CN111744435A

CN111744435A - Esterification process of hydroxylate

Info

Publication number: CN111744435A
Application number: CN202010638578.5A
Authority: CN
Inventors: 阮煜翔; 潘飞翔; 沈海锋; 钟功源
Original assignee: Zhejiang Huixiang Chemical Industry Co ltd
Current assignee: Zhejiang Huixiang Chemical Industry Co ltd
Priority date: 2020-07-06
Filing date: 2020-07-06
Publication date: 2020-10-09
Anticipated expiration: 2040-07-06
Also published as: CN111744435B

Abstract

The invention discloses an esterification process of hydroxylate, which comprises the following steps: a. adding dehydrated hydroxylate and acetic acid into a reaction barrel, wherein the dehydrated hydroxylate and the acetic acid are fed according to the mol ratio of the contained hydroxyethyl to the acetic acid of 1:1-1: 10; heating while stirring, and promoting esterification reaction by rectification and dehydration when the temperature is raised to 110-150 ℃; b. adding a molecular sieve with the channel aperture smaller than 9A into the reaction barrel after the esterification reaction, wherein the reaction after the esterification reaction means that the conversion rate of the dehydrated hydroxylate is more than 80 percent, the adding mass of the molecular sieve is 1 to 25 percent of the mass of the dehydrated hydroxylate, and continuously reacting under the reflux state at the temperature of 110 ℃ and 140 ℃ until the reaction is finished; c. after the esterification reaction is finished, separating the product from the molecular sieve to obtain high-purity esterified liquid; d. the separated molecular sieve is subjected to regeneration and activation treatment, and the regenerated and activated molecular sieve is recycled.

Description

Esterification process of hydroxylate

Technical Field

The invention belongs to the technical field of esterification production methods of dye intermediates, and particularly relates to an esterification process of a hydroxylate.

Background

The esterification liquid is an important coupling intermediate in the production process of disperse dyes, and comprises dark blue esterification liquid (3- [ N, N- (diacetoxyethyl) amino ] -4-methoxy acetanilide), ruby esterification liquid (3- (N, N-diacetoxyethyl) aminoacetanilide), yellowish brown esterification liquid (N-cyanoethyl-N-acetoxyethylaniline) and other esterification liquids. The esterification liquid is prepared by using corresponding hydroxylate as a starting material and carrying out one-step esterification reaction on the hydroxylate and carboxylic acid or anhydride. The acid anhydride has stronger activity and can be used for the acylation of alcoholic hydroxyl with small activity or larger steric hindrance, and in the traditional industrial production, the production of the esterification liquid usually adopts acetic anhydride as the acylating agent.

Although the addition of the catalyst can improve the reaction rate, the esterification reaction is a reversible process, and the added catalyst cannot change the reaction equilibrium state. In industrial production, the product yield is improved by removing water generated by the reaction and the like, the dehydration can be realized by direct distillation dehydration or azeotropic dehydration by using a water-carrying agent, and the reaction is promoted by using molecular sieve dehydration, for example, in the literature [ green synthesis process research of isopropyl palmitate, chemical world, No. 10 in 2015 ] and in the literature 6[3A type molecular sieve as a dehydrating agent to synthesize ethyl hexanoate, perfume and essence cosmetics, No. 2 in 1997 ], the esterification catalyst is added, and the reaction is promoted by using a method of dehydrating and recycling alcohol-water azeotrope distilled out in the reaction process by using the molecular sieve.

The characteristics of the reaction materials of the dye intermediate esterification liquid are different from those of other esterification materials, and not all esterification modes are suitable for producing the dye intermediate esterification liquid. Both the esterified material hydroxylate and the esterified liquid product are heat-sensitive substances, and are not suitable for dehydration at higher temperature, the used acylating agent acetic acid and water do not form an azeotrope, but the boiling points of the acylating agent acetic acid and the water are close, the relative volatility of the acetic acid and the water is lower, and the acylating agent acetic acid and the water belong to a highly non-ideal system, so that the direct distillation and dehydration at the later stage of the esterification reaction become abnormally difficult, and further the product yield is not high; similarly, the water-carrying agent is used in a small amount, which cannot achieve a good water-carrying effect, and the excessive amount of the water-carrying agent causes the reaction temperature to be too low, so that the chemical kinetics in the reaction system becomes a control step, which causes the esterification reaction to be slow and cannot be normally carried out.

In conclusion, the synthesis method of the dye intermediate esterification solution, which has the advantages of low energy consumption, mild reaction conditions, high reaction speed, high product purity and high yield, is of great significance.

Disclosure of Invention

The invention provides an esterification process of a hydroxylate, aiming at overcoming the defects of the prior art.

In order to achieve the purpose, the invention adopts the following technical scheme: a process for the esterification of a hydroxylate comprising:

a. adding dehydrated hydroxylate and acetic acid into a reaction barrel, wherein the dehydrated hydroxylate and the acetic acid are fed according to the mol ratio of the contained hydroxyethyl to the acetic acid of 1:1-1: 10; heating while stirring, and promoting esterification reaction by rectification and dehydration when the temperature is raised to 110-150 ℃;

b. adding a molecular sieve with the channel aperture smaller than 9A into the reaction barrel after the esterification reaction, wherein the reaction after the esterification reaction means that the conversion rate of the dehydrated hydroxylate is more than 80 percent, the adding mass of the molecular sieve is 1 to 25 percent of the mass of the dehydrated hydroxylate, and continuously reacting under the reflux state at the temperature of 110 ℃ and 140 ℃ until the reaction is finished;

c. after the esterification reaction is finished, separating the product from the molecular sieve to obtain high-purity esterified liquid;

d. carrying out regeneration and activation treatment on the separated molecular sieve, and recycling the regenerated and activated molecular sieve;

a first cover plate is arranged at the top of the reaction barrel in the step a, a first through hole is formed in the first cover plate, a material loading box corresponding to the first through hole is arranged in the reaction barrel, a first movable groove is formed in the inner wall of the first through hole, a connecting ring is arranged in the first movable groove, a first connecting plate is arranged at the bottom of the connecting ring, a first sliding groove is formed in the first connecting plate, a first sliding block matched with the first sliding groove is arranged on the material loading box, a transmission ring is arranged on the connecting ring, and a first driving motor used for driving the transmission ring to rotate is arranged on the first cover plate; the bottom of the reaction barrel is provided with a first movable cavity, a first sleeve is arranged in the first movable cavity in a penetrating manner, a second sleeve is arranged in the first sleeve in a penetrating manner, the material carrying box is arranged at the top of the second sleeve, and when the material carrying box rotates, the first sleeve moves into the first movable cavity; a discharge pipe is arranged at the bottom of the reaction barrel, and a heating block is arranged in the reaction barrel; after the hydroxylate and the acetic acid are put into the reaction barrel, the first driving motor drives the transmission ring to rotate, the first connecting plate rotates in the reaction barrel, and the solution is heated by the heating block; putting a molecular sieve on a material carrying box, putting the material carrying box into a reaction barrel, allowing the material carrying box to fall to the top of a second sleeve along a first connecting plate, continuously driving a transmission ring to rotate by a first driving motor, driving the material carrying box to rotate by the first connecting plate, allowing the molecular sieve to be in contact with a solution, allowing the first sleeve to move into a first movable cavity when the material carrying box rotates, allowing the material carrying box to move downwards along with the movement of the first sleeve, and allowing the molecular sieve to move from the middle of the reaction barrel to the bottom of the reaction barrel; and after the reaction is finished, opening the discharge pipe, discharging the solution from the discharge pipe, pushing the material carrying box upwards, taking the material carrying box out of the reaction barrel, and recovering the molecular sieve in the reaction barrel.

