CN111747849B - Method for synthesizing n-propyl acetate by continuous catalytic esterification of benzenesulfonic acid and derivatives thereof - Google Patents
Method for synthesizing n-propyl acetate by continuous catalytic esterification of benzenesulfonic acid and derivatives thereof Download PDFInfo
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- 238000005886 esterification reaction Methods 0.000 title claims abstract description 100
- 230000032050 esterification Effects 0.000 title claims abstract description 92
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229940092714 benzenesulfonic acid Drugs 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 99
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 94
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011259 mixed solution Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 150000002148 esters Chemical class 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims description 25
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 239000007858 starting material Substances 0.000 claims description 11
- 230000001502 supplementing effect Effects 0.000 claims description 8
- FEPBITJSIHRMRT-UHFFFAOYSA-N 4-hydroxybenzenesulfonic acid Chemical compound OC1=CC=C(S(O)(=O)=O)C=C1 FEPBITJSIHRMRT-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- CHZLVSBMXZSPNN-UHFFFAOYSA-N 2,4-dimethylbenzenesulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C(C)=C1 CHZLVSBMXZSPNN-UHFFFAOYSA-N 0.000 claims description 4
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 24
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 26
- 239000012535 impurity Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007599 discharging Methods 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000008346 aqueous phase Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011831 acidic ionic liquid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0229—Sulfur-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0214
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing n-propyl acetate by using benzenesulfonic acid and derivatives thereof through continuous catalytic esterification, which comprises the following steps: mixing a catalyst and acetic acid to form a mixed solution, adding the mixed solution and n-propanol into an esterification kettle in advance, and continuously introducing raw materials consisting of acetic acid and n-propanol into the esterification kettle, wherein the heating temperature of the esterification kettle is 100-110 ℃; the esterification reaction liquid obtained by the reaction in the esterification kettle enters a deacidification tower for deacidification treatment; and after the top discharge of the deacidification tower is condensed by a condenser, one part of the top discharge of the deacidification tower is returned to the deacidification tower, and the other part of the top discharge of the deacidification tower enters an ester-water separator for layering, and n-propyl acetate serving as a product is positioned in an upper ester phase obtained by layering. The method can solve the problems of side reaction, equipment corrosion and the like caused by the adoption of a sulfuric acid catalyst in the existing continuous esterification synthesis process of n-propyl acetate.
Description
Technical Field
The invention relates to the field of chemical industry; in particular to a method for synthesizing n-propyl acetate by continuous esterification.
Background
Sulfuric acid is a catalyst commonly used in the esterification reaction industry, however, because of its strong oxidizing and strong acidity, side reactions and equipment corrosion are easily caused in the reaction process, and the sulfuric acid is easy to consume and difficult to recycle. Especially in the continuous esterification synthesis process of n-propyl acetate, sulfuric acid catalyst is easy to consume, kettle liquid becomes more and more viscous, the kettle liquid needs to be replaced regularly, the production efficiency is seriously affected, and a large amount of acidic waste liquid which is difficult to treat is produced (Chinese patent CN 202766435U).
The traditional production process of n-propyl acetate has more intermittent operation, large amount of discharged waste liquid, low production efficiency, large pollution to the environment and high production cost, and is replaced by a continuous method (green chemical industry, 2016, 8:79-80). With the increasing attention of energy consumption and environmental protection in recent years, n-propyl acetate manufacturers are urgently required to develop novel esterification catalysts to replace sulfuric acid. Chinese patent CN 102001936a provides Lewis acidic ionic liquid catalysts, CN 101863760a and CN 104610055A both provide catalyst strong acid cation exchange resins, however the catalyst cost is much higher than sulfuric acid and the ratio of usage to column bottoms is up to 20% significantly greater than 2% when sulfuric acid catalyst is used. In addition, copper sulfate (applied chemical industry, 2014, 43 (12): 2249-2251), p-toluenesulfonic acid (chinese patent CN108911976 a; chemical industry intermediate, 2011, 9:47-48), heteropolyacid (applied chemical industry, 2008, 37 (8): 896-898) and sulfonated silica gel (guangzhou chemical industry, 2014, 42 (19): 34-36) have been developed as catalysts by researchers in recent years. However, the above-mentioned catalysts such as p-toluenesulfonic acid are limited to batch reactions due to various objective reasons such as process conditions, and have not been reported for use in continuous esterification synthesis processes.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for synthesizing n-propyl acetate by using benzenesulfonic acid and derivatives thereof through continuous catalytic esterification, which can solve the problems of side reaction, equipment corrosion and the like caused by adopting a sulfuric acid catalyst in the existing continuous esterification process for synthesizing n-propyl acetate.
