CN213388443U

CN213388443U - Reinforcing system for preparing 1, 4-butanediol from butadiene and acetic acid

Info

Publication number: CN213388443U
Application number: CN201921477713.1U
Authority: CN
Inventors: 张志炳; 周政; 孟为民; 王宝荣; 杨高东; 罗华勋; 张锋; 李磊; 杨国强; 田洪舟; 曹宇
Original assignee: Nanjing Institute of Microinterface Technology Co Ltd
Current assignee: Nanjing Institute of Microinterface Technology Co Ltd
Priority date: 2019-09-06
Filing date: 2019-09-06
Publication date: 2021-06-08
Anticipated expiration: 2029-09-06

Abstract

The utility model is suitable for the technical field of butanediol production, and provides a strengthening system and a strengthening process for preparing 1, 4-butanediol from butadiene and acetic acid, which comprises a diacetyl oxidation reactor, a first rectifying tower, a hydrogenation reaction device, a hydrolysis reactor and a second rectifying tower which are connected correspondingly in sequence, and also comprises an intelligent control device; the hydrogenation reaction device comprises a main reaction kettle and an auxiliary reaction kettle; the inlet end of the main reaction kettle is connected with a hydrogen tank, the hydrogen tank is connected with a micro-interface generator arranged in the main reaction kettle, and the micro-interface generator breaks hydrogen into micron-sized bubbles with the diameter of more than or equal to 1 mu m and less than 1 mm; the outlet end of the secondary reaction kettle is connected with a catalyst recoverer; the intelligent control device is electrically connected with the reaction parameter controller. Therefore, the utility model discloses can improve the output of reaction efficiency and 1, 4-butanediol under the unchangeable circumstances such as catalyst, material ratio, reduce energy consumption, material consumption and water consumption, realize intelligent operation simultaneously.

Description

Reinforcing system for preparing 1, 4-butanediol from butadiene and acetic acid

Technical Field

The utility model relates to a production technical field of butanediol especially relates to a system is reinforceed to butadiene and acetic acid preparation 1, 4-butanediol.

Background

1, 4-butanediol is one of methanol series product chains and is an important basic organic chemical and fine chemical raw material, a manufacturer generally does not use 1, 4-butanediol as a final product in the process of producing 1, 4-butanediol, but pays attention to the extension of a 1, 4-butanediol derivative, and the 1, 4-butanediol derivative is a fine chemical product with higher added value and is widely used as a solvent, a medicine, a cosmetic, a plasticizer, a curing agent, a pesticide, an herbicide, foamed artificial leather, fiber, engineering plastics and the like; because of the wide application and large consumption of 1, 4-butanediol, the production technology of 1, 4-butanediol needs to be improved continuously.

The production method of the 1, 4-butanediol mainly comprises the following steps: (1) a Reppe method (alkynal method) using formaldehyde and acetylene as raw materials; (2) butadiene acetoxylation with butadiene and acetic acid as raw materials; (3) a propylene oxide process using propylene oxide/propylene alcohol as a raw material; (4) davy method using n-butane/maleic anhydride as a raw material.

Butadiene acetoxylation is a three-step process, namely firstly butadiene reacts with acetic acid and oxygen for acetylation to generate 1, 4-diacetyloxybutene and a byproduct of 3, 4-diacetyloxybutene; then the 1, 4-diacetoxybutene is catalyzed and hydrogenated to generate the 1, 4-diene acetoxy butane, and finally hydrolysis reaction is carried out to obtain the 1, 4-butanediol.

The reaction in the hydrogenation section is to mix 1, 4-diacetoxybutene and hydrogen to generate 1, 4-diene acetoxybutane, and bubbles are easily formed in the process of mixing hydrogen and a 1, 4-diacetoxybutene solution, so that the hydrogen and the solution are not uniformly mixed, the reaction of the hydrogen and the 1, 4-diacetoxybutene is insufficient, the yield of the 1, 4-diene acetoxybutane is reduced, and the yield of the 1, 4-butanediol is directly influenced.

In the prior art, in order to improve the mixing effect of hydrogen and 1, 4-diacetyloxy butene and enable the reaction to be more sufficient so as to improve the yield of 1, 4-butanediol, a hydrogenation working section generally adopts a stirring or bubbling mode, while a traditional stirring paddle or a bubbling tower reactor can only generate turbulent eddies with the size of centimeters or millimeters, therefore, even if the power of a stirring motor is increased, most energy of the energy can only be converted into heat energy and can not be converted into surface energy required by small bubble generation, so that the hydrogen and the 1, 4-diacetyloxy butene are not uniformly mixed; meanwhile, in order to further promote the reaction to fully progress, the dosage of the catalyst is increased in the hydrogenation process.