According to the method, the molecular sieve is added in the later stage of esterification, so that the reaction is accelerated by utilizing the characteristic of catalytic esterification of the molecular sieve, the esterification reaction is promoted to further proceed by utilizing the characteristic of water absorption of the molecular sieve, and the conversion rate and the product yield are obviously improved; meanwhile, the structure of the material loading box is adopted, the molecular sieve is placed in the material loading box and then placed in the reaction barrel, the molecular sieve is collected at one position in a centralized manner, the molecular sieve is prevented from scattering at each position in the reaction barrel, so that the molecular sieve is collected uniformly, the recovery of the molecular sieve can be finished in a manner that the material loading box is directly taken out from the reaction barrel after the reaction is finished, and the recovery difficulty of the molecular sieve is greatly reduced; the first connecting plate drives the material loading box to rotate while stirring the solution, so that the molecular sieve in the material loading box is in a motion state, the molecular sieve is better contacted with the solution in the reaction barrel, the solution is conveniently screened, and the conversion rate of the hydroxylate is ensured; the material loading box is guided by the first connecting plate and moves up and down in the vertical direction, so that a certain space is reserved between the material loading box and the inner wall of the reaction barrel all the time, the material loading box is prevented from colliding with the inner wall of the reaction barrel, and the reaction barrel and the material loading box are protected.

In the step d, the regeneration and activation treatment method of the molecular sieve is a heating regeneration method, a replacement regeneration method or a combination of the heating regeneration method and the replacement regeneration method;

the heating regeneration method comprises the following steps: after the molecular sieve subjected to reaction separation is washed and filtered by hot acetic acid and water, activation and regeneration are realized by a hot air heating or microwave dehydration method, and the acetic acid washing liquid subjected to filtration separation is used as a washing liquid and/or an esterification reaction raw material according to the concentration of acetic acid;

the replacement regeneration method comprises the following steps: the molecular sieve separated by reaction is washed and filtered by hot acetic acid, acetic acid washing liquid separated by filtration is used as washing liquid and/or esterification reaction raw materials according to the concentration of acetic acid, the molecular sieve separated by filtration is soaked in heated glacial acetic acid to realize the regeneration of the molecular sieve, or the molecular sieve is regenerated in the glacial acetic acid heated to a reflux state, the regenerated molecular sieve and acetic acid regeneration liquid are obtained by filtration and separation, and the acetic acid regeneration liquid is used as the washing liquid and/or the esterification reaction raw materials.

In the step d, the acetic acid washing liquid used for washing the molecular sieve is hot acetic acid with the mass concentration of more than 90%.

In the step a, the acetic acid is glacial acetic acid and/or acetic acid with the mass concentration of more than 90%.

In the step a, the water content of the dehydrated hydroxylate is less than 10%.

A first air delivery passage and a second air delivery passage are arranged on the side wall of the first movable cavity, the first air delivery passage is communicated with an air delivery pipe, an installation cavity is arranged in the second air delivery passage, a stop block is arranged in the installation cavity, a second through hole is formed in the stop block, a second movable cavity is further arranged on the stop block, and a sealing block matched with the second through hole is arranged in the second movable cavity; a movable rod is arranged in the second sleeve, a first connecting shaft penetrates through the movable rod and is connected to the inner wall of the second sleeve, a first bump for driving the movable rod to rotate is arranged at the bottom of the material loading box, and when the movable rod rotates, the sealing block moves into the second movable cavity; after the molecular sieve is placed into the material carrying box, the material carrying box descends to the second sleeve, the first driving motor drives the material carrying box to rotate, the first protruding block discontinuously pushes the movable rod to rotate around the first connecting shaft when rotating along with the material carrying box, the sealing block moves towards the second movable cavity when the movable rod rotates, air flow in the first movable cavity is discharged from the second air conveying channel when the second through hole is opened, the second sleeve moves downwards after the air flow in the first movable cavity is reduced, the material carrying box moves downwards along with the second sleeve, the first driving motor continuously drives the material carrying box to rotate, the first connecting plate stirs solution, and esterification of hydroxylate is completed.

The side wall of the reaction barrel is provided with a mounting plate, the mounting plate is provided with a second driving motor, an output shaft of the second driving motor is provided with a spool, a first connecting rope is wound on the spool, the top of the material receiving box is provided with a wiring end, and the other end of the first connecting rope is sleeved on the wiring end; the side wall of the reaction barrel is provided with an installation block, the installation block is provided with a third movable cavity, a first connecting rod penetrates through the third movable cavity, the top of the first connecting rod is provided with a second movable groove, and a guide wheel is arranged in the second movable groove; a first limiting plate is arranged at the bottom of the first connecting rod, and a first supporting spring is arranged at the bottom of the first limiting plate; a third movable groove is formed in the inner wall of the third movable cavity, a limiting block is arranged in the third movable groove, and the limiting block enters the third movable groove after the first sliding block moves to the bottom of the first sliding groove; when the first driving motor drives the material carrying box to rotate, the material carrying box moves downwards along with the first sleeve, the first sliding block moves to the bottom of the first sliding groove, the limiting block enters the third movable groove, the first supporting spring pushes the first connecting rod to generate an upward movement trend, air flow is injected into the first movable cavity, the first sleeve is pushed by air pressure to move upwards, the material carrying box is pushed by the first sleeve and the second sleeve to move upwards, the material carrying box moves to the middle of the reaction barrel, the first supporting spring pushes the first connecting rod to move upwards, and the middle of the first connecting rope arches; after the reaction is finished, the discharging pipe is opened to discharge the solution from the discharging pipe, the second driving motor drives the bobbin to rotate, the first connecting rope winds the bobbin, the first connecting rope pulls the material carrying box to move upwards, the material carrying box rises from the first through hole, and the molecular sieve in the reaction barrel is taken out.

The invention has the following advantages:

1. according to the method, the molecular sieve is added in the later stage of esterification, so that the reaction is accelerated by utilizing the catalytic esterification characteristic of the molecular sieve, the esterification reaction is promoted to further proceed by utilizing the water absorption characteristic of the molecular sieve, and the conversion rate and the product yield are obviously improved.

2. The method has the advantages of mild reaction conditions, easy control and high reaction rate, and avoids the reaction materials from being in a high-temperature state for a long time.

3. The high-molecular sieve with the product purity can be recycled after being activated and regenerated by hot acetic acid, so that the cost of raw materials is effectively saved.

Drawings

FIG. 1 is a schematic structural view of a reaction barrel in example 1 of the present invention.