In order to solve the technical problems, the invention provides a method for synthesizing n-propyl acetate by using benzenesulfonic acid and derivatives thereof through continuous catalytic esterification, which comprises the following steps:
mixing the catalyst with acetic acid to form a mixed solution, wherein the mole fraction of the catalyst in the mixed solution is 1-3%; firstly, adding a mixed solution and n-propanol into an esterification kettle in advance to serve as starting materials, wherein the mixed solution is prepared from the starting materials by the following steps of: n-propanol=3 (1±0.1);
then continuously introducing raw materials into an esterification kettle, wherein the raw materials are prepared from the following components in a molar ratio of 1:1 with n-propanol; the heating temperature of the esterification kettle is 100-110 ℃ (the temperature is kept all the time in the reaction process);
the esterification reaction liquid obtained by the reaction in the esterification kettle enters a deacidification tower for deacidification treatment; after the tower ejection of the deacidification tower is performed and current reflux is performed, setting the volume reflux ratio to be 0.5-1: 1 (i.e., the overhead feed back to the deacidification column: the overhead feed to the ester-water separator = 0.5-1:1 by volume); condensing the top discharge of the deacidification tower by a condenser, returning one part of the top discharge of the deacidification tower to the deacidification tower, and separating the other part of the top discharge of the deacidification tower by an ester-water separator to obtain n-propyl acetate serving as a product, wherein the n-propyl acetate serving as a product is positioned in an upper ester phase obtained by layering;
the catalyst is benzenesulfonic acid and/or derivatives thereof.
As an improvement of the method for synthesizing n-propyl acetate by continuous esterification, the invention comprises the following steps:
1) Adding the mixed solution into the esterification kettle through a mixed solution feeding valve b, adding n-propanol into the esterification kettle through an n-propanol feeding valve c, and closing the mixed solution feeding valve b after the mixed solution is fed; after the addition of the n-propanol is finished, closing an n-propanol addition valve c;
2) Heating the esterification kettle to 100-110 ℃, and starting a condenser; the esterification reaction liquid obtained by the reaction in the esterification kettle enters a deacidification tower for deacidification treatment; cooling the discharged material at the top of the deacidification tower through a condenser, and then completely refluxing to the top of the deacidification tower;
3) When the top of the deacidification tower is refluxed, a raw material feeding valve a is opened, raw materials are continuously added into the esterification kettle through the raw material feeding valve a, and after the total reflux is (30+/-5) min, the reflux ratio of the deacidification tower is set to be 0.5-1: 1, starting material collection; part of the top discharge of the condensed deacidification tower enters the ester-water separator for layering, the upper ester phase is discharged out of the ester-water separator through an ester phase discharge valve f, and the lower aqueous phase is discharged out of the ester-water separator through an aqueous phase discharge valve g.
As a further improvement of the method for synthesizing n-propyl acetate by continuous esterification, the mixed solution accounting for 30-45 percent of the volume of the esterification kettle is added into the esterification kettle.
As a further improvement of the method for synthesizing n-propyl acetate by continuous esterification, the catalyst is at least one of the following: p-hydroxybenzenesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, 2, 4-dimethylbenzenesulfonic acid and 2-naphthalenesulfonic acid.
