CN105693514A - Continuous production system and production method of polyalcohol low-carbon carboxylate ester - Google Patents
Continuous production system and production method of polyalcohol low-carbon carboxylate ester Download PDFInfo
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Abstract
The invention provides a continuous production system and a production method of polyalcohol low-carbon carboxylate ester. Polyalcohol (such as ethylene glycol, propylene glycol and glycerin) and low-carbon carboxylic acid (such as acetic acid and propionic acid) serve as raw materials, an azeotropic agent is adopted for dehydration, strong acid is adopted as a catalyst, a segmented esterification rectifying tower and a plurality of esterification autoclaves connected in series form an esterification distillation system, and a continuous production technology for producing corresponding ester is achieved.
Description
Technical field
The present invention relates to the continuous production technology of the low-carbon (LC) carboxylate of polyhydric alcohol, and be suitable for the ester of different polyhydric alcohol and different low-carbon (LC) carboxylic acids and the continuous prodution of their mixed ester。
Background technology
Different polyhydric alcohol is (such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, neopentyl glycol, tetramethylolmethane etc.) and different low-carbon (LC) carboxylic acid (acetic acid, propanoic acid etc.) the low-carbon (LC) carboxylate (including the ester of part not exclusively ester and mixed alcohol or mixed acid) of a variety of polyhydric alcohol can be synthesized, constitute the esters product cluster of a huge intermediate molecular weight, belong to nontoxic (or low toxicity), low volatility, the environment-friendly materials of easily biological-degradable, and its boiling point, lipophile, hydrophilic and the intermiscibility with various macromolecular materials are respectively arranged with feature。Along with the purposes of macromolecular material particularly bio-based macromolecular material is more and more extensive, kind increases, yield expands, and the kind of required corresponding solvent and plasticizer and quantity are also increasing。And macromolecular material as different purposes time solvent or plasticizer are also had the requirement differed, therefore the various esters of polyhydric alcohol there has also been corresponding market prospect。
Traditional production method of these esters adopts batch production method: add esterifying kettle with excessive sour and a certain proportion of polyhydric alcohol, with strong acid (such as sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid or solid acid etc.) for catalyst, and adding the method that water entrainer adopts azeotropic distillation, the water removing reaction generation completes esterification。In order to avoid introducing impurity, water entrainer generally can be selected for the corresponding ester of starting carboxylic acid, such as n-propyl acetate (or butyl acetate), ethyl propionate, they azeotropic points with water are 82.4 DEG C, 81.2 DEG C respectively, easily separate (azeotropic point and sour boiling-point difference are followed successively by 35.6 DEG C, 59.9 DEG C) with acid, and in azeotropic component, the composition of water is 14%, 10% successively, and the dissolubility in water is all less, all can reach the effect of good azeotropic dehydration, complete corresponding esterification, obtain thick finished product。Thick finished product obtains finished product through deacidification, neutralization, rectification (or deacidification, neutralization, dehydration, filtration)。For alcohol more than trihydroxylic alcohol and ternary, due to the existence of steric hindrance, separately need to add the esterification of corresponding anhydride (acetas acetic anhydride, the propionic ester propionic andydride) degree of depth, then obtain highly purified product。
When adopting batch production method, it is generally adopted the method that carboxylic acid is excessive。Partly in order to polyhydric alcohol relatively complete (for primary alconol, esterification degree can reach more than 99%) can be made, simultaneously because the boiling point of carboxylic acid is much lower compared with its ester, therefore easily separate from product。In batch process produces, the esterification incipient stage is all higher due to the concentration of acid and polyhydric alcohol, response speed quickly, generally just can complete the reaction of 80%, along with the response time elapses backward with the time of the 25% of whole esterification, the concentration of acid is relatively low, the concentration of unreacted alcohol is then more and more lower, and response speed is increasingly slower, and the water of generation is fewer and feweri, in order to reach the product purity that polyhydric alcohol makes full use of and is satisfied with, it is necessary to the increase response time ensures the degree of depth of reaction。Response time length, investment is many, utilization rate of equipment and installations is low, yield is little is the big shortcoming of one。