However, the hydrogenation section of the prior art still has the following problems:

1. in order to promote the reaction in the hydrogenation section, manufacturers increase the amount of catalyst, and increase the production cost.

2. Because the amount of the catalyst in the hydrogenation section is increased, the incomplete reaction of the catalyst often occurs, the waste of the residual catalyst is caused, and the normal production of a subsequent system is influenced after the residual catalyst enters the subsequent system.

3. In the process of mixing and stirring hydrogen and a 1, 4-diacetoxybutylene solution, a stirring dead angle still exists, and the problems of uneven stirring of hydrogen, a catalyst and the solution still exist, so that the reaction in a hydrogenation section is insufficient, and the yield of 1, 4-butanediol is influenced.

4. The stirring cannot or cannot completely break the bubbles of the hydrogen gas, and the hydrogen gas cannot be uniformly mixed with the solution.

In view of the above, the prior art is obviously inconvenient and disadvantageous in practical use, and needs to be improved.

SUMMERY OF THE UTILITY MODEL

Aiming at the defects, the utility model aims to provide a system is reinforceed to butadiene and acetic acid preparation 1, 4-butanediol, it can realize under the unchangeable circumstances such as catalyst, material ratio that reaction efficiency improves at double, makes 1, 4-butanediol's output more, and energy consumption, material consumption, water consumption reduce by a wide margin, realizes intelligent operation simultaneously.

In order to achieve the purpose, the utility model provides an enhancement system for preparing 1, 4-butanediol from butadiene and acetic acid, which comprises a diacetoxy reactor, a first rectifying tower, a hydrogenation reaction device, a hydrolysis reactor and a second rectifying tower which are correspondingly connected in sequence; the intelligent control device is further included.

The hydrogenation reaction device comprises a hydrogenation reaction kettle, and the hydrogenation reaction kettle comprises a main reaction kettle and an auxiliary reaction kettle which are connected with each other; and the outlet end of the secondary reaction kettle is connected with a catalyst recoverer, and the catalyst recoverer is connected with the hydrolysis reactor.

The micro-interface generator is arranged at the bottom end inside the main reaction kettle and used for crushing reactant hydrogen, and the diameter of the micro-scale bubbles formed by crushing is larger than or equal to 1 micrometer and smaller than 1 mm.

The inlet end of the main reaction kettle is respectively connected with a feeding pump, a catalyst feeding structure and a hydrogen tank, the hydrogen tank is connected with the micro-interface generator, and the feeding pump is connected with the first rectifying tower.

The intelligent control device is electrically connected with the reaction parameter controllers in the diacetation oxidation reactor, the first rectifying tower, the hydrogenation reaction device, the hydrolysis reactor and the second rectifying tower.

According to the utility model discloses a system is reinforceed to butadiene and acetic acid preparation 1, 4-butanediol, catalyst feeding structure includes the feeder hopper, the relative both sides in well lower part of feeder hopper are equipped with the backup pad, all be provided with the cylinder in the backup pad, the cylinder is connected and is stretched into the inside feeding baffle of feeder hopper.

According to the utility model discloses a system is reinforceed to butadiene and acetic acid preparation 1, 4-butanediol, catalyst recoverer is including connecting thrust plate and the pressure strip at the frame both ends, connect filtration between thrust plate and the pressure strip, the pressure strip is connected compact structure.

According to the utility model discloses a strengthening system of butadiene and acetic acid preparation 1, 4-butanediol, filtration includes a plurality of filter, the inside concave yield in middle part of filter, per two constitute a filter chamber between the filter.

According to the utility model discloses a butadiene and acetic acid preparation 1, 4-butanediol intensification system, the top of the tower of first rectifying column and second rectifying column all is equipped with the cooler that is used for controlling the top of the tower temperature.

According to the utility model discloses a butadiene and acetic acid preparation 1, 4-butanediol intensification system, all be equipped with the backwash pump that is used for controlling top of the tower backward flow volume on the top of the tower back flow line of first rectifying column and second rectifying column.

According to the utility model discloses a system is reinforceed to butadiene and acetic acid preparation 1, 4-butanediol, intelligent control device is connected to the catalyst recoverer.