That is, the catalyst is one or a mixture of more of benzenesulfonic acid and its derivatives.
As a further improvement of the method for synthesizing the n-propyl acetate by continuous esterification, the volume of the raw material continuously fed into the esterification kettle per hour is 1/5-1/4 of the volume of the starting material in the esterification kettle.
As a further improvement of the method for synthesizing n-propyl acetate by continuous esterification, when the minimum value of the temperature fluctuation at the top of the deacidification tower is less than 80 ℃ and the fluctuation frequency is more than or equal to 3 times, the catalyst is judged to be needed to be supplemented;
the supplementing method of the catalyst comprises the following steps: the mixed solution is selected as a catalyst replenishing solution, the catalyst replenishing solution is added into the esterification kettle through a mixed solution feeding valve b, and the volume dosage of the catalyst replenishing solution is 0.1 percent of the volume dosage of the mixed solution which is added into the esterification kettle (1) in advance.
Description: the temperature of the top of the deacidification tower is mainly influenced by the composition and pressure of the tower top, and the temperature of the top of the deacidification tower is naturally 80-83 ℃ under the set technological parameters of the invention; the column top pressure is hardly changed under normal pressure operation, and thus the column top composition change causes the column top temperature to fluctuate in the vicinity of 80 to 83 ℃. At below 80 ℃, this indicates a decrease in rising vapors (resulting from the decrease in reaction product esters) in the column; when the temperature is higher than 83 ℃, the composition heavy components at the top of the tower are increased, and the separation effect is not achieved.
Since the catalyst is gradually lost as the continuous reaction is prolonged in the homogeneous reaction, the catalyst needs to be periodically replenished. However, the concentration of the catalyst in the kettle liquid is used as a basis for judging whether to supplement the catalyst, so that the measurement is long in time consumption and large in workload, and the catalyst cannot be timely judged, and the productivity and the product quality are seriously affected. The temperature of the tower top is closely related to the composition of the azeotrope, and the temperature of the tower top is reduced because the n-propanol which is not converted in time at the tower bottom rises to the tower top. Therefore, the invention provides a method for taking the lowest value of the temperature fluctuation of the tower top as a judgment criterion, which is more timely and effective, can further prolong the replacement period of the kettle liquid and ensures the productivity and the product quality. According to the invention, when the tower top temperature is lower than 80 ℃ again 24 hours after the catalyst is replenished or when the liquid in the esterification kettle reaches 75% of the volume of the liquid, the kettle liquid needs to be replaced.
In the present invention:
the upper ester phase is refined to obtain high purity n-propyl acetate, which is a conventional rectification technique.
Compared with the prior art, the invention has the following beneficial effects:
1) The invention adopts benzenesulfonic acid and its derivative catalyst to replace sulfuric acid, the continuous catalytic esterification activity is equivalent, but the oxidability and acidity are obviously weakened, the generation of side reaction and the corrosiveness to equipment are reduced, and the invention is cheap and easy to obtain, and the use method is simple.
Namely, the invention applies one or more mixed acids of p-hydroxy benzene sulfonic acid, p-methyl benzene sulfonic acid, 2, 4-dimethyl benzene sulfonic acid, 2-naphthalene sulfonic acid and the like to continuously esterify and synthesize n-propyl acetate for the first time, and compared with the traditional continuous esterification catalyst sulfuric acid, the catalyst has the advantages of similar usage amount, obviously reduced byproducts, lower acidity and less corrosion to equipment.
2) Aiming at the problem of gradual catalyst loss in the long-term continuous reaction process, the invention provides a set of rapid and simple judgment method, and the catalyst is timely supplemented, namely, according to the temperature change of the top of the deacidification tower, the mixed solution of the catalyst and the acetic acid is supplemented through a valve; is beneficial to improving the production efficiency.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 is a process flow diagram of the present invention.