Batch process produces the water removal reaction system that another problem is that along with major part esterification generates of low-carbon (LC) carboxylate, and the always loss of some water entrainer, sometimes for supplementary part water entrainer in bigger reaction system。Amount owing to reacting deuterogenic water is little, and the flow minimizing of tower can reduce the separation efficiency of tower。Therefore the flow that must keep of a relatively high just can make overhead condensed fluid can have good oil-water separation, and ensure the carboxylic acid concentration in aqueous phase relatively low reach acceptable level (because water in water entrainer can reclaim, acid therein then cannot be reclaimed)。Therefore, at the later stage of reaction, though the ratio that the degree of esterification of increase accounts for whole esterification degree is little, but energy expenditure occupies very big ratio, and energy consumption height is the maximum shortcoming that batch process produces。
External Kening Co., Ltd adopts tower rectification esterification to produce thriacetic acid glycerine ester, namely the glycerol of preheated 99.5% is added at the upper middle part of tower, acetic acid is being added at the bottom of tower, at the water that tower top generates by water entrainer separation esterification, glycerol contacts with acetic acid from top to bottom, step-reaction is obtaining the triacetate of glycerol, diacetate esters and monoacetate at the bottom of tower, obtain highly purified esterification finished product then through the esterification of the acetic anhydride degree of depth。But to be tower significantly high and investment big for the shortcoming of the method, and the degree of esterification of early stage is relatively low, and it is higher that product per ton need to consume acetic anhydride, the batch process being conventional at present consumes 5-8 times of acetic anhydride quantity。Owing to acetic anhydride price is usually about 2 times of acetic acid, and its esterification mark is only 1.18 times of acetic acid, therefore adds production cost, can be greatly increased production cost oneself not producing in the enterprise of acetic anhydride。
Summary of the invention
The present invention is directed to the deficiencies in the prior art, provide and a kind of solve existing batch process and produce that the device efficiency of low-carbon (LC) polyol carboxylic acid ester is low, yield is little, energy consumption crosses the shortcomings such as height, it is achieved the continuous production system of the low-carbon (LC) carboxylate of the polyhydric alcohol of the continuous prodution that energy-efficient and DCS controls and operational approach thereof。
For realizing the object of the invention, provide techniques below scheme: the continuous production system of the low-carbon (LC) carboxylate of a kind of polyhydric alcohol, including at least 3 esterifying kettles sequentially concatenated that esterification tower is connected with esterification tower bottom discharging opening, it is characterized in that described esterification tower is made up of three, upper, middle and lower tower joint, upper tower joint is provided with water preparation backflow distributor in top, water entrainer backflow distributor pipeline connects the outlet of oil water separator epipelagic zone water preparation, and middle tower joint is provided with mixing gas charging aperture；Lower tower joint is the loss of essence water tower of carboxylic acid dehydration, and tower bottom is provided with water preparation charging aperture, is provided with heater at the bottom of lower Ta Jieta；Described esterification tower tower top is attached to condenser, oil water separator and esterification water recovery tower-, the azeotropic mixture outlet of esterification tower top connects condenser, condenser connects oil water separator, the outlet of oil water separator epipelagic zone water preparation connects the water entrainer charging aperture above the lower tower joint bottom discharging opening of the water entrainer backflow distributor in the upper tower joint top of esterification tower and nearly esterification tower respectively by pipeline, the outlet of oil water separator lower layer of water connects the esterification water import of esterification water recovery tower top, the azeotropic mixture outlet of esterification water recovery tower top connects oil water separator by recovery channel, esterification water recovery tower bottom discharge outlet connects sewage disposal system, the described esterifying kettle top mixed gas outlet pipeline sequentially concatenated connects the mixing gas charging aperture of tower joint in esterification tower。
Described esterification water recovery tower, refers to that tower top is with esterification water charging aperture, and tower top is water entrainer and water azeotropy rectification column, and tower bottom is the distillation column with heater or reboiler。
As preferably, becoming notch cuttype arrangement, form the difference in height being gradually lowered when the esterifying kettle sequentially concatenated is installed, the first esterifying kettle is the highest。
As preferably, esterifying kettle is set to 3 or 4。
As preferably, the first esterifying kettle top is connected to polyol starting material tank and catalyst basin, and the connection pipeline of esterification tower bottom discharging opening and the first esterifying kettle is provided with carboxylic acid basin。
As preferably, esterification tower bottom discharging opening is respectively provided with pipeline and connects each esterifying kettle。