According to the utility model discloses a butadiene and acetic acid preparation 1, 4-butanediol strengthen system, be equipped with the agitating unit who is used for accelerating the reaction rate of oxygen acetylation in the diacetyl oxidation reactor.

According to the utility model discloses a butadiene and acetic acid preparation 1, 4-butanediol intensification system, all be equipped with temperature sensor in main reation kettle and the accessory reaction cauldron.

The utility model aims at providing a strengthening system for preparing 1, 4-butanediol from butadiene and acetic acid, which is provided with a diacetation oxidation reactor, a first rectifying tower, a hydrogenation reaction device, a hydrolysis reactor and a second rectifying tower which are correspondingly connected in sequence; the hydrogenation reaction device comprises a hydrogenation reaction kettle, and the hydrogenation reaction kettle comprises a main reaction kettle and an auxiliary reaction kettle which are connected with each other; the inlet end of the main reaction kettle is respectively connected with a feeding pump, a catalyst feeding structure and a hydrogen tank, and the outlet end of the auxiliary reaction kettle is connected with a catalyst recoverer; a micro-interface generator is also arranged at the confluence position of the feeding pump and the hydrogen tank; the micro-interface generator is used for crushing reactant hydrogen, the diameter of micron-sized bubbles formed by crushing is larger than or equal to 1 mu m and smaller than 1mm, meanwhile, the micron-sized bubbles and an intermediate product 1, 4-diacetoxybutylene are mixed to form a gas-liquid emulsion, the contact area of the hydrogen and the 1, 4-diacetoxybutylene is increased, the hydrogen and the 1, 4-diacetoxybutylene are mixed more uniformly, the reaction is more complete, and the amount of the generated 1, 4-butanediol is more; the catalyst recoverer can collect the residual catalyst, so that waste is avoided, and the catalyst is prevented from influencing the normal production of a subsequent system; the utility model discloses still set up intelligent control device, realize that intelligence selects the best reaction condition, make the reaction high-efficient go on, avoid manual operation and the waste time and energy that causes. To sum up, the beneficial effects of the utility model are that: under the condition that the catalyst and the material proportion are not changed, the reaction efficiency is improved in multiples, the yield of the 1, 4-butanediol is increased, the energy consumption, the material consumption, the water consumption and the like are greatly reduced, and meanwhile, the intelligent operation is realized.

Drawings

FIG. 1 is a schematic structural view of the present invention;

FIG. 2 is a schematic diagram of the catalyst feed structure of the present invention;

FIG. 3 is a schematic view of the catalyst recoverer of the present invention;

in the figure, 1-diacetation oxidation reactor, 2-first rectifying tower, 3-hydrogenation reaction device, 31-main reaction kettle, 311-auxiliary reaction kettle; 32-feeding pump, 33-catalyst feeding structure, 331-feeding hopper, 332-feeding baffle, 333-cylinder, 334-supporting plate; 34-hydrogen tank, 35-catalyst recoverer, 351-thrust plate, 352-compacting plate and 353-filter plate; 36-a micro-interface generator; 4-hydrolysis reactor, 5-second rectifying tower.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

It should be noted that in the description of the present invention, the terms of direction or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, which are only for convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention.

Furthermore, it should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meaning of the above terms in the present invention can be understood by those skilled in the art according to specific situations.

Referring to fig. 1, the utility model provides a system is reinforceed to butadiene and acetic acid preparation 1, 4-butanediol, including the diacetyl oxidation reactor 1, first rectifying column 2, hydrogenation device 3, hydrolysis reactor 4 and the second rectifying column 5 that correspond the connection in proper order, still include intelligent control device.

The diacetyl oxidation reactor 1 and the diacetyl oxidation reactor 1 mainly have the functions of carrying out the acetylation reaction on butadiene, acetic acid and oxygen serving as raw materials under the action of an acetylation catalyst to prepare the 1, 4-diacetyloxy butene. In the utility model, a stirring device is arranged in the diacetation oxidation reactor 1 to accelerate the reaction speed of the acetylation reaction; the stirring device can be a motor driving the stirring shaft to rotate, the stirring shaft is provided with a stirring paddle, and the stirring device can also be a submersible stirring machine.

The first rectifying tower 2 and the first rectifying tower 2 are mainly used for separating 1, 4-diacetoxybutene and a byproduct 3, 4-diacetoxybutene, removing other impurities and avoiding the system complexity.

