Continuous operation is realized, and the conversion rate reaches more than 99 percent.
Description
Technical field
The utility model relates to the reaction unit field that the preparation carboxylate is used, and particularly is used for the tubular type continuous esterification device of the synthetic dicarboxylic esters of dicarboxylic acids and C1-C4 low-carbon alcohols.
Background technology
Dicarboxylic esters such as succinate, glutarate is a colourless transparent liquid, is soluble in alcohol, ether, and is water insoluble, be widely used as to produce solvent and plasticizer, and be important organic synthesis raw material.It is raw material esterification prepared in reaction that dicarboxylic esters generally adopts with carboxylic acid and alcohol, and reaction principle is the hydroxyl hydrogen atom in the pure molecule is generated ester again under the catalyst action by acyl substituted reaction.This reaction belongs to the irreversible thermodynamic balanced reaction, in course of reaction, deviates to help to promote reaction to carry out to positive direction continuously in the water in the product.
At present; The tradition esterification technique is as catalyst with liquid mineral acid such as sulfuric acid, nitric acid; In the still reaction still, carry out intermittent reaction; Promptly in the reaction kettle of the esterification of certain volume, drop into dicarboxylic acids, alcohol and catalyst, under uniform temperature and pressure, carry out esterification, generate dicarboxylic esters and water byproduct.Water byproduct is taken out of through the alcohol evaporation, and alcohol and steam use water quench to carry out rectifying for thick alcohol gets into pure distillation process, when reactant mixture reaches the acid number of regulation, stop heating, and product is emitted, and drop into raw material in the agitated reactor again and carry out the next group reaction again.For example the disclosed process of BP (GB143069) is: use the concentrated sulfuric acid as catalyst, adopt the tank reactor reaction, the method for distillation dewaters.This kind technology esterification is carried out not exclusively, and the conversion rate of esterification of dicarboxylic acids is not high, the highlyest only can reach 60-70%, also has the problem of environmental pollutions such as three wastes processing of inorganic acid serious to corrosion on Equipment in product.Deutsche Bundespatent (DE19610564) is disclosed to be a plurality of tank reactor series connection, is reflected under the stirring condition and carries out, and technological operation is complicated, and equipment investment is bigger.World patent (WO9008127) is disclosed to be that tubular reactor inside is divided into a plurality of beds, and the solid catalyst loosely is contained in the bed, and pure steam reaches with acid, solid catalyst with the mode of bubbling in acid solution and contacts, and under certain pressure, reacts.But the reactor of this kind technology has a plurality of beds, and catalyst filling and replacing operation are more loaded down with trivial details.
The utility model content
The purpose of the utility model is: a kind of tubular type continuous esterification device of synthetic dicarboxylic esters is provided, is used for the synthetic dicarboxylic esters of dicarboxylic acids and low-carbon alcohols.
The technical scheme that the utility model adopts is: the tubular type continuous esterification device of synthetic dicarboxylic esters comprises tower still, tubular reactor, reflux column, tower head, first condenser, second condenser, return channel, useless pure receiving tank, dicarboxylic acids head tank, low-carbon alcohols head tank, product storage tank, first feed pump, second feed pump, first preheater and second preheater.It is characterized in that: the tower still exports down with tubular reactor and links to each other; The outlet of tubular reactor upper end exports down with reflux column and links to each other; The reflux column upper outlet links to each other with the tower head import; Reflux column is used for the backflow of the product dicarboxylic esters that the moisture low carbon alcohol vapor of continuous esterification process carries secretly in uphill process, to reduce the loss of purpose product dicarboxylic esters; The tower head outlet at bottom links to each other with first condenser, and first condenser is used for the condensing and recycling that the continuous esterification process distills out the moisture useless alcohol of thing, and return channel links to each other with first condensator outlet, and the return channel outlet links to each other with useless pure receiving tank inlet; The outlet of dicarboxylic acids head tank links to each other with first feed pump inlet; The first charging delivery side of pump links to each other with first preheater; The outlet of low-carbon alcohols head tank links to each other with second feed pump inlet; The second charging delivery side of pump links to each other with second preheater, and tower still outlet at bottom links to each other with second condenser inlet, and second condensator outlet links to each other with the product storage tank.
Described tower still is that product receives still.The tower still is provided with liquid level sensor and electric heating bag heater, and the bottom of tower still has the product sample tap.Be connected with magnetic valve on the pipeline between second condensator outlet and the product storage tank, regulate tower still product discharge rate, the liquid level equilibrium of control tower still through magnetic valve.
Described tubular reactor is a jacket type electrical heat tracing reactor; Adopt single bed structure; Catalyst filling part is equipped with in inside, and the tubular reactor top has catalyst filler and carboxylic acid material inlet, and the tubular reactor bottom has catalyst discharge port and low-carbon alcohols charging aperture.