In the figure: 1-esterifying kettle, 2-deacidifying tower, 3-condenser, 4-ester water separator, a-raw material feed valve (i.e. acetic acid and n-propanol raw material feed valve), b-mixed liquor feed valve (catalyst and acetic acid mixed liquor feed valve), c-n-propanol feed valve, d-top material collecting valve, e-reflux valve, f-ester phase discharge valve and g-water phase discharge valve.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
device example 1,
The device comprises an esterification kettle 1, a deacidification tower 2, a condenser 3 and an ester-water separator 4, wherein the esterification kettle 1 is respectively provided with a raw material feed valve a, a mixed liquid feed valve b, a normal propyl alcohol feed valve c and a discharge port of the esterification kettle 1 which are communicated with a bottom feed port of the deacidification tower 2, the top outlet of the deacidification tower 2 is divided into two paths after passing through the condenser 3, one path of the outlet is communicated with a reflux port of the deacidification tower 2 through a reflux valve e (the reflux port is positioned at the top of the deacidification tower 2 or positioned near the side wall feed back of the top of the deacidification tower), and the other path of the outlet is communicated with an inlet of the ester-water separator 4 through a top material collecting valve d; the side wall of the ester-water separator 4 is provided with an ester phase discharging pipe, and the ester phase discharging pipe is provided with an ester phase discharging valve f; the bottom of the ester-water separator 4 is provided with an aqueous phase discharging pipe, and the aqueous phase discharging pipe is provided with an aqueous phase discharging valve g.
In general, the volume of the esterification reactor 1 is 0.1 times the volume of the deacidification tower 2.
The process flow of the invention is as follows:
when the mixed liquor feeding valve b, the n-propanol feeding valve c and the reflux valve e are all in an open state during the initial operation; and the top material collecting valve d is closed.
Mixing the catalyst and acetic acid to form a mixed solution, and adding the mixed solution into the esterification kettle 1 through a mixed solution feed valve b until the volume of the mixed solution is 30-45% of the volume of the esterification kettle 1; n-propanol is added into the esterification kettle 1 through an n-propanol charging valve c, and the mixed solution is as follows: n-propanol=3:1 by volume; after the mixed solution is fed, the mixed solution feeding valve b is closed, and after the n-propanol is fed, the n-propanol feeding valve c is closed; thus, the starting materials composed of the mixed liquid and n-propanol are previously added to the esterification vessel 1.
Then heating the esterification kettle 1 to 100-110 ℃ (the esterification kettle 1 always keeps the temperature in the whole reaction process), and starting a condenser 3; the gas generated by evaporation of the esterification reaction liquid (the esterification reaction liquid consists of n-propyl acetate, acetic acid, n-propanol, water, a catalyst and trace byproducts) obtained by the reaction in the esterification kettle 1 enters a deacidification tower 2 for deacidification treatment; the steam at the top of the deacidification tower 2 enters a condenser 3 to be condensed into liquid, and all the liquid flows back into the deacidification tower 2 through a reflux valve e.
When reflux occurs at the top of the deacidification tower 2, a raw material feeding valve a is opened, and the raw material is continuously fed into the esterification kettle 1 through the raw material feeding valve a, wherein the molar ratio is 1:1 and n-propanol, wherein the volume amount of the raw materials added per hour is 1/5-1/4 of the volume of the starting materials in the esterification kettle 1; after the reflux time reaches (30+ -5) min (after total reflux for the above time), the reflux ratio of the deacidification tower 1 is set to be 1:1, starting material collection; the top discharge of the condensed deacidification tower enters an ester-water separator 4 for layering, the upper ester phase is discharged through an ester phase discharge valve f and then is refined, and the lower water phase is discharged through a water phase discharge valve g and then is treated.