Because diacetyl oxidation reactor 1 and first rectifying column 2 are the ripe equipment among the prior art, even the utility model discloses do not specifically describe to two above devices, the preparation work of 1, 4-diacetoxybutene also can be realized according to prior art to the technical staff in the field, consequently, the utility model discloses no longer describe repeatedly to diacetyl oxidation reactor 1 and first rectifying column 2.

The hydrogenation reaction device 3, the function of the hydrogenation reaction device 3 is to react hydrogen with 1, 4-diacetyloxy butene to obtain 1, 4-diacetyloxy butane in the presence of a hydrogenation catalyst. The hydrogenation reaction device 3 comprises a hydrogenation reaction kettle, and the hydrogenation reaction kettle comprises a main reaction kettle 31 and an auxiliary reaction kettle 311 which are connected with each other; the outlet end of the secondary reaction kettle 311 is connected with a catalyst recoverer 35, and the catalyst recoverer 35 is connected with the hydrolysis reactor 4; the inside bottom of main reation kettle 31 is equipped with micro-interface generator 36, and the entry end of main reation kettle 31 is connected feed pump 32, catalyst feed structure 33 and hydrogen jar 34 respectively, and micro-interface generator 36 is connected to hydrogen jar 34, and feed pump 32 is connected first rectifying column 2.

In the using process, a hydrogenation catalyst is added into the main reaction kettle 31 through the

catalyst feeding structure

33, and 1, 4-diacetyloxybutene is conveyed into the main reaction kettle 31 through the feeding pump 32; in the process of conveying hydrogen to the main reaction kettle 31, the hydrogen tank 34 firstly enters the micro-interface generator 36 at the bottom end, the micro-interface generator 36 converts the pressure energy of the hydrogen into bubble surface energy and transmits the bubble surface energy to the hydrogen, so that the hydrogen is crushed to form micron-sized bubbles with the diameter being more than or equal to 1 mu m and less than 1mm, the contact area of the hydrogen and the 1, 4-diacetoxybutylene is increased, the thickness of a liquid film is reduced, and the contact resistance of the hydrogen and the 1, 4-diacetoxybutylene is reduced; micron-sized bubbles on the hydrogen are discharged from the micro-interface generator 36, enter the main reaction kettle 31, meet with the 1, 4-diacetyloxy butylene and the hydrogenation catalyst, and are fully mixed to form a gas-liquid emulsion under the action of a stirrer, so that the reaction is more sufficient, and the amount of the generated 1, 4-diacetyloxy butane is more; 1, 4-diacetoxybutane is obtained.

Because the boiling points of the reactant 1, 4-diacetoxybutene and the product 1, 4-diacetoxybutane are very close, the separation of two compounds by distillation is very difficult, therefore, the utility model uses a two-stage hydrogenation process, the first stage is carried out in the main reaction kettle 31, the reaction temperature is 70-120 ℃, 80-95% of the reactant 1, 4-diacetoxybutene can be converted into 1, 4-diacetoxybutane; the second stage is carried out in a secondary reaction kettle 311, the materials in the main reaction kettle 31 are introduced into the secondary reaction kettle 311 after reaction, the reaction temperature is 90-160 ℃, and the residual reactant 1, 4-diacetoxybutene can be converted to generate 1, 4-diacetoxybutane; temperature sensors are arranged in the main reaction kettle 31 and the auxiliary reaction kettle 311 and are connected with an intelligent control device.

It is understood that the micro-interface generator 36 of the present invention can also be used in other multi-phase reactions, such as micro-mixing, micro-nano-interface, micro-interface, micro-bubble biochemical reactor or micro-bubble bioreactor, using micro-mixing, micro-fluidization, micro-bubble fermentation, micro-bubble bubbling, micro-bubble mass transfer, micro-bubble reaction, micro-bubble absorption, micro-bubble oxygenation, micro-bubble contact, etc. to form multi-phase micro-mixed flow, multi-phase micro-nano flow, multi-phase emulsified flow, multi-phase micro-structured flow, gas-liquid-solid micro-mixed flow, gas-liquid-solid micro-nano flow, gas-liquid-solid emulsified flow, gas-liquid-solid micro-structured flow, micro-bubbles, micro-micron-sized bubble flow, micro-foam flow, micro-gas-liquid flow, micro-nano-emulsified flow, micro-flow, micro-bubble flow, The multiphase fluid formed by micron-sized particles such as micro-nano bubbling and micro-nano bubbling flow or the multiphase fluid formed by micro-nano particles (micro-interface fluid for short) effectively increases the phase boundary mass transfer area between a gas phase and/or a liquid phase and/or a solid phase in the reaction process.