FIG. 2 is a front view of a reaction tank in example 1 of the present invention.

Fig. 3 is a cross-sectional view taken along a-a in fig. 2.

Fig. 4 is an enlarged view of a portion a in fig. 3.

Fig. 5 is an enlarged view of fig. 3 at B.

Fig. 6 is an enlarged view of fig. 3 at C.

Fig. 7 is an enlarged view of fig. 5 at D.

Fig. 8 is a cross-sectional view taken along line B-B of fig. 2.

Fig. 9 is an enlarged view of fig. 8 at E.

Fig. 10 is a cross-sectional view taken along line C-C of fig. 2.

Fig. 11 is an enlarged view of fig. 10 at F.

Fig. 12 is an enlarged view at G in fig. 11.

FIG. 13 is a right side view of the reaction tank in example 1 of the present invention.

Fig. 14 is a cross-sectional view taken along line D-D of fig. 13.

Fig. 15 is an enlarged view of fig. 14 at H.

Fig. 16 is an enlarged view at I in fig. 14.

Fig. 17 is an enlarged view at J in fig. 14.

Fig. 18 is an enlarged view at K in fig. 16.

Fig. 19 is an enlarged view at L in fig. 17.

Fig. 20 is a cross-sectional view taken along line E-E of fig. 13.

Fig. 21 is an enlarged view of fig. 20 at M.

Fig. 22 is a cross-sectional view taken along F-F in fig. 13.

Fig. 23 is an enlarged view of fig. 22 at N.

Fig. 24 is an enlarged view at O in fig. 23.

Fig. 25 is an enlarged view at P in fig. 23.

Fig. 26 is a cross-sectional view taken along G-G in fig. 13.

Fig. 27 is an enlarged view at Q in fig. 26.

Fig. 28 is an enlarged view of fig. 27 at R.

Fig. 29 is a sectional view taken along H-H in fig. 13.

Fig. 30 is an enlarged view of fig. 29 at S.

Detailed Description

Example 1:

a process for the esterification of a hydroxylate comprising: adding 22.0g of deep blue hydroxylate containing 10% of water and 42.6ml of glacial acetic acid into a reaction barrel, heating to 130 ℃ for reaction, and carrying out dehydration reaction for 5 hours; adding 2.2g of 5A molecular sieve into the flask, and continuing to perform full reflux reaction for 3.0h at the temperature of 120 ℃; cooling to 50-60 ℃, filtering, removing the molecular sieve, and removing acetic acid under reduced pressure to obtain 26.82g of a product, namely, a dark blue esterified liquid; HPLC detection shows that the product purity is 98.5% and the product yield is 98.0%.

Washing and filtering the separated molecular sieve with acetic acid (glacial acetic acid heated) at 80 ℃, soaking for 4 hours with acetic acid (glacial acetic acid heated) at 105 ℃, filtering and separating to obtain regenerated molecular sieve for later use, wherein the acetic acid washing liquid and the acetic acid regenerated liquid which are subjected to filtering and separation can be recycled.

As shown in fig. 1-30, a first cover plate 2 is arranged on the top of the reaction barrel 1 in the step a, a first through hole is formed in the first cover plate 2, a material carrying box 4 corresponding to the first through hole is arranged in the reaction barrel 1, a plurality of third through holes are formed in the material carrying box, a second cover plate 41 is arranged on the top of the material carrying box, a plurality of fourth through holes are formed in the second cover plate, and the solution enters the material carrying box to fully contact with the molecular sieve under the arrangement of the third through holes and the fourth through holes; a first movable groove is formed in the inner wall of the first through hole, a connecting ring 22 is arranged in the first movable groove, a first connecting plate 23 is arranged at the bottom of the connecting ring 22, a first sliding groove 231 is formed in the first connecting plate 23, a first sliding block 44 matched with the first sliding groove 231 is arranged on the carrier box 4, a transmission ring 221 is arranged on the connecting ring 22, and a first driving motor 31 used for driving the transmission ring 221 to rotate is arranged on the first cover plate 2; a first movable cavity 160 is arranged at the bottom of the reaction barrel 1, a first sleeve 15 penetrates through the first movable cavity 160, a second sleeve 16 penetrates through the first sleeve 15, the carrier box 4 is arranged at the top of the second sleeve 16, and when the carrier box 4 rotates, the first sleeve 15 moves into the first movable cavity 160; a discharge pipe 11 is arranged at the bottom of the reaction barrel 1, an electromagnetic valve is arranged in the discharge pipe, and a heating block is arranged in the reaction barrel 1; after the hydroxylate and the acetic acid are put into the reaction barrel 1, the first driving motor 31 drives the transmission ring 221 to rotate, the first connecting plate 23 rotates in the reaction barrel 1, and the solution is heated by the heating block; putting a molecular sieve on the material carrying box 4, putting the material carrying box 4 into the reaction barrel 1, allowing the material carrying box 4 to fall to the top of the second sleeve 16 along the first connecting plate 23, continuously driving the transmission ring 221 to rotate by the first driving motor 31, allowing the first connecting plate 23 to drive the material carrying box 4 to rotate, allowing the molecular sieve to be in contact with a solution, allowing the first sleeve 15 to move into the first movable cavity 160 when the material carrying box 4 rotates, allowing the material carrying box 4 to move downwards along with the movement of the first sleeve 15, and allowing the molecular sieve to move from the middle of the reaction barrel 1 to the bottom of the reaction barrel 1; after the reaction is finished, the discharge pipe 11 is opened, the solution is discharged from the discharge pipe 11, the material carrying box 4 is pushed upwards, the material carrying box 4 is taken out of the reaction barrel 1, and the molecular sieve in the reaction barrel 1 is recovered.

The structure of the material loading box is adopted, the molecular sieve is placed in the material loading box and then placed in the reaction barrel, the molecular sieve is collected at one position in a centralized manner, the molecular sieve is prevented from scattering at each position in the reaction barrel, so that the molecular sieve is collected uniformly, the recovery of the molecular sieve can be finished by taking the material loading box out of the reaction barrel directly after the reaction is finished, and the recovery difficulty of the molecular sieve is greatly reduced; the first connecting plate drives the material loading box to rotate while stirring the solution, so that the molecular sieve in the material loading box is in a motion state, the molecular sieve is better contacted with the solution in the reaction barrel, the solution is conveniently screened, and the conversion rate of the hydroxylate is ensured; the material loading box is guided by the first connecting plate and moves up and down in the vertical direction, so that a certain space is reserved between the material loading box and the inner wall of the reaction barrel all the time, the material loading box is prevented from colliding with the inner wall of the reaction barrel, and the reaction barrel and the material loading box are protected.