Example 1, method for continuous catalytic esterification synthesis of n-propyl acetate:
p-hydroxy benzene sulfonic acid is selected as a catalyst; the mole fraction of the catalyst in the mixed solution of the catalyst and acetic acid was 2.0%.
Adding the mixed solution into the esterification kettle 1 until the mixed solution is 30% of the volume of the esterification kettle 1; then 10% of n-propanol is added into the esterification kettle 1 volume percent, namely, n-propanol: mixed liquor = 1:3 volume ratio; heating the esterification kettle 1 to 100-110 ℃ and starting a condenser 3;
when reflux occurs at the top of the deacidification tower 2, continuously adding the catalyst into the esterification kettle 1, wherein the molar ratio is 1:1 and n-propanol, the volume of the added raw materials per hour is 10 percent of the volume of the esterification kettle 1 (namely, 25 percent of the volume of the starting materials). After total reflux for 30min, the reflux ratio of the deacidification tower 2 is set to be 1:1, starting to collect materials. The top discharge of the deacidification tower 2 is condensed by a condenser 3 and layered in an ester-water separator 4, the upper ester phase is refined, and the lower water phase is treated.
When the reaction proceeded to 92 hours, the minimum value of the temperature fluctuation at the top of the deacidification tower 2 was 80 ℃, and then 3 times of the minimum value was lower than 80 ℃ continuously appeared, so that it was judged that the catalyst was required to be replenished; the supplementing method of the catalyst comprises the following steps: the mixed liquor feed valve b was opened, 0.03% of the mixed liquor of the volume of the esterification vessel 1 was added, and then the mixed liquor feed valve b was closed. That is, the mixed liquid is selected as the catalyst replenishment liquid, and the volume amount of the catalyst replenishment liquid is 0.1% of the volume amount of the mixed liquid previously added to the esterification reactor, so that the total amount of the replenished catalyst is 0.1% of the catalyst originally added.
After 100h of reaction, the upper ester phase obtained by the ester-water separator 4 had the following contents: 96.30% of n-propyl acetate, 1.65% of n-propanol, less than 0.002% of acetic acid, 2.01% of water and the balance of impurities. The above% is mass%.
Example 2, method for continuous catalytic esterification synthesis of n-propyl acetate:
p-toluenesulfonic acid is selected as a catalyst; the mole fraction of the catalyst in the mixed solution formed by the catalyst and acetic acid is 2.0%; the remainder was identical to example 1.
When the reaction proceeded to 76 hours, the minimum value of the temperature fluctuation at the top of the deacidification tower 2 was 80 ℃, and then 3 times of the minimum value was lower than 80 ℃ continuously appeared, so that it was judged that the catalyst was required to be replenished; the supplementing method of the catalyst comprises the following steps: the mixed liquor feed valve b was opened, 0.03% of the mixed liquor by volume of the esterification vessel 1 was added, and then the mixed liquor feed valve b was closed. That is, in this case, the total amount of the supplementary catalyst was 0.1% of the catalyst originally added.
After 100h of reaction, the upper ester phase obtained by the ester-water separator 4 had the following contents: 96.05% of n-propyl acetate, 1.91% of n-propanol, less than 0.002% of acetic acid, 2.01% of water and the balance of impurities.
Example 3, method for continuous catalytic esterification synthesis of n-propyl acetate:
a mixture of equimolar amounts of p-toluenesulfonic acid and benzenesulfonic acid is selected as a catalyst; the mole fraction of the catalyst in the mixed solution formed by the catalyst and acetic acid is 2.0%; the remainder was identical to example 1.
When the reaction proceeded to 89 hours, the minimum value of the temperature fluctuation at the top of the deacidification tower 2 was 80 ℃, and then 3 times of the minimum value was lower than 80 ℃ continuously appeared, so that it was judged that the catalyst was required to be replenished; the supplementing method of the catalyst comprises the following steps: the mixed liquor feed valve b was opened, 0.03% of the mixed liquor by volume of the esterification vessel 1 was added, and then the mixed liquor feed valve b was closed. That is, in this case, the total amount of the supplementary catalyst was 0.1% of the catalyst originally added.