Referring to fig. 2, in the present invention, the catalyst feeding structure 33 includes an inverted cone-shaped feeding hopper 331 for storing the solid catalyst. Support plates 334 are arranged on two opposite sides of the middle lower part of the feed hopper 331, air cylinders 33 are arranged on the support plates 334, and the air cylinders 33 are connected with a feed baffle 332 extending into the feed hopper 331; certainly, the feeding hopper 331 is located above the supporting plate 334 and is provided with a long hole corresponding to the feeding baffle 332, so that the feeding baffle 332 can move smoothly in the long hole; when the system is operating, the air cylinder 33 can control the length of the two feed baffles 332 entering the feed hopper 331, thereby controlling the flow of catalyst.

Referring to fig. 3, the catalyst recoverer 35 includes a thrust plate 351 and a compression plate 352 connected to both ends of the frame, the filter structure is connected between the thrust plate 351 and the compression plate 352, and the compression plate 352 is connected to the compression structure. The filtering structure comprises a plurality of filtering plates 353, the middle parts of the filtering plates 353 are recessed inwards, a filtering chamber is formed between every two filtering plates 353, and the water guide groove can enable 1, 4-diacetoxybutane solution to be quickly and uniformly injected into the filtering chamber; the compacting structure compacts the filter plate 353 located between the compacting plate 352 and the thrust plate 351 to ensure that the 1, 4-diacetoxybutane solution with pressure is pressure filtered in the filter chamber, and at the same time, the solid catalyst in the 1, 4-diacetoxybutane solution remains outside the filter plate 353, and a filter cake is formed under the force of compaction.

In the working process, an independent filter chamber is formed between every two

filter plates

353, 1, 4-diacetoxybutane solution enters the filter chamber from a water guide groove under the action of a water pump, a solid catalyst is stored on one side of each filter plate 353, and the 1, 4-diacetoxybutane finally converges to an outlet and enters the hydrolysis reactor 4. When the surface of the filter layer on one side of the filter plate 353 reaches a certain solid thickness, backwashing can be carried out, the water inlet direction is changed into the water outlet direction, and the backwashing solid catalyst is discharged into the catalyst collecting system, so that the waste of the residual catalyst is avoided, and meanwhile, the catalyst is prevented from influencing the normal production of a subsequent system.

Hydrolysis reactor 4, the main function of hydrolysis reactor 4 is to hydrolyze 1, 4-diacetoxybutane under the action of an ion exchange resin catalyst to produce crude 1, 4-butanediol.

The second rectifying tower 5 is mainly used for rectifying the crude 1, 4-butanediol to obtain a high-purity 1, 4-butanediol product. In the using process, crude 1, 4-butanediol enters a second rectifying tower 5 from the middle part of the tower, the crude 1, 4-butanediol is dehydrated and concentrated under the pressure of 60-90 KPa until the mass concentration is more than or equal to 94%, most of water, butanol and other byproducts are primarily separated from the crude 1, 4-butanediol, after the 1, 4-butanediol with the mass concentration more than or equal to 94% is led out from the concentrating tower, impurities are removed sequentially through a salt tower with the vacuum pressure of less than or equal to 15KPaA, a low-boiling tower and a high-boiling tower, the salt tower mainly removes metal salts, generated heavy components, tar and trace water, the low-boiling tower and the high-boiling tower remove impurities with high and low boiling points relative to the 1, 4-butanediol, and the high-purity 1, 4-butanediol is obtained after the impurities.

In the utility model, the top of the first rectifying tower 2 and the second rectifying tower 5 are both provided with coolers for controlling the temperature at the top of the towers; reflux pumps are arranged on the top reflux pipelines of the first rectifying tower 2 and the second rectifying tower 5 respectively and used for controlling the top reflux quantity.

Because second rectifying column 5 is the ripe equipment among the prior art, even the utility model discloses do not specifically describe the device, the purification work of thick 1, 4-butanediol also can be realized according to prior art to the technical personnel in the field, consequently, the utility model discloses no longer describe to second rectifying column 5 repeatedly.