A first air delivery passage 140 and a second air delivery passage 160 are arranged on the side wall of the first movable cavity 160, the first air delivery passage 140 is communicated with an air delivery pipe 150, the other end of the air delivery cavity is connected with an air pump or other air supply equipment, an installation cavity is arranged in the second air delivery passage 160, a stop block 170 is arranged in the installation cavity, a second through hole is formed in the stop block 170, a second movable cavity is further arranged on the stop block 170, and a sealing block 1701 matched with the second through hole is arranged in the second movable cavity; the two sealing blocks are matched with each other to seal the second through hole; a movable rod 161 is arranged in the second sleeve 16, a first connecting shaft 162 penetrates through the movable rod 161, the first connecting shaft 162 is connected to the inner wall of the second sleeve 16, a first bump 431 for driving the movable rod 161 to rotate is arranged at the bottom of the carrier box 4, and when the movable rod 161 rotates, the sealing block 1701 moves into the second movable cavity; after the molecular sieve is placed in the material carrying box 4, the material carrying box 4 descends to the second sleeve 16, the first driving motor 31 drives the material carrying box 4 to rotate, the first bump 431 intermittently pushes the movable rod 161 to rotate around the first connecting shaft 162 when rotating along with the material carrying box 4, the sealing block 1701 moves towards the second movable cavity when the movable rod 161 rotates, airflow in the first movable cavity 160 is discharged from the second air conveying channel 150 when the second through hole is opened, the second sleeve 16 moves downwards after the airflow in the first movable cavity 160 is reduced, the material carrying box 4 moves downwards along with the second sleeve 16, the first driving motor 31 continuously drives the material carrying box 4 to rotate, and the first connecting plate 23 stirs the solution to complete esterification of the hydroxylate.

After putting hydroxylate and acetic acid into a reaction barrel, introducing airflow into a first movable cavity through an air conveying pipe, pushing a first sleeve and a second sleeve to move upwards under the action of air pressure, lifting the second sleeve to the middle of the reaction barrel, sealing a second through hole by a sealing block, forming a sealing environment in the first movable cavity, and keeping the air pressure in the first movable cavity to provide a good supporting effect for the second sleeve; after the molecular sieve is loaded into the material loading box, the first slide block is aligned with the first chute, the material loading box is loaded into the reaction barrel, and the second sleeve provides supporting force for the material loading box; the second through hole is discontinuously opened when the material carrying box rotates, so that gas in the first movable cavity is gradually discharged, the supporting force of the second sleeve is reduced after the air pressure in the first movable cavity is reduced, the second sleeve descends for a short distance under the action of gravity of the material carrying box, the material carrying box gradually descends to the bottom of the reaction barrel along with the rotation of the material carrying box, the material carrying box is stopped at different positions of the reaction barrel, the contact effect of the molecular sieve and the solution is further improved, and dead angles are avoided.

First sleeve pipe bottom is equipped with second limiting plate 152, second limiting plate bottom is equipped with second supporting spring 151, second sleeve pipe bottom is equipped with the third limiting plate, under the limiting plate effect, guarantee sheathed tube connection effect, prevent that the sleeve pipe from deviating from the reaction barrel bottom, provide the holding power for first sleeve pipe under the second supporting spring effect, make the gaseous outflow back of first activity intracavity, the first sleeve pipe of second sleeve pipe first downstream earlier, after the second sleeve pipe entered into first sleeve pipe, first sleeve pipe downstream again, enter into first activity intracavity until first sleeve pipe, make the carrier box normally remove to the reaction barrel bottom.

A first connecting block is arranged on the side wall of the stop block, a fourth movable cavity communicated with the second movable cavity is arranged on the first connecting block, a fifth through hole is formed in the side wall of the fourth movable cavity, a second connecting rope 166 is arranged on the sealing block, the other end of the second connecting rope is connected to the bottom end of the movable rod, a bottom plate 1620 at the bottom of the second sleeve is provided with a sixth through hole, the second connecting rope penetrates through the sixth through hole, and a guiding effect is provided for the second connecting rope through the sixth through hole; the sealing blocks are provided with sealing springs, and the two sealing blocks are mutually attached under the action of the sealing springs so as to seal the second through hole; a first opening is formed in the side wall of the second sleeve, a second bump 169 penetrates through the first opening, a second slider 1610 is arranged on the inner wall of the first opening, a second sliding groove matched with the second slider is formed in the bottom of the second bump, and a return spring 16101 is arranged on the second slider; a supporting plate 167 is arranged at the top of the second sleeve, a connecting pipe 43 matched with the supporting plate is arranged at the bottom of the material loading box, a first convex block is arranged on the inner wall of the connecting pipe, and a first through groove 471 matched with the first convex block is arranged on the supporting plate; the first through groove is matched with the first lug to position the material loading box, so that the first lug and the second lug are staggered when the material loading plate is loaded on the supporting plate, and the second lug is prevented from blocking the installation of the first lug; first lug and second lug are convex structure, carry the material box and drive the connecting pipe when rotating and rotate, first lug rotates along with the connecting pipe, first lug contacts with the second lug, first lug pushes second lug propelling movement to first opening in, the second lug contacts with movable rod one end, it rotates around the tie point to push the movable rod under the effect of second lug, thereby make the movable rod bottom pulling second connect the rope and remove, the second is connected the rope pulling sealed piece and is removed toward the second activity intracavity, two sealed piece phase separation make the second through-hole open, so that discharge the air current in the first activity intracavity, make and carry the material box and descend slowly, promote the contact effect of molecular sieve and solution.

The first connecting shaft penetrates through the position, close to the top, of the movable rod, and the second bump is connected with the first connecting shaft, so that the bottom of the movable rod moves by a larger distance when the movable rod contacts with the first connecting shaft, and the second connecting rope can pull the sealing block to have a sufficient movement stroke.

The side wall of the reaction barrel 1 is provided with a mounting plate 13, the mounting plate 13 is provided with a second driving motor 131, an output shaft of the second driving motor 131 is provided with a spool 132, a first connecting rope is wound on the spool 132, the top of the material receiving box 4 is provided with a wiring terminal 45, and the other end of the first connecting rope is sleeved on the wiring terminal 45; the side wall of the reaction barrel 1 is provided with an installation block 12, the installation block 12 is provided with a third movable cavity 121, a first connecting rod 14 penetrates through the third movable cavity 121, the top of the first connecting rod 14 is provided with a second movable groove, a guide wheel 19 is arranged in the second movable groove, and a first annular groove is arranged on the guide wheel; a first limiting plate 141 is arranged at the bottom of the first connecting rod 14, and a first supporting spring 142 is arranged at the bottom of the first limiting plate 141; a third movable groove is formed in the inner wall of the third movable cavity 121, a limiting block 180 is arranged in the third movable groove, and after the first sliding block 44 moves to the bottom of the first sliding groove 231, the limiting block 180 enters the third movable groove; when the first driving motor 31 drives the material carrying box 4 to rotate, the material carrying box 4 moves downwards along with the first sleeve 15, the first slider 44 moves to the bottom of the first sliding groove 231, the limiting block 180 enters the third movable groove, the first supporting spring 142 pushes the first connecting rod 14 to generate an upward movement trend, air flow is injected into the first movable cavity 160, the first sleeve 15 is pushed to move upwards by air pressure, the material carrying box 4 is pushed to move upwards by the first sleeve 15 and the second sleeve 16, the material carrying box 4 moves to the middle of the reaction barrel 1, the first supporting spring 142 pushes the first connecting rod 14 to move upwards, and the middle of the first connecting rod arches; after the reaction is finished, the discharging pipe 11 is opened to discharge the solution from the discharging pipe 11, the second driving motor 131 drives the bobbin 132 to rotate, the first connecting rope winds the bobbin 132, the first connecting rope pulls the material loading box 4 to move upwards, the material loading box 4 rises from the first through hole, and the molecular sieve in the reaction barrel 1 is taken out.