After 100h of reaction, the upper ester phase obtained by the ester-water separator 4 had the following contents: 96.25% of n-propyl acetate, 1.68% of n-propanol, less than 0.002% of acetic acid, 2.00% of water and the balance of impurities.
Example 4, method for continuous catalytic esterification synthesis of n-propyl acetate:
a mixture of equimolar amounts of p-toluenesulfonic acid and 2, 4-dimethylbenzenesulfonic acid is selected as a catalyst; the mole fraction of the catalyst in the mixed solution formed by the catalyst and acetic acid is 2.0%; the remainder was identical to example 1.
When the reaction was carried out for 83 hours, the minimum value of the temperature fluctuation at the top of the deacidification column 2 was 80 ℃, and then the minimum value was lower than 80 ℃ continuously appeared 3 times, so that it was judged that the catalyst was required to be replenished; the supplementing method of the catalyst comprises the following steps: the mixed liquor feed valve b was opened, 0.03% of the mixed liquor by volume of the esterification vessel 1 was added, and then the mixed liquor feed valve b was closed. That is, in this case, the total amount of the supplementary catalyst was 0.1% of the catalyst originally added.
After 100h of reaction, the upper ester phase obtained by the ester-water separator 4 had the following contents: 96.07% of n-propyl acetate, 1.83% of n-propanol, less than 0.002% of acetic acid, 2.01% of water and the balance of impurities.
Example 5, method for continuous catalytic esterification synthesis of n-propyl acetate:
a mixture of equimolar amounts of p-toluenesulfonic acid and 2-naphthalene sulfonic acid is selected as a catalyst; the mole fraction of the catalyst in the mixed solution formed by the catalyst and acetic acid is 2.0%; the remainder was identical to example 1.
When the reaction proceeded to 69 hours, the minimum value of the temperature fluctuation at the top of the deacidification tower 2 was 80 ℃, and then 3 times of the minimum value was lower than 80 ℃ continuously appeared, so that it was judged that the catalyst was required to be replenished; the supplementing method of the catalyst comprises the following steps: the mixed liquor feed valve b was opened, 0.03% by volume of the mixed liquor was added to the volume of the esterification vessel 1, and then the mixed liquor feed valve b was closed. That is, in this case, the total amount of the supplementary catalyst was 0.1% of the catalyst originally added.
After 100h of reaction, the upper ester phase obtained by the ester-water separator 4 had the following contents: 95.90% of n-propyl acetate, 1.93% of n-propanol, less than 0.002% of acetic acid, 2.03% of water and the balance of impurities.
Example 6, continuous catalytic esterification method for synthesizing n-propyl acetate:
selecting a mixture of equimolar amounts of p-hydroxy benzene sulfonic acid and p-toluene sulfonic acid as a catalyst; the mole fraction of the catalyst in the mixed solution formed by the catalyst and acetic acid is 2.0%; the remainder was identical to example 1.
The reaction is carried out within 100 hours, and the temperature of the top of the deacidification tower 2 is all in a range of 80-83 ℃ and thus the catalyst is not required to be supplemented.
After 100h of reaction, the upper ester phase obtained by the ester-water separator 4 had the following contents: 96.61% of n-propyl acetate, 1.32% of n-propanol, less than 0.002% of acetic acid, 2.02% of water and the balance of impurities.
Example 7, method for continuous catalytic esterification synthesis of n-propyl acetate:
selecting a mixture of equimolar amounts of p-hydroxy benzene sulfonic acid and p-toluene sulfonic acid as a catalyst; the mole fraction of the catalyst in the mixed solution formed by the catalyst and acetic acid is 3.0%;
adding the mixed solution into an esterification kettle 1 until the volume of the esterification kettle 1 is 45%; then adding 15% of n-propanol which is the volume of the esterification kettle 1, namely, n-propanol: mixed liquor = 1:3 volume ratio;
when reflux occurs at the top of the deacidification tower 2, continuously adding the catalyst into the esterification kettle 1, wherein the molar ratio is 1:1 and n-propanol, the volume of the added raw materials per hour is 12 percent of the volume of the esterification kettle 1 (namely, 20 percent of the volume of the starting materials).