Described first condenser and second condenser are to adopt jacket structured heat transfer unit (HTU), are the cooling heat transferring medium in the chuck.
Described dicarboxylic acids is aliphatic or the aromatic binary carboxylic acid of C2～C10.Described low-carbon alcohols is the aliphatic low-carbon alcohols of C1～C4.
The beneficial effect of the utility model: the tubular type continuous esterification device of the synthetic dicarboxylic esters of the utility model; Adopt single bed tubular reactor; Catalyst filling part is equipped with in inside, is used for the filling of catalyst, can solve in the course of reaction owing to bed pressure drop and the big problem that general tower takes place of resistance; And fully contact at catalyst surface when making the dicarboxylic acids raw material with low-carbon alcohols raw material adverse current, to reach the optimum response effect.Reduce the loss of purpose product dicarboxylic esters through the reflux column backflow, thereby improve product yield.Can continuous feed in the course of reaction and discharging continuously, realized the continuity operation, and can take a sample at any time and survey the product acid number, according to the timely parameters such as adjustment reaction temperature and charging rate of acid number size, with the acquisition maximum conversion.This reaction unit carboxylic acid conversion ratio can reach more than 99%, simple to operate, quick detachable, be prone to clean, environmental pollution is little, is easier to realize suitability for industrialized production.
Description of drawings
Fig. 1 is the tubular type continuous esterification apparatus structure generalized section of the synthetic dicarboxylic esters of the utility model.
Among the figure, 1-tower still, 2-tubular reactor, 3-reflux column, 4-tower head, 5-first condenser; 6-second condenser, 7-return channel, the 8-pure receiving tank that gives up, 9-dicarboxylic acids head tank, 10-low-carbon alcohols head tank; 11-product storage tank, 12-first feed pump, 13-second feed pump, 14-first preheater, 15-second preheater; The 16-liquid level gauge, 17-dicarboxylic acids charging aperture, 18-low-carbon alcohols charging aperture, 19-electric heating bag heater, 20-product sample tap; The 21-magnetic valve, 22-catalyst filling part, 23-catalyst filler, 24-catalyst discharge port, 25-backflow form.
The specific embodiment
Embodiment 1: the tubular type continuous esterification device with a synthetic dicarboxylic esters is an example, and the utility model is done further explain.
Consult Fig. 1.The tubular type continuous esterification device of the synthetic dicarboxylic esters of the utility model comprises tower still 1, tubular reactor 2, reflux column 3, tower head 4, first condenser 5, second condenser 6, return channel 7, useless pure receiving tank 8, dicarboxylic acids head tank 9, low-carbon alcohols head tank 10, product storage tank 11, first feed pump 12, second feed pump 13, first preheater 14 and second preheater 15.
Tower still 1 is that product receives still, and tower still 1 is provided with liquid level sensor 16 and electric heating bag heater 19, and the bottom of tower still 1 has product sample tap 20.Be connected with magnetic valve 21 on the pipeline between 6 outlets of second condenser and the product storage tank 11.2 times outlets of tower still 1 and tubular reactor link to each other; Tubular reactor 2 is jacket type electrical heat tracing reactors; Adopt single bed structure; Catalyst filling part 22 is equipped with in inside, and tubular reactor 2 tops have catalyst filler 23 and carboxylic acid material inlet 17, and tubular reactor 2 bottoms have catalyst discharge port 24 and low-carbon alcohols charging aperture 18.The outlet of tubular reactor 2 upper ends links to each other with 3 times outlets of reflux column, and reflux column 3 upper outlets link to each other with tower head 4 imports; Tower head 4 outlet at bottoms link to each other with first condenser 5; Return channel 7 links to each other with 5 outlets of first condenser, and return channel 7 outlets link to each other with useless pure receiving tank 8 inlets; 9 outlets of dicarboxylic acids head tank link to each other with first feed pump, 12 inlets; The outlet of first feed pump 12 links to each other with first preheater 14; 10 outlets of low-carbon alcohols head tank link to each other with second feed pump, 13 inlets; The outlet of second feed pump 13 links to each other with second preheater 15, and tower still 1 outlet at bottom links to each other with second condenser, 6 inlets, and 6 outlets of second condenser link to each other with product storage tank 11.
First condenser 5 and second condenser 6 are to adopt jacket structured heat transfer unit (HTU), are the cooling heat transferring medium in the chuck.
The technological operation flow process of the tubular type continuous esterification device of synthetic dicarboxylic esters is following: consult Fig. 1.Strong acid cation exchange resin catalyst is loaded in the tubular reactor 2; Tower still 1, tubular reactor 2, first preheater 14, preheater 15 are warmed up to assigned temperature respectively; First condenser 5, second condenser, 6 logical cooling mediums, second feed pump 13 is opened in return channel 7 control infinite refluxs; Observing has when backflow to open first feed pump 12 in the backflow form 25, return channel 7 control reflux ratios.