A sixth movable cavity 110 communicated with the third movable groove is arranged on the side wall of the third movable cavity, a transmission rod 120 is arranged in the sixth movable cavity, and the middle part of the transmission rod is rotatably connected to the inner wall of the sixth movable cavity; a limiting spring 1801 is arranged on the side wall of the limiting block, a third connecting rope is arranged at one end of the transmission rod, and the other end of the third connecting rope is fixedly connected to the limiting block; a through cavity is formed in the top of the sixth movable cavity, a first push rod 130 penetrates through the through cavity, a seventh movable cavity is formed in the inner wall of the through cavity, a limiting rod 1301 is arranged on the first push rod, a third supporting spring 1302 is arranged at the bottom of the limiting rod, a second annular groove 180 is formed in the top of the reaction barrel, the first push rod penetrates through the second annular groove, a fourth supporting spring 172 is arranged in the second annular groove, a movable ring 17 is arranged at the top of the fourth supporting spring, and when the first sliding block moves to the bottom of the first sliding groove, the movable ring moves towards the second annular groove; after the molecular sieve is placed in the material carrying box, the material carrying box is placed in the reaction barrel, the first driving motor drives the material carrying box to rotate, the first lug is in contact with the second lug to push the movable rod to rotate, the second connecting rope pulls the sealing block to move to open the second through hole, the second through hole is opened to discharge airflow in the first movable cavity, the second sleeve pipe moves downwards, the first sliding block moves downwards along with the material carrying box to the bottom of the first sliding chute, the movable ring moves towards the bottom of the second circular chute and is in contact with the top of the first push rod, the first push rod is pushed to move downwards under the action of the movable ring, the first push rod is in contact with one end of the transmission rod, the transmission rod rotates around the connecting point, the other end of the transmission rod moves upwards, the third connecting rope pulls the limiting block to move towards the sixth movable cavity, the limiting block is separated from the first limiting plate to make the first connecting rod move upwards under the action of the first supporting spring, so that the first connecting rope is in a tightening state under the action of the first connecting rod, and the knotting phenomenon of the first connecting rope is avoided.

The inner wall of the reaction barrel is provided with a second connecting plate 18, the second connecting plate is provided with a fifth movable cavity 181, a movable plate 182 is arranged in the fifth movable cavity, the bottom of the movable plate is provided with a fifth supporting spring 183, the fifth movable cavity is communicated with the second annular groove, the bottom of the movable ring is provided with a fourth connecting rope 171, and the bottom end of the fourth connecting rope is fixedly connected to the movable plate; a sixth through hole is formed in the bottom of the first sliding chute, a second push rod 232 penetrates through the sixth through hole, a first push plate 233 is arranged at the top of the second push rod, and a sixth supporting spring 234 is arranged at the bottom of the second push plate; a seventh through hole corresponding to the sixth through hole is formed in the bottom of the fifth movable cavity; when the first sliding block moves to the bottom of the first sliding groove, the first sliding block is pressed on the first push plate, the first push plate pushes the second push rod to move downwards, the second push rod is inserted into the seventh through hole, the movable plate is pushed to move downwards under the action of the second push rod, the movable plate pulls the fourth connecting rope to move downwards, the fourth connecting rope pulls the movable ring to move downwards, the movable ring pushes the first push rod to move downwards, the first push rod moves downwards to be in contact with the transmission rod, the limiting block enters the sixth movable cavity, so that the first connecting rod is lifted when the first sleeve and the second sleeve push box push the material carrying box to move upwards, the first connecting rope is always in a tight state, the first connecting rope is directly wound on a spool, and knotting of the first connecting rope is prevented.

The stopper top is equipped with the cambered surface, and when the limiting plate down moved from the top, first limiting plate bottom surface contacted with the cambered surface at stopper top, can directly with stopper propelling movement to third activity inslot under the cambered surface effect, make the natural removal of first limiting plate to the stopper opposite side, make head rod automatic re-setting.

The bottom of the material loading box is provided with an eighth through hole, the inner wall of the eighth through hole is provided with a fourth movable groove, a third connecting plate is arranged in the fourth movable groove, the third connecting plate is provided with a second connecting rod 42, the second connecting rod is provided with a plurality of stirring rods 421, the bottom of the third connecting plate is provided with a third connecting rod 422, the supporting plate is provided with a connecting groove matched with the third connecting rod, the inner wall of the connecting groove is provided with a fifth movable groove, the fifth movable groove is internally provided with a movable block 162, the side wall of the movable block is provided with a first connecting spring 163, the movable block is provided with a second connecting block 164, the second connecting block is provided with a third connecting block 165, and the third connecting rod is provided with a limiting groove; a sixth movable groove 1650 is formed in the bottom of the connecting groove, a seventh supporting spring 1640 is arranged in the sixth movable groove, and a second push plate 1630 is arranged at the top of the seventh supporting spring; the diameter of the connecting groove is larger than that of the third connecting rod; when the material loading box is placed into the reaction barrel, the connecting pipe is sleeved on the supporting disc, the third connecting rod is inserted into the connecting groove and is in contact with the second push plate, the third connecting rod pushes the second push plate to move downwards, the second push plate enters the sixth movable groove, the second push plate is moved away from one side of the movable block, the first connecting spring pushes the movable block to move towards the middle of the connecting groove, and the third connecting block is embedded into the limiting groove, so that the third connecting rod and the supporting disc are in rotation stopping fit; when the first driving motor drives the first connecting plate to rotate, the material loading box rotates along with the first connecting plate, and the third connecting rod is in a static state under the action of the supporting plate, so that the material loading box rotates relative to the stirring rod, the molecular sieve in the material loading box is pushed to move by stirring, the molecular sieve is prevented from being stacked, and the molecular sieve is better contacted with the solution; through second push pedal and movable block setting, make the third connecting rod change and pack into the spread groove in, no matter what kind of angle the third connecting rod packs into the spread groove in, the third connecting block must insert the spacing inslot after carrying the material box and rotating, makes third connecting rod and supporting disk form and ends the cooperation of changeing to turn the molecular sieve in carrying the material box.