As preferably, recovery channel being provided with condenser II。
As preferably, each esterifying kettle is provided with agitating device and heater。
For realizing the object of the invention, provide the production method of the continuous production system of a kind of low-carbon (LC) carboxylate utilizing polyhydric alcohol, it is characterized in that with polyhydric alcohol and low-carbon (LC) carboxylic acid for raw material, with strong acid for catalyst, with corresponding low-carbon (LC) carboxylate for water entrainer, deposit in case in excess carboxylic acid, in esterifying kettle, add catalyst, polyhydric alcohol and low-carbon (LC) carboxylic acid continuously, obtain thick finished product by the continuous production system of the low-carbon (LC) carboxylate of polyhydric alcohol, obtain qualified products then through post processing；
Described polyhydric alcohol includes ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, neopentyl glycol, tetramethylolmethane is a kind of or combines；
Described low-carbon (LC) carboxylic acid includes acetic acid, propanoic acid, formic acid or butyrate；
Described strong acid catalyst includes sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid or heteropoly acid；
Described excess carboxylic acid, refers to the carboxylic acid being previously added in esterifying kettle, the excessive esterification being conducive to alcohol in course of reaction of acid completely or reach higher value；
Described catalyst, polyhydric alcohol and low-carbon (LC) carboxylic acid, refer to and obtain the catalyst of corresponding proportion, polyhydric alcohol and the low-carbon (LC) carboxylic acid that target product (thick finished product) consumes；
Described post processing, refers to the process for refining such as deacidification, neutralization of general high boiling ester series products, dehydration, decolorization filtering or vacuum distilling；
Corresponding low-carbon (LC) carboxylate is water entrainer, refers to the ester of low-carbon (LC) carboxylic acid used。Such as produce the polynary acid alcohol acetas of acetic acid, it is preferable that n-propyl acetate or butyl acetate；Propanoic acid polyol ester propionic ester, it is preferable that ethyl propionate。
Technical scheme for a better understanding of the present invention, is below operation principle:
In the batch process of prior art produces, backflow bottom esterification column is owing to constantly contacting with the mixture of the carboxylic acid distilled in esterifying kettle and water, so can contain a certain amount of moisture in this backflow, being directly entered esterifying kettle will have a certain impact to esterification speed。In the present invention, this backflow continues to flow downward, the lower tower joint bottom discharging opening of nearly esterification tower is provided above water entrainer charging aperture, draw sub-fraction by the water entrainer in oil water separator and enter this water entrainer charging aperture, water entrainer upwards evaporates, contact with top-down carboxylic acid liquid, the moisture wherein contained is delivered to tower top, at the bottom of tower, obtaining the carboxylic acid that water content is very low。The carboxylic acid that this water content is very low is then sent through esterifying kettle and reacts, and greatly facilitates the carrying out of esterification。
Before system is driven, it is necessary to oil water separator injects a certain amount of water entrainer and water so that it is remain close to duty。In esterifying kettle, inject carboxylic acid, polyhydric alcohol, catalyst and quantitative water entrainer, a part of water (in order to quickly can form the azeotropic mixture of water entrainer and water at the very start at tower top) can also be added if desired。Carboxylic acid must be excessive, by calculating or empirically determined。Begin to warm up rear a period of time, the material of last still is extracted out and progressively circulates to the first esterifying kettle, until the material detection degree of esterification of last still makes it and can start discharging。Start to react to interstage of discharging, the liquid level according to each still, suitably supplement part carboxylic acid by a certain percentage and compound that polyhydric alcohol forms。
After discharging starts, being continuously added to the quantitative catalyst of certainty ratio, polynary alcohol and carboxylic acid, and add the carboxylic acid quantity that thick finished product is taken out of in the first esterifying kettle, after thick finished product deacidification is normal, the carboxylic acid deviate from enters esterifying kettle, gets final product normal operating。As required, the carboxylic acid of these additions, including from the moisture little carboxylic acid obtained at the bottom of tower, it is possible to all add the first esterifying kettle, it is also possible to separate a part and be separately added into each esterifying kettle below。