The intelligent control device is electrically connected with the reaction parameter controllers in the diacetation oxidation reactor, the first rectifying tower, the hydrogenation reaction device, the hydrolysis reactor and the second rectifying tower; the intelligent control device comprises a strategy setting unit, a parameter control unit and a model setting unit; the strategy setting unit is used for setting the range of the reaction parameters and the learning strategy; the parameter control unit is used for controlling the reaction parameters of the diacetation oxidation reactor, the first rectifying tower, the hydrogenation reaction device, the hydrolysis reactor and the second rectifying tower according to a preset strategy and the range of the reaction parameters; the model setting unit is used for establishing a correlation model of the reaction parameters and the target object parameters.

For example, the pressure of the diacetation oxidation reactor is 6.7-6.9 MPa, the temperature of the hydrolysis reactor is 25-35 ℃, and the internal vacuum pressure of the salt tower, the low-boiling tower and the high-boiling tower is less than or equal to 15 KPaA. The strategy setting unit sets the ranges of the three parameters to be 6.7, 6.72, 6.75, 6.8, 6.84, 6.85, 6.81, 6.87 and 6.9MPa of pressure of the diacetation oxidation reactor, 25, 26, 28, 29, 31, 32, 33, 34 and 35KPa of internal pressure of the concentration tower, 15, 14.5, 14, 13.6, 13.2, 13, 12.8, 12.4 and 12KPaA of internal vacuum pressure of the salt tower, the low-boiling tower and the high-boiling tower respectively, and of course, the actual operation process is not limited to the three parameters and the range of each parameter is not limited to the characteristic values; the parameter control unit takes a value from the range of each parameter, combines a plurality of taken parameter values into a reaction condition, and simultaneously carries out reaction according to the reaction condition until the characteristic values of all the parameters are traversed, and each reaction condition records a reaction result; the model setting unit selects the best reaction result from all the reaction results, and finds the reaction condition corresponding to the reaction result, i.e. finds the characteristic value of each reaction parameter, and controls or adjusts the characteristic value through the controller (e.g. temperature controller, pressure controller, flow controller, etc.) of each reaction parameter.

The utility model discloses in, catalyst recoverer can realize intelligent operation through the control of intelligent control device. The back-flushing time of the catalyst reclaimer 35 may be controlled by an automatic control system.

By using the strengthening system, the utility model also provides a process for preparing 1, 4-butanediol from butadiene and acetic acid, which comprises the following steps:

step one

Adding acetic acid and a Pd-Te/C catalyst into a titanium material diacetoxy reactor 1, discharging air in the diacetoxy reactor 1 by using inert gas, pressurizing to 1.0MPa, introducing butadiene and oxygen until the pressure is 6.7-6.9 MPa, continuously reacting for 5-6 h, and stopping the reaction to obtain 1, 4-diacetoxybutene and a byproduct 3, 4-diacetoxybutene;

in the utility model, the inert gas is argon or nitrogen; the stirring speed of the diacetation oxidation reactor 1 is 900-1200 rpm, and the reaction temperature is 70-85 ℃; in the utility model, the volume ratio of butadiene to oxygen is 1: 1.

Step two

And (3) introducing a product obtained by the reaction in the diacetyl oxidation reactor 1 into a first rectifying tower 2, washing with water for 3-5 times, introducing organic matters into an oil phase, and rectifying and purifying to obtain the 1, 4-diacetyloxy butene.

Step three

Introducing the hydrogen in the hydrogen tank 34 and the 1, 4-diacetoxybutene prepared in the second step into a micro-interface generator 36; the micro-interface generator 36 crushes the hydrogen big bubbles to form micron-sized bubbles, and then the micron-sized bubbles and the 1, 4-diacetyloxybutene are fully mixed to form gas-liquid emulsion;

introducing the gas-liquid emulsion into a hydrogenation reaction kettle added with a catalyst for reaction, and continuously stirring in the reaction process; obtaining 1, 4-diacetyloxy butane;

wherein, the catalyst carrier adopts active carbon which is resistant to acetic acid corrosion and does not generate high-boiling by-products; the specific surface area of the activated carbon is preferably 1000-1500 cm²The preferred adsorption pore volume is 0.60-1.00 cm/g³/g。

The active components of the catalyst comprise Pt element and promoter element, wherein the content of Pt is preferably 1.00-8.00 g/L, and the content of the promoter element is preferably 0.50-10.00 g/L; the promoter element comprises at least one metal element of alkali metal or IIIB group metal; the alkali metal is preferably at least one of Li, Na, K, Rb and Cs, and the group IIIB metal is preferably at least one of Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Yb and Lu.