A second connecting shaft 191 is arranged on each of two sides of the guide wheel, an eighth movable cavity 192 is arranged on each second connecting shaft, a second opening is formed in the top of each eighth movable cavity, a third push plate 193 is arranged on the top of each eighth movable cavity, an eighth supporting spring is arranged on each third push plate, a ninth movable cavity 195 communicated with each eighth movable cavity is arranged on each first ring groove, a fourth connecting rod 194 is arranged in each ninth movable cavity, and a third ring groove 1941 is formed in each fourth connecting rod; a tenth movable cavity 143 is formed in the first connecting rod, a fourth connecting plate 146 and a fifth connecting plate 145 are arranged in the tenth movable cavity, a second connecting spring is arranged at the bottom of the fourth connecting plate, the fifth connecting plate is arranged at the bottom of the second connecting spring, a second through groove is formed in the fourth connecting plate, a fourth push plate 1451 matched with the second through groove is arranged on the fifth connecting plate, and a seventh movable groove matched with the fourth push plate is formed in the top of the tenth movable cavity; a cushion block 144 is arranged in the tenth movable cavity, a push block 1452 is arranged at the bottom of the fifth connecting plate, and an eighth movable groove 1441 matched with the push block is arranged on the cushion block; a third through groove 1431 matched with the push block is formed in the bottom of the tenth movable cavity, and the push block can be inserted into the eighth movable cavity through the third through groove; after the material loading box is taken out of the reaction barrel by the first connecting rope, the first connecting rope is taken out from the terminal end, so that the material loading box can be directly and completely taken out of the reaction barrel, and the molecular sieve on the material loading box can be conveniently recycled; after the first connecting rope is taken out of the material loading box, a fourth push plate is pushed to one end of a seventh movable groove, the fourth push plate drives a fourth connecting plate and a fifth connecting plate to move, the fifth connecting plate is moved away from the top of a cushion block, a second connecting spring pushes the fifth connecting plate to move downwards, a push block moves downwards along with the fifth connecting plate, the push block is inserted into a second opening, the third push plate is pushed to move downwards under the action of the push block, airflow in an eighth movable cavity enters a ninth movable cavity, a fourth connecting rod is pushed out of the ninth movable cavity under the action of air pressure, a third annular groove extends out of the top of the ninth movable cavity, the first connecting rope at one end taken out of a wiring terminal is wound in the third annular groove, the first connecting rope is fixed, the first connecting rope is prevented from being wound on a wire roller completely, and the first connecting rope can be found quickly when the reaction barrel is used; when the first connecting rope is reloaded on the material loading box, the first connecting rope is taken out of the third ring groove, the fourth push plate is pulled upwards, the fourth push plate drives the fifth connecting plate to move upwards, the fifth connecting plate is pushed to the top of the cushion block along the seventh movable groove after rising to the top of the cushion block, and the cushion block is utilized to provide supporting force for the fifth connecting plate; the third push pedal up-moves under eighth supporting spring effect, and the air current of ninth activity intracavity enters into the eighth activity intracavity, and the fourth connecting rod down-moves, makes the fourth connecting rod enter into the ninth activity intracavity, and first connecting rope inlays in first annular to be fixed a position to the movement track of first connecting rope, make the material carrying box change under the effect of first connecting rope and take out from the reaction barrel.

The first cover plate is provided with an installation frame 3, the first driving motor is arranged on the installation frame, the bottom of the installation frame is provided with a third sliding block, the first cover plate is provided with a third sliding groove matched with the third sliding block, the third sliding block is provided with a sixth connecting plate 33, one end of the sixth connecting plate is provided with a threaded hole, a screw 34 penetrates through the threaded hole, and the installation frame is fixed on the first cover plate under the action of the screw; the output shaft of the first driving motor is provided with a driving wheel 32 matched with the driving ring, the top of the driving ring is provided with a third cover plate 21, and the reaction barrel can be sealed as required.

When preparing the esterified substance, putting the hydroxylated substance and acetic acid into a reaction barrel, operating a heating block, driving a transmission ring to rotate by a first driving motor, and stirring the solution by a first connecting plate to normally perform the esterification reaction; inputting airflow into the first movable cavity through the air conveying pipe, and enabling the first sleeve and the second sleeve to move upwards under the action of the airflow to enable the second sleeve to move to the highest position; putting the molecular sieve into a material carrying box, covering a second cover plate, connecting a first connecting rope to a connecting terminal, temporarily stopping a first driving motor, embedding a first sliding block into a first sliding groove, moving the material carrying box downwards to the top of a second sleeve, driving a transmission ring to continuously rotate by the first driving motor, placing the material carrying box on a supporting plate, driving a first lug to rotate when the material carrying box rotates, enabling the first lug to be in contact with a second lug, enabling a sealing block to discontinuously move, enabling a second through hole to discontinuously start, gradually discharging airflow from a second air delivery passage, gradually descending the second sleeve, slowly moving the material carrying box downwards after losing the supporting force, moving the material carrying box downwards to pull the first connecting rope to rotate from a wire roller, enabling the material carrying box to rotate at different heights in a reaction barrel, and increasing the contact effect of the molecular sieve and a solution; when the material loading box is lowered to the lowest position, the first sliding block moves to the bottom of the first sliding groove, the second push rod pushes the movable plate to move downwards, the movable plate pulls the movable ring to move downwards, the movable ring pushes the first push rod to move downwards, the first push rod pushes the transmission rod to rotate to pull the limiting block into the third movable groove, the first supporting spring pushes the first connecting rod to move upwards, and the guide wheel abuts against the first connecting rope; after the material carrying box rotates at the bottom of the reaction barrel for a specified time, airflow is introduced into the first movable cavity again through the gas pipe, the first sleeve and the second sleeve are dragged to move upwards under the action of air pressure after the airflow in the first movable cavity is increased, the second sleeve pushes the material carrying box to move upwards, the first connecting rope does not extrude the first connecting rod any more when the material carrying box moves, the first connecting rod moves upwards to abut against the first connecting rope, the first connecting rope is in a tightened state, and the first connecting rope is prevented from knotting; the material loading box is pushed to ascend by utilizing the ascending of the first sleeve and the second sleeve, so that the burden of the first driving motor is reduced, the installation of control is reduced, and the cost of the reaction barrel is reduced; after the second sleeve pipe rises to the highest point, the material carrying box continues to rotate until the reaction in the reaction barrel is finished; after reaction contact is carried out in the reaction barrel, the discharge pipe is opened, solution is discharged from the discharge pipe, the first driving motor drives the wire roller to rotate, the first connecting rope pulls the material carrying box to move upwards, the material carrying box is pulled out of the reaction barrel to provide limit for the top of the material carrying box, the wire roller rotates to pull the first connecting rope until the first connecting rope is pulled to be in a tightened state, the tightened first connecting rope pushes the first connecting rod to move downwards, the first connecting rod moves downwards to enable the first limiting plate to be in contact with the cambered surface at the top of the limiting block, the first limiting plate pushes the limiting block to enter the third movable groove, the first limiting plate moves to the position below the limiting block, the first connecting rod is fixed in the third movable cavity again, and resetting of the first connecting rod is completed; the material loading box is taken out of the reaction barrel, the first connecting rope is taken out of the wiring end, the guide wheel is rotated, a fourth connecting rod on the guide wheel is rotated to the upward state, the second opening is rotated to the lower part of the third through groove, a fourth push plate is pushed along the seventh movable groove, the fourth push plate drives the fourth connecting plate and the fifth connecting plate to move, the push block pushes the third push plate to move downwards, the fourth connecting rod is pushed out of the ninth movable cavity, so that the first connecting rope is wound in the third annular groove to be fixed, and the first connecting rope is found quickly when the material loading box is used next time.