The method have the benefit that compared with producing with batch process, batch process when starting to react in order to form azeotropic on esterification tower top and make the carboxylic acid in aqueous phase drop to relatively low level to need the infinite reflux of long period；In early stage and the mid-term of reaction, batch process has moisture carboxylic acid to pass back into esterifying kettle, have impact on esterification speed；In the later stage of reaction, batch process is ensure that esterification tower tower top has moisture to go out and need to control bigger flow；For ensureing that esterification products purity needs long time。And this situation is to produce all necessary repetitive cycling every time。In the present invention, drive normal after, entering the carboxylic acid of esterifying kettle is all anhydrous or moisture seldom to keep except the first esterifying kettle except bigger flow, as long as after all less flow of each still, the distillation total amount that stable less flow greatly reduces；By rectifying column through water entrainer azeotropic dehydration together with the water that distillation generates with the first esterifying kettle after entering esterification tower, do not worry the operating mode appearance that profit layering is unclear。Thus save energy resource consumption significantly。
Adopting the present invention, the duty of esterifying kettle can control the good situation in the batch process early stage a certain stage always。Therefore, reach same yield compared with many set batch processes, the large-scale production that the project of the present invention is taken up an area less, construction area is little, equipment manufacturing cost is low, be easily achieved overall process DCS controls, recruitment number is greatly reduced, reduces every business administration expense。
Accompanying drawing explanation
Fig. 1 is the structural representation of embodiment 1。
Detailed description of the invention
Embodiment 1:A kind of continuous production system of the low-carbon (LC) carboxylate of polyhydric alcohol, including 3 esterifying kettles sequentially concatenated (2,3,4) that esterification tower 1 is connected with esterification tower 1 bottom discharging opening, described esterification tower 1 is made up of three, upper, middle and lower tower joint, upper tower joint 1.1 is provided with water preparation backflow distributor 1.1.1 in top, water entrainer backflow distributor 1.1.1 pipeline connects oil water separator 5 epipelagic zone water preparation outlet 5.1, and middle tower joint 1.2 is provided with mixing gas charging aperture 1.2.1；Lower tower joint 1.3 is the loss of essence water tower of carboxylic acid dehydration, and tower bottom is provided with water preparation charging aperture 1.3.1, and lower tower saves and is provided with heater 1.3.2 at the bottom of 1.3 towers；Described esterification tower 1 tower top is attached to condenser 6, oil water separator 5 and esterification water recovery tower-7, esterification tower 1 top azeotropic mixture outlet 1.4 connection condenser 6, condenser 6 connects oil water separator 5, oil water separator 5 epipelagic zone water preparation outlet 5.1 is connected the lower tower of the water entrainer backflow distributor 1.1.1 in upper tower joint 1.1 top of esterification tower 1 and nearly esterification tower 1 respectively and saves the water entrainer charging aperture 1.3.1 above 1.3 bottom discharging openings by pipeline, oil water separator 5 lower layer of water outlet 5.2 connection esterification water recovery tower 7 top esterification water import 7.1, esterification water recovery tower 7 top azeotropic mixture outlet 7.2 connects oil water separator 5 by recovery channel 8, esterification water recovery tower 7 bottom discharge outlet 7.3 connects sewage disposal system, the described esterifying kettle (2 sequentially concatenated, 3, 4) top mixed gas outlet pipeline 9 connects the mixing gas charging aperture 1.2.1 of tower joint 1.2 in esterification tower 1。Becoming notch cuttype arrangement when the esterifying kettle (2,3,4) sequentially concatenated is installed, form the difference in height being gradually lowered, the first esterifying kettle 2 is the highest。First esterifying kettle 2 top is connected to polyol starting material tank 10 and catalyst basin 11, and the connection pipeline of esterification tower 1 bottom discharging opening and the first esterifying kettle 2 is provided with carboxylic acid basin 12。Recovery channel 8 is provided with condenser II 13。Esterifying kettle (2,3,4) is provided with agitating device and heater。
Embodiment 2: with reference to embodiment 1, esterification tower 1 bottom discharging opening is respectively provided with pipeline and connects each esterifying kettle。
Embodiment 3: the production method of the continuous production system of a kind of low-carbon (LC) carboxylate utilizing polyhydric alcohol, with polyhydric alcohol and low-carbon (LC) carboxylic acid for raw material, with strong acid for catalyst, with corresponding low-carbon (LC) carboxylate for water entrainer, deposit in case in excess carboxylic acid, in esterifying kettle, add catalyst, polyhydric alcohol and low-carbon (LC) carboxylic acid continuously, obtain thick finished product by the continuous production system of the low-carbon (LC) carboxylate of polyhydric alcohol, obtain qualified products then through post processing；
Described polyhydric alcohol includes ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, neopentyl glycol, tetramethylolmethane is a kind of or combines；
Described low-carbon (LC) carboxylic acid includes acetic acid, propanoic acid, formic acid or butyrate；
Described strong acid catalyst includes sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid or heteropoly acid；