The utility model discloses in, the temperature of hydrogenation is 80 ~ 110 ℃, and the pressure of hydrogenation is 6 ~ 10MPa, and the time of hydrogenation is 3 ~ 4 h.

Step four

Adding 1, 4-diacetoxybutane, toluene-water and benzenesulfonic acid into a hydrolysis reactor 4, discharging air in the hydrolysis reactor 4 by using inert gas, pressurizing to 0.5MPa, heating to 25-35 ℃, stirring and keeping the temperature constant for 4-6 hours to hydrolyze the 1, 4-diacetoxybutane, thereby obtaining crude 1, 4-butanediol.

The inert gas is argon or nitrogen.

Step five

Guiding the crude 1, 4-butanediol prepared in the fourth step into a second rectifying tower 5, concentrating the mass concentration of the crude 1, 4-butanediol to be more than or equal to 94% under the pressure of 60-90 KPa, and separating out most of water, butanol and other byproducts contained in the crude 1, 4-butanediol;

and (3) sequentially passing the concentrated crude 1, 4-butanediol through a salt tower with vacuum pressure less than or equal to 15KPaA, a low-boiling tower and a high-boiling tower to remove impurities, and obtaining the high-purity 1, 4-butanediol.

In order to verify the system and the process of the process for preparing 1, 4-butanediol from butadiene and acetic acid, the present invention provides a plurality of embodiments as follows.

Example 1

Step one

Adding acetic acid and a Pd-Te/C catalyst into a diacetation oxidation reactor, then discharging air in the diacetation oxidation reactor by using inert gas, and pressurizing to 1.0 MPa;

introducing butadiene and oxygen into the diacetation oxidation reactor, and continuously pressurizing until the pressure of the diacetation oxidation reactor is 6.7 MPa;

after the reaction is continued for 5.2h, 1, 4-diacetoxybutene and a byproduct 3, 4-diacetoxybutene are obtained;

step two

Introducing the 1, 4-diacetoxybutene and the byproduct 3, 4-diacetoxybutene into a first rectifying tower, washing with water for 3 times, and rectifying and purifying to obtain 1, 4-diacetoxybutene;

step three

Introducing hydrogen in a hydrogen tank and the 1, 4-diacetoxybutene into a micro-interface generator; after the micro-interface generator crushes the large hydrogen bubbles into micron-sized bubbles, the micron-sized bubbles are fully and uniformly mixed with the 1, 4-diacetyloxy butene to form a gas-liquid emulsion;

introducing the gas-liquid emulsion into a hydrogenation reaction kettle added with a hydrogenation catalyst for reaction, and continuously stirring in the reaction process to obtain 1, 4-diacetyloxy butane;

step four

Adding toluene-water, benzenesulfonic acid and the 1, 4-diacetoxybutane to a hydrolysis reactor, and then exhausting air from the hydrolysis reactor with an inert gas;

pressurizing the hydrolysis reactor to 0.5MPa, heating to 26 ℃, stirring and keeping the temperature constant for 4.5 hours to hydrolyze the 1, 4-diacetoxybutane to obtain crude 1, 4-butanediol;

step five

Introducing the crude 1, 4-butanediol into a second rectifying tower, and enabling the mass concentration of the crude 1, 4-butanediol to be 95% under 63KPa pressure, and simultaneously separating water and butanol contained in the crude 1, 4-butanediol;

and (3) sequentially passing the concentrated crude 1, 4-butanediol through a salt tower with the vacuum pressure of 15KPaA, a low-boiling tower and a high-boiling tower to remove impurities, and obtaining the high-purity 1, 4-butanediol after removing the impurities.