The reaction time is 200h; the remainder was identical to example 1.
When the reaction was progressed to 179 hours, the minimum value of the temperature fluctuation at the top of the deacidification column 2 was 80 ℃, and then 3 times of the minimum value was lower than 80 ℃ continuously appeared, so that it was judged that the catalyst replenishment was required; the supplementing method of the catalyst comprises the following steps: the mixed liquor feed valve b was opened, 0.045% of the mixed liquor of the volume of the esterification vessel 1 was added, and then the mixed liquor feed valve b was closed. That is, in this case, the total amount of the supplementary catalyst was 0.1% of the catalyst originally added.
The upper ester phase obtained from the ester-water separator 4 was each formed and contained in the amount shown in Table 1 below at various reaction times.
TABLE 1 esterification reaction results
| Reaction time (h) | N-propyl acetate (%) | N-propanol (%) | Acetic acid (%) | Water (%) |
| 10 | 96.70 | 1.23 | ＜0.002 | 1.97 |
| 20 | 96.65 | 1.27 | ＜0.001 | 1.99 |
| 30 | 96.60 | 1.28 | ＜0.002 | 2.01 |
| 40 | 96.63 | 1.31 | ＜0.002 | 2.02 |
| 50 | 96.65 | 1.29 | ＜0.002 | 2.00 |
| 100 | 96.61 | 1.32 | ＜0.002 | 2.01 |
| 150 | 96.59 | 1.34 | ＜0.002 | 2.01 |
| 200 | 96.62 | 1.31 | ＜0.002 | 2.02 |
Comparative example 1 the catalyst of example 1 was changed to sulfuric acid, the replenishment of the catalyst of example 1 was omitted, and the remainder was identical to example 1.
The results obtained were:
when the reaction was carried out for 52 hours, the minimum value of the temperature fluctuation at the top of the deacidification column 2 was 80℃and then the minimum value was lower than 80℃continuously appeared. After 100 hours of reaction, the upper ester phase obtained from the ester-water separator 4 had the following contents: 95.26% of n-propyl acetate, 2.5% of n-propanol, less than 0.002% of acetic acid, 2.10% of water and the balance of impurities.
The comparative example 1 has drawbacks in that sulfuric acid, a catalyst, is used, is easily consumed, and impurities generated by side reactions are relatively large.
What needs to be further explained is: the yield improvement of 0.1% reduces the energy consumption of the whole process due to the large annual yield.
Comparative example 2, the catalyst addition in example 1 was omitted, and the remainder was identical to example 1.
The results obtained were:
after 100h of reaction, the upper ester phase obtained by the ester-water separator 4 had the following contents: 96.0% of n-propyl acetate, 1.71% of n-propanol, less than 0.002% of acetic acid, 2.01% of water and the balance of impurities.
The disadvantage of this comparative example 2 is that the catalytic esterification efficiency of the esterification vessel 1 is reduced, resulting in a higher n-propanol content in the crude ester product.
Comparative example 3-1 the reflux ratio in example 1 was defined by "1:1 "change to" 0.5:1", the remainder being identical to example 1.
The results obtained were:
after 100h of reaction, the upper ester phase obtained by the ester-water separator 4 had the following contents: 95.85% of n-propyl acetate, 2.04% of n-propanol, less than 0.003% of acetic acid, 2.06% of water and the balance of impurities.
The comparative example 3-1 has the defects that the separation effect of the deacidification tower 2 is reduced, the purity of the n-propyl acetate in the crude ester product is reduced, and the n-propanol content is higher.