Described excess carboxylic acid, refers to the carboxylic acid being previously added in esterifying kettle, the excessive esterification being conducive to alcohol in course of reaction of acid completely or reach higher value；
Described catalyst, polyhydric alcohol and low-carbon (LC) carboxylic acid, refer to and obtain the catalyst of corresponding proportion, polyhydric alcohol and the low-carbon (LC) carboxylic acid that target product (thick finished product) consumes；
Described post processing, refers to the process for refining such as deacidification, neutralization of general high boiling ester series products, dehydration, decolorization filtering or vacuum distilling；
Corresponding low-carbon (LC) carboxylate is water entrainer, refers to the ester of low-carbon (LC) carboxylic acid used。Such as produce the polynary acid alcohol acetas of acetic acid, it is preferable that n-propyl acetate or butyl acetate；Propanoic acid polyol ester propionic ester, it is preferable that ethyl propionate。
Polyhydric alcohol, catalyst, carboxylic acid enters esterifying kettle by proportioning flow, the mixing gas of the esterification water, part water entrainer and the carboxylic acid composition that generate in esterifying kettle, and the middle part of entrance esterification tower, water and water entrainer form azeotropic mixture at tower top and enter condenser。Gas phase conversion is liquid phase, enters oil water separator, water entrainer and water stratification, and water entrainer flows back into esterification column, and the carboxylic acid condensed by water entrainer in tower flows downward, and it contains a small amount of water and continues up with the water entrainer of evaporation under tower that to be evaporated to tower top separated。Esterification water continuously enters recovery tower, and from the charging of recovery tower top, a small amount of water entrainer contained in esterification water in recovery tower and water azeotropic distillate condensed entrance oil water separator from tower top and be circulated utilization, and the water at the bottom of recovery tower is discharged into sewage disposal system。
Embodiment 4:
For ethylene acetate: first with ethylene glycol in still: acetic acid: the weight ratio of sulphuric acid is for 100:22(± 2): the ratio of 0.12 puts into each esterifying kettle to the 85% of still volume。The n-propyl acetate of 2-2.5 times of oil water separator effective volume and the water of 60% is added at tower top。Then beginning to warm up, when tower top has material to distillate, the interface location of the water in control oil water separator, water entrainer and water all pass back in tower, when the acid number < 0.1% of the water separated, water can be delivered to recovery tower and reclaim。Control esterification column tower top temperature 83.5(± 1) DEG C, push up temperature rise, then add part water entrainer。Then in still, acetic acid is added, target level is all reached to each still, start the reactant liquor pump of last still to deliver to the 1st esterifying kettle with certain speed, when the ratio of ethylene acetate and ethylene monoacetate is 99.5:0.5 in esterifying kettle 3 material to be detected to last, start thick finished product。While going out thick finished product, the first still being added material liquid, its ratio is acetic acid: the mol ratio 2.01:1 of ethylene glycol, and with the sulphuric acid (the 0.1% of the gross weight of ethylene glycol and acetic acid) of respective amount with add the acetic acid of the respective amount taken away by the thick finished product of discharging。Thick finished product enters the refining system of continuous deacidification, when the acetic acid deviate from may return to esterification system, stops adding acetic acid。After operation is normal, each still still temperature raises successively, and the excessive ratio owing to acting expect middle acid and alcohol can be different, so each still still temperature height is also not quite similar, general first still is at 120-123 DEG C, and the second still is at 128-132 DEG C, and the 3rd still is in the scope of 137-140 DEG C。In each still, the esterification degree of ethylene glycol is respectively in the scope of 85-89%, 96-97%, 99.4-99.8%。The crude product of discharging containing acetic acid between 35-40%。The n-propyl acetate of tower top, wherein 80% at overhead reflux, and 20% is refluxing at the bottom of tower, the water content situation according to the acetic acid at the bottom of tower, it is possible to suitably increases or reduces the ratio of the n-propyl acetate of backflow at the bottom of tower。
Claims (8)