Example 2

Step one

introducing butadiene and oxygen into the diacetation oxidation reactor, and continuously pressurizing until the pressure of the diacetation oxidation reactor is 6.8 MPa;

after the reaction is continued for 5.4 hours, 1, 4-diacetoxybutene and a byproduct 3, 4-diacetoxybutene are obtained;

step two

Introducing the 1, 4-diacetoxybutene and the byproduct 3, 4-diacetoxybutene into a first rectifying tower, washing with water for 4 times, and rectifying and purifying to obtain 1, 4-diacetoxybutene;

step three

step four

pressurizing the hydrolysis reactor to 0.5MPa, heating to 30 ℃, stirring and keeping the temperature constant for 5 hours to hydrolyze the 1, 4-diacetoxybutane to obtain crude 1, 4-butanediol;

step five

Introducing the crude 1, 4-butanediol into a second rectifying tower, and separating water and butanol contained in the crude 1, 4-butanediol at 82KPa pressure to ensure that the mass concentration of the crude 1, 4-butanediol is 96%;

and (3) sequentially passing the concentrated crude 1, 4-butanediol through a salt tower with vacuum pressure of 13KPaA, a low-boiling tower and a high-boiling tower to remove impurities, and obtaining the high-purity 1, 4-butanediol after removing the impurities.

Example 3

Step one

introducing butadiene and oxygen into the diacetation oxidation reactor, and continuously pressurizing until the pressure of the diacetation oxidation reactor is 6.9 MPa;

after the reaction is continued for 5.9h, 1, 4-diacetoxybutene and a byproduct 3, 4-diacetoxybutene are obtained;

step two

Introducing the 1, 4-diacetoxybutene and the byproduct 3, 4-diacetoxybutene into a first rectifying tower, washing with water for 5 times, and rectifying and purifying to obtain 1, 4-diacetoxybutene;

step three

step four

pressurizing the hydrolysis reactor to 0.5MPa, heating to 34 ℃, stirring and keeping the temperature constant for 5.8 hours to hydrolyze the 1, 4-diacetoxybutane to obtain crude 1, 4-butanediol;

step five

Introducing the crude 1, 4-butanediol into a second rectifying tower, and enabling the mass concentration of the crude 1, 4-butanediol to be 95% under the pressure of 86KPa, and simultaneously separating water and butanol contained in the crude 1, 4-butanediol;

and (3) sequentially passing the concentrated crude 1, 4-butanediol through a salt tower with the vacuum pressure of 14KPaA, a low-boiling tower and a high-boiling tower to remove impurities, and obtaining the high-purity 1, 4-butanediol after removing the impurities.

The staff also carries out other embodiments which are not listed one by one, and the experimental data of other embodiments are shown in the table I.

TABLE Experimental data for several other examples

The 1, 4-butanediol produced in the above examples was produced in a large amount, and the reaction was relatively sufficient.

In summary, the utility model is provided with a diacetation oxidation reactor, a first rectifying tower, a hydrogenation reaction device, a hydrolysis reactor and a second rectifying tower which are correspondingly connected in sequence; the hydrogenation reaction device comprises a hydrogenation reaction kettle, and the hydrogenation reaction kettle comprises a main reaction kettle and an auxiliary reaction kettle which are connected with each other; the inlet end of the main reaction kettle is respectively connected with a feeding pump, a catalyst feeding structure and a hydrogen tank, and the outlet end of the auxiliary reaction kettle is connected with a catalyst recoverer; a micro-interface generator is also arranged at the confluence position of the feeding pump and the hydrogen tank; the micro-interface generator is used for crushing reactant hydrogen, the diameter of micron-sized bubbles formed by crushing is larger than or equal to 1 mu m and smaller than 1mm, meanwhile, the micron-sized bubbles and an intermediate product 1, 4-diacetoxybutylene are mixed to form a gas-liquid emulsion, the contact area of the hydrogen and the 1, 4-diacetoxybutylene is increased, the hydrogen and the 1, 4-diacetoxybutylene are mixed more uniformly, the reaction is more complete, and the amount of the generated 1, 4-butanediol is more; the catalyst recoverer can collect the residual catalyst, so that waste is avoided, and the catalyst is prevented from influencing the normal production of a subsequent system; the utility model discloses still set up intelligent control device, realize that intelligence selects the best reaction condition, make the reaction high-efficient go on, avoid manual operation and the waste time and energy that causes. To sum up, the beneficial effects of the utility model are that: under the condition that the catalyst and the material proportion are not changed, the reaction efficiency is improved in multiples, the yield of the 1, 4-butanediol is increased, the energy consumption, the material consumption, the water consumption and the like are greatly reduced, and meanwhile, the intelligent operation is realized.

Naturally, the present invention can be embodied in many other forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be made by one skilled in the art without departing from the spirit or essential attributes thereof, and it is intended that all such changes and modifications be considered as within the scope of the appended claims.

Claims

1. An enhancement system for preparing 1, 4-butanediol from butadiene and