The process condition scope of dicarboxylic acids and low-carbon alcohols continuous esterification is following: low-carbon alcohols is 1.5: 1～3.0: 1 with dicarboxylic acids charging rate ratio; Low-carbon alcohols charging rate 100-500g/h; 105～120 ℃ of tower still control temperature; 110～130 ℃ of tubular reactor control temperature, 90～100 ℃ of preheater control temperature.
Claims (4)
1. the tubular type continuous esterification device of a synthetic dicarboxylic esters comprises tower still (1), tubular reactor (2), reflux column (3), tower head (4), first condenser (5), second condenser (6), return channel (7), useless pure receiving tank (8), dicarboxylic acids head tank (9), low-carbon alcohols head tank (10), product storage tank (11), first feed pump (12), second feed pump (13), first preheater (14) and second preheater (15); It is characterized in that: tower still (1) and tubular reactor (2) outlet down link to each other, export under the outlet of tubular reactor (2) upper end and the reflux column (3) to link to each other, and reflux column (3) upper outlet links to each other with tower head (4) import; Tower head (4) outlet at bottom links to each other with first condenser (5); Return channel (7) links to each other with first condenser (5) outlet, and return channel (7) outlet links to each other with useless pure receiving tank (8) inlet; Dicarboxylic acids head tank (9) outlet links to each other with first feed pump (12) inlet; The outlet of first feed pump (12) links to each other with first preheater (14); Low-carbon alcohols head tank (10) outlet links to each other with second feed pump (13) inlet; The outlet of second feed pump (13) links to each other with second preheater (15), and tower still (1) outlet at bottom links to each other with second condenser (6) inlet, and second condenser (6) outlet links to each other with product storage tank (11).
2. the tubular type continuous esterification device of synthetic dicarboxylic esters according to claim 1; It is characterized in that: described tower still (1) is that product receives still; Tower still (1) is provided with liquid level sensor (16) and electric heating bag heater (19), and the bottom of tower still (1) has product sample tap (20); Be connected with magnetic valve (21) on the pipeline between second condenser (6) outlet and the product storage tank (11).
3. the tubular type continuous esterification device of synthetic dicarboxylic esters according to claim 1; It is characterized in that: described tubular reactor (2) is a jacket type electrical heat tracing reactor; Adopt single bed structure; Catalyst filling part (22) is equipped with in inside, and tubular reactor (2) top has catalyst filler (23) and carboxylic acid material inlet (17), and tubular reactor (2) bottom has catalyst discharge port (24) and low-carbon alcohols charging aperture (18).
4. the tubular type continuous esterification device of synthetic dicarboxylic esters according to claim 1 is characterized in that: described first condenser (5) and second condenser (6) are to adopt jacket structured heat transfer unit (HTU), are the cooling heat transferring medium in the chuck.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011205034468U CN202376971U (en) | 2011-12-06 | 2011-12-06 | Tubular continuous esterification reaction device for synthesizing dicarboxylic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011205034468U CN202376971U (en) | 2011-12-06 | 2011-12-06 | Tubular continuous esterification reaction device for synthesizing dicarboxylic ester |
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| Publication Number | Publication Date |
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| CN202376971U true CN202376971U (en) | 2012-08-15 |
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| CN2011205034468U Expired - Lifetime CN202376971U (en) | 2011-12-06 | 2011-12-06 | Tubular continuous esterification reaction device for synthesizing dicarboxylic ester |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107021889A (en) * | 2017-06-08 | 2017-08-08 | 联化科技（台州）有限公司 | The preparation method and device of a kind of aromatic chlorinated thing |
| CN114749111A (en) * | 2022-04-21 | 2022-07-15 | 云南电网有限责任公司电力科学研究院 | Reactor for testing hydrogen absorption and desorption performance of organic liquid hydrogen storage material |
-
2011
- 2011-12-06 CN CN2011205034468U patent/CN202376971U/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107021889A (en) * | 2017-06-08 | 2017-08-08 | 联化科技（台州）有限公司 | The preparation method and device of a kind of aromatic chlorinated thing |
| CN114749111A (en) * | 2022-04-21 | 2022-07-15 | 云南电网有限责任公司电力科学研究院 | Reactor for testing hydrogen absorption and desorption performance of organic liquid hydrogen storage material |
| CN114749111B (en) * | 2022-04-21 | 2024-03-19 | 云南电网有限责任公司电力科学研究院 | Reactor for testing hydrogen absorption and desorption performance of organic liquid hydrogen storage material |
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| Date | Code | Title | Description |
|---|---|---|---|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20120815 |