First driving motor, the second driving motor of this application are the schematic diagram, and its concrete structure is the same with the motor structure among the prior art.

Example 2:

a process for the esterification of a hydroxylate comprising: adding dehydrated yellow brown hydroxide 25.5g with water content of 2% and 20.1ml of 93% recovered acetic acid into a reaction barrel, heating to 122 deg.C for reaction, and dehydrating for 7.0 h. 5.0g of 3A molecular sieve was added to the flask and the reaction was continued at 120 ℃ under reflux for 4 h. Cooling to 60-70 ℃, filtering, and removing the molecular sieve to obtain 40.21g of yellow brown esterified liquid. The HPLC detection shows that the product purity is 97.5% and the product yield is 97.0%.

The molecular sieve obtained by separation is washed by recycling acetic acid with the concentration of 98% at the temperature of 70 ℃, glacial acetic acid is added at the temperature of 120 ℃, the mixture is filtered and separated after being subjected to heat preservation and reflux for 5 hours, the obtained molecular sieve is regenerated for later use, and the acetic acid washing solution and the acetic acid regeneration solution which are filtered and separated can be recycled.

The reaction barrel structure is the same as that of example 1.

Example 3:

a process for the esterification of a hydroxylate comprising: adding dehydrated yellow brown hydroxylate 25.5g with water content of 2% and 98% recycled acetic acid 38.4ml into a reaction barrel, heating to 130 deg.C for reaction, and dehydrating for 5 hr. 1.3g of 3A molecular sieve was added to the flask and the reaction was continued at 120 ℃ under reflux for 3.5 h. Cooling to 60-70 ℃, filtering, removing the molecular sieve, and removing acetic acid under reduced pressure to obtain 30.95g of product yellow brown esterified liquid. The HPLC detection shows that the product purity is 97.7 percent and the product yield is 97.2 percent.

Washing the separated molecular sieve with 91% recovered acetic acid at 80 ℃, filtering, separating, washing with water for three times, drying and regenerating in a microwave dryer, and recycling the filtered acetic acid washing liquid.

The reaction barrel structure is the same as that of example 1.

Example 4:

a process for the esterification of a hydroxylate comprising: 20.4g of a deep blue hydroxylate containing 2% of water, 10ml of glacial acetic acid and 35ml of 98% recycled acetic acid are added into a reaction barrel, and after heating to 132 ℃, dehydration reaction is carried out for 5 hours. 4.0g of 5A molecular sieve from example 1 after regeneration was added to a three-necked flask and the reaction was continued under reflux at 120 ℃ for 3.0 h. Cooling to 50-60 ℃, filtering, removing the molecular sieve, and removing acetic acid under reduced pressure to obtain 26.74g of the product, namely, the dark blue esterified liquid. The HPLC detection shows that the product purity is 97.8 percent and the product yield is 97.1 percent.

The molecular sieve obtained by separation is soaked in glacial acetic acid for 4 hours at 105 ℃ after being washed by 98% recovered acetic acid at 70 ℃, the molecular sieve is filtered and separated, the obtained molecular sieve is regenerated for later use, and the acetic acid washing liquid and the acetic acid regeneration liquid which are filtered and separated can be recycled.

The reaction barrel structure is the same as that in example 1

Example 5:

a process for the esterification of a hydroxylate comprising: 22.0g of a deep blue hydroxylate containing 10% of water and 59.7ml of glacial acetic acid are added into a reaction barrel, the mixture is heated to 140 ℃ for reaction, and dehydration reaction is carried out for 4 hours. 4.0g of 5A molecular sieve was added to the flask and the reaction was continued at 130 ℃ for 1.0h under total reflux. Cooling to 50-60 ℃, filtering, removing the molecular sieve, and removing acetic acid under reduced pressure to obtain 27.31g of the product, namely the dark blue esterified liquid. The HPLC detection shows that the product purity is 98.1% and the product yield is 97.5%.

The molecular sieve obtained by separation is washed by 98% recovered acetic acid (from the acetic acid regeneration liquid recycled in the acetic acid regeneration process of example 1) at 80 ℃, filtered and separated, washed by three times of water, put into a microwave dryer for drying and regeneration, and the regenerated molecular sieve is reserved.

The reaction barrel structure is the same as that of example 1.

Example 6:

a process for the esterification of a hydroxylate comprising: 22.0g of a deep blue hydroxylate containing 10% of water and 9.4ml of glacial acetic acid are added into a reaction barrel, the mixture is heated to 120 ℃ for reaction, and dehydration reaction is carried out for 7 hours. 1.0g of 3A molecular sieve was added to the flask and the reaction was continued at 118 ℃ for 5.0h under total reflux. Cooling to 50-60 ℃, filtering and removing the molecular sieve to obtain 27.48g of the product, namely the dark blue esterified liquid. The HPLC detection shows that the product purity is 96.9 percent and the product yield is 96.0 percent.

The molecular sieve obtained by separation is washed by recovered acetic acid (from the acetic acid washing liquid recycled in the acetic acid washing process of the embodiment 1) with the temperature of 80 ℃ and 95 percent, and after filtration and separation, the molecular sieve is subjected to heat preservation and reflux for 1 hour by glacial acetic acid at the temperature of 120 ℃, then filtration and separation are carried out, the obtained molecular sieve is regenerated for later use, and the filtered and separated acetic acid washing liquid and the acetic acid regeneration liquid can be recycled.

Example 7:

a process for the esterification of a hydroxylate comprising: 22.0g of jasper hydroxide containing 10% of water and 51.6ml of 93% recovered acetic acid were added to a reaction tank, and after heating to 125 ℃, dehydration reaction was carried out for 5.5 hours. 4.0g of 10X type molecular sieve was added to the flask and the reaction was continued at 120 ℃ under reflux for 2.5 h. Cooling to 50-60 ℃, filtering, removing the molecular sieve, and removing acetic acid under reduced pressure to obtain 27.67g of ruby esterified liquid. The HPLC detection shows that the product purity is 97.7 percent and the product yield is 96.9 percent.

Washing and filtering the separated molecular sieve with glacial acetic acid at 80 ℃, soaking the molecular sieve with glacial acetic acid for 4 hours at 110 ℃, filtering and separating to obtain the molecular sieve for later use, wherein the acetic acid washing liquid and the acetic acid regeneration liquid which are subjected to filtering and separation can be recycled.

The reaction barrel structure is the same as that of example 1.