1. the continuous production system of the low-carbon (LC) carboxylate of a polyhydric alcohol, including at least 3 esterifying kettles sequentially concatenated that esterification tower is connected with esterification tower bottom discharging opening, it is characterized in that described esterification tower is made up of three, upper, middle and lower tower joint, upper tower joint is provided with water preparation backflow distributor in top, water entrainer backflow distributor pipeline connects the outlet of oil water separator epipelagic zone water preparation, and middle tower joint is provided with mixing gas charging aperture；Lower tower joint is the loss of essence water tower of carboxylic acid dehydration, and tower bottom is provided with water preparation charging aperture, is provided with heater at the bottom of lower Ta Jieta；Described esterification tower tower top is attached to condenser, oil water separator and esterification water recovery tower-, the azeotropic mixture outlet of esterification tower top connects condenser, condenser connects oil water separator, the outlet of oil water separator epipelagic zone water preparation connects the water entrainer charging aperture above the lower tower joint bottom discharging opening of the water entrainer backflow distributor in the upper tower joint top of esterification tower and nearly esterification tower respectively by pipeline, the outlet of oil water separator lower layer of water connects the esterification water import of esterification water recovery tower top, the azeotropic mixture outlet of esterification water recovery tower top connects oil water separator by recovery channel, esterification water recovery tower bottom discharge outlet connects sewage disposal system, the described esterifying kettle top mixed gas outlet pipeline sequentially concatenated connects the mixing gas charging aperture of tower joint in esterification tower。
2. the continuous production system of the low-carbon (LC) carboxylate of a kind of polyhydric alcohol according to claim 1, it is characterised in that becoming notch cuttype arrangement when the esterifying kettle sequentially concatenated is installed, form the difference in height being gradually lowered, the first esterifying kettle is the highest。
3. the continuous production system of the low-carbon (LC) carboxylate of a kind of polyhydric alcohol according to claim 2, it is characterised in that esterifying kettle is set to 3 or 4。
4. the continuous production system of the low-carbon (LC) carboxylate of a kind of polyhydric alcohol according to claim 2, it is characterized in that the first esterifying kettle top is connected to polyol starting material tank and catalyst basin, the connection pipeline of esterification tower bottom discharging opening and the first esterifying kettle is provided with carboxylic acid basin。
5. the continuous production system of the low-carbon (LC) carboxylate of a kind of polyhydric alcohol according to claim 1, it is characterised in that esterification tower bottom discharging opening is respectively provided with pipeline and connects each esterifying kettle。
6. the continuous production system of the low-carbon (LC) carboxylate of a kind of polyhydric alcohol according to claim 1, it is characterised in that be provided with condenser II on recovery channel。
7. the continuous production system of the low-carbon (LC) carboxylate of a kind of polyhydric alcohol according to claim 1, it is characterised in that each esterifying kettle is provided with agitating device and heater。
8. the production method of the continuous production system of the low-carbon (LC) carboxylate utilizing one of claim 1 ~ 7 polyhydric alcohol, it is characterized in that with polyhydric alcohol and low-carbon (LC) carboxylic acid for raw material, with strong acid for catalyst, with corresponding low-carbon (LC) carboxylate for water entrainer, deposit in case in excess carboxylic acid, in esterifying kettle, add catalyst, polyhydric alcohol and low-carbon (LC) carboxylic acid continuously, obtain thick finished product by the continuous production system of the low-carbon (LC) carboxylate of polyhydric alcohol, obtain qualified products then through post processing；
Described polyhydric alcohol includes ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, glycerol, neopentyl glycol, tetramethylolmethane is a kind of or combines；
Described low-carbon (LC) carboxylic acid includes acetic acid, propanoic acid, formic acid or butyrate；
Described strong acid catalyst includes sulphuric acid, phosphoric acid, p-methyl benzenesulfonic acid or heteropoly acid；
Described excess carboxylic acid, refers to the carboxylic acid being previously added in esterifying kettle, the excessive esterification being conducive to alcohol in course of reaction of acid completely or reach higher value；
Described catalyst, polyhydric alcohol and low-carbon (LC) carboxylic acid, refer to and obtain the catalyst of corresponding proportion, polyhydric alcohol and the low-carbon (LC) carboxylic acid that target product (thick finished product) consumes；
Described post processing, refers to the process for refining such as deacidification, neutralization of general high boiling ester series products, dehydration, decolorization filtering or vacuum distilling；
Corresponding low-carbon (LC) carboxylate is water entrainer, refers to the ester of low-carbon (LC) carboxylic acid used。
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| CN109265340A (en) * | 2018-11-19 | 2019-01-25 | 深圳市前海博扬研究院有限公司 | A kind of glycol ChanShuDing ether carboxylate and preparation method thereof |
| CN110452116A (en) * | 2019-07-17 | 2019-11-15 | 江苏新东风化工科技有限公司 | A kind of n-butyl acrylate esterification device and its reaction process |
| CN111253253A (en) * | 2020-03-13 | 2020-06-09 | 何关印 | Continuous esterification equipment and method |
| CN114195300A (en) * | 2021-12-08 | 2022-03-18 | 珠海谦信新材料有限公司 | Processing system of acetic acid ester esterification cauldron waste residue liquid |
| CN114195300B (en) * | 2021-12-08 | 2023-12-05 | 珠海谦信新材料有限公司 | Treatment system for waste residue liquid of acetate esterification kettle |
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