Comparative example 3-2 the reflux ratio in example 1 was defined by "1:1 "change to" 2:1", the remainder being identical to example 1.
The results obtained were:
after 100h of reaction, the upper ester phase obtained by the ester-water separator 4 had the following contents: 96.31% of n-propyl acetate, 1.65% of n-propanol, less than 0.002% of acetic acid, 2.01% of water and the balance of impurities.
The comparative example 3-2 has the disadvantage that the reflux ratio of the deacidification column 2 is increased, the energy consumption is higher, however, the separation effect of n-propyl acetate is hardly changed.
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (3)
1. The method for synthesizing n-propyl acetate by using benzenesulfonic acid and derivatives thereof through continuous catalytic esterification is characterized by comprising the following steps:
1) Mixing the catalyst with acetic acid to form a mixed solution, wherein the mole fraction of the catalyst in the mixed solution is 1-3%; the mixed liquor is added into the esterification kettle (1) through a mixed liquor feeding valve b, n-propanol is added into the esterification kettle (1) through a n-propanol feeding valve c, and after the mixed liquor is fed, the mixed liquor feeding valve b is closed; after the addition of the n-propanol is finished, closing an n-propanol addition valve c;
the mixed liquid and the normal propyl alcohol are used as starting materials, wherein the mixed liquid is as follows: n-propanol=3 (1±0.1);
2) Heating the esterification kettle (1) to 100-110 ℃ and starting a condenser (3); the esterification reaction liquid obtained by the reaction in the esterification kettle (1) enters a deacidification tower (2) for deacidification treatment;
the top discharge of the deacidification tower (2) is cooled by a condenser (3) and then totally flows back to the top of the deacidification tower (2);
3) When reflux occurs at the top of the deacidification tower (2), a raw material feeding valve a is opened, raw materials are continuously added into the esterification kettle (1) through the raw material feeding valve a, and the raw materials are prepared from the following components in a molar ratio of 1:1 with n-propanol; after total reflux is (30+/-5) min, setting the reflux ratio of the deacidification tower (2) to be 0.5-1: 1, condensing the top discharge of a deacidification tower (2) through a condenser (3), returning one part to the deacidification tower (2), and layering the other part in an ester-water separator (4), wherein n-propyl acetate serving as a product is positioned in an upper ester phase obtained by layering; the upper-layer ester phase is discharged from the ester-water separator (4) through an ester-phase discharge valve f, and the lower-layer water phase is discharged from the ester-water separator (4) through a water-phase discharge valve g;
the catalyst is at least one of the following: p-hydroxybenzenesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, 2, 4-dimethylbenzenesulfonic acid and 2-naphthalenesulfonic acid;
when the lowest value of the temperature fluctuation of the top of the deacidification tower (2) is less than 80 ℃ and the fluctuation frequency is more than or equal to 3 times, judging that the catalyst needs to be supplemented;
the supplementing method of the catalyst comprises the following steps: the mixed solution is selected as a catalyst replenishing solution, the catalyst replenishing solution is added into the esterification kettle (1) through a mixed solution feeding valve b, and the volume dosage of the catalyst replenishing solution is 0.1 percent of the volume dosage of the mixed solution which is added into the esterification kettle (1) in advance.
2. The method for synthesizing n-propyl acetate by continuous catalytic esterification of benzenesulfonic acid and derivatives thereof according to claim 1, wherein the method comprises the steps of: and adding mixed liquid accounting for 30-45% of the volume of the esterification kettle (1) into the esterification kettle (1).
3. The method for synthesizing n-propyl acetate by continuous catalytic esterification of benzenesulfonic acid and derivatives thereof according to claim 2, wherein the method comprises the steps of: the volume of the raw material continuously fed into the esterification kettle (1) per hour is 1/5-1/4 of the volume of the starting material in the esterification kettle (1).
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