Claims

1. A process for esterifying a hydroxylated compound, comprising: the method comprises the following steps:

adding dehydrated hydroxylate and acetic acid into a reaction barrel (1), wherein the dehydrated hydroxylate and the acetic acid are fed according to the mol ratio of the contained hydroxyethyl to the acetic acid of 1:1-1: 10; heating while stirring, and promoting esterification reaction by rectification and dehydration when the temperature is raised to 110-150 ℃;

adding a molecular sieve with a channel pore diameter smaller than 9A into the reaction barrel (1) after the esterification reaction, wherein the reaction after process means that the conversion rate of the dehydrated hydroxylate is more than 80%, the adding mass of the molecular sieve is 1-25% of the mass of the dehydrated hydroxylate, and continuing the reaction under the reflux state of 110-140 ℃ until the reaction is finished;

after the esterification reaction is finished, separating the product from the molecular sieve to obtain high-purity esterified liquid;

carrying out regeneration and activation treatment on the separated molecular sieve, and recycling the regenerated and activated molecular sieve;

a first cover plate (2) is arranged at the top of the reaction barrel (1) in the step a, a first through hole is formed in the first cover plate (2), a material carrying box (4) corresponding to the first through hole is arranged in the reaction barrel (1), a first movable groove is formed in the inner wall of the first through hole, a connecting ring (22) is arranged in the first movable groove, a first connecting plate (23) is arranged at the bottom of the connecting ring (22), a first sliding groove (231) is formed in the first connecting plate (23), a first sliding block (44) matched with the first sliding groove (231) is arranged on the material carrying box (4), a transmission ring (221) is arranged on the connecting ring (22), and a first driving motor (31) used for driving the transmission ring (221) to rotate is arranged on the first cover plate (2); a first movable cavity (160) is arranged at the bottom of the reaction barrel (1), a first sleeve (15) penetrates through the first movable cavity (160), a second sleeve (16) penetrates through the first sleeve (15), the carrier box (4) is arranged at the top of the second sleeve (16), and when the carrier box (4) rotates, the first sleeve (15) moves into the first movable cavity (160); a discharge pipe (11) is arranged at the bottom of the reaction barrel (1), and a heating block is arranged in the reaction barrel (1); after putting hydroxylate and acetic acid into the reaction barrel (1), a first driving motor (31) drives a transmission ring (221) to rotate, a first connecting plate (23) rotates in the reaction barrel (1), and a heating block heats the solution; putting a molecular sieve on a material carrying box (4), putting the material carrying box (4) into a reaction barrel (1), allowing the material carrying box (4) to fall to the top of a second sleeve (16) along a first connecting plate (23), continuously driving a transmission ring (221) to rotate by a first driving motor (31), driving the material carrying box (4) to rotate by the first connecting plate (23), allowing the molecular sieve to be in contact with a solution, allowing a first sleeve (15) to move into a first movable cavity (160) when the material carrying box (4) rotates, allowing the material carrying box (4) to move downwards along with the movement of the first sleeve (15), and allowing the molecular sieve to move from the middle of the reaction barrel (1) to the bottom of the reaction barrel (1); after the reaction is finished, the discharge pipe (11) is opened, the solution is discharged from the discharge pipe (11), the material carrying box (4) is pushed upwards, the material carrying box (4) is taken out of the reaction barrel (1), and the molecular sieve in the reaction barrel (1) is recovered.

2. The esterification process according to claim 1, wherein: in the step d, the regeneration and activation treatment method of the molecular sieve is a heating regeneration method, a replacement regeneration method or a combination of the heating regeneration method and the replacement regeneration method;

3. The esterification process according to claim 1, wherein: in the step d, the acetic acid washing liquid used for washing the molecular sieve is hot acetic acid with the mass concentration of more than 90%.

4. The esterification process according to claim 1, wherein: in the step a, the acetic acid is glacial acetic acid and/or acetic acid with the mass concentration of more than 90%.

5. The esterification process according to claim 1, wherein: in the step a, the water content of the dehydrated hydroxylate is less than 10%.

6. The esterification process according to claim 1, wherein: a first air delivery passage (140) and a second air delivery passage (160) are arranged on the side wall of the first movable cavity (160), the first air delivery passage (140) is communicated with an air delivery pipe (150), an installation cavity is arranged in the second air delivery passage (160), a stop block (170) is arranged in the installation cavity, a second through hole is formed in the stop block (170), a second movable cavity is also arranged on the stop block (170), and a sealing block (1701) matched with the second through hole is arranged in the second movable cavity; a movable rod (161) is arranged in the second sleeve (16), a first connecting shaft (162) penetrates through the movable rod (161), the first connecting shaft (162) is connected to the inner wall of the second sleeve (16), a first bump (431) for driving the movable rod (161) to rotate is arranged at the bottom of the carrier box (4), and when the movable rod (161) rotates, the sealing block (1701) moves into the second movable cavity; after the molecular sieve is placed into the carrier box (4), the carrier box (4) descends onto the second sleeve (16), the first driving motor (31) drives the carrier box (4) to rotate, the first bump (431) intermittently pushes the movable rod (161) to rotate around the first connecting shaft (162) when rotating along with the carrier box (4), the sealing block (1701) moves into the second movable cavity when rotating along with the movable rod (161), airflow in the first movable cavity (160) is discharged from the second air conveying passage (150) when the second through hole is opened, the second sleeve (16) moves downwards after airflow in the first movable cavity (160) is reduced, the carrier box (4) moves downwards along with the second sleeve (16), the first driving motor (31) continuously drives the carrier box (4) to rotate, the first connecting plate (23) stirs an esterification solution, and esterification of hydroxylation is completed.

7. The esterification process according to claim 1, wherein: the side wall of the reaction barrel (1) is provided with a mounting plate (13), the mounting plate (13) is provided with a second driving motor (131), an output shaft of the second driving motor (131) is provided with a spool (132), a first connecting rope is wound on the spool (132), the top of the material receiving box (4) is provided with a wiring end (45), and the other end of the first connecting rope is sleeved on the wiring end (45); the side wall of the reaction barrel (1) is provided with a mounting block (12), the mounting block (12) is provided with a third movable cavity (121), a first connecting rod (14) penetrates through the third movable cavity (121), the top of the first connecting rod (14) is provided with a second movable groove, and a guide wheel (19) is arranged in the second movable groove; a first limiting plate (141) is arranged at the bottom of the first connecting rod (14), and a first supporting spring (142) is arranged at the bottom of the first limiting plate (141); a third movable groove is formed in the inner wall of the third movable cavity (121), a limiting block (180) is arranged in the third movable groove, and when the first sliding block (44) moves to the bottom of the first sliding groove (231), the limiting block (180) enters the third movable groove; when the first driving motor (31) drives the material carrying box (4) to rotate, the material carrying box (4) moves downwards along with the first sleeve (15), the first sliding block (44) moves to the bottom of the first sliding groove (231), the limiting block (180) enters the third movable groove, the first supporting spring (142) pushes the first connecting rod (14) to generate an upward movement trend, air flow is injected into the first movable cavity (160), air pressure pushes the first sleeve (15) to move upwards, the first sleeve (15) and the second sleeve (16) push the material carrying box (4) to move upwards, the material carrying box (4) moves to the middle of the reaction barrel (1), the first supporting spring (142) pushes the first connecting rod (14) to move upwards, and the middle of the first connecting rope arches; after the reaction is finished, the discharging pipe (11) is opened to discharge the solution from the discharging pipe (11), the second driving motor (131) drives the bobbin (132) to rotate, the first connecting rope winds the bobbin (132), the first connecting rope pulls the carrier box (4) to move upwards, the carrier box (4) rises from the first through hole, and the molecular sieve in the reaction barrel (1) is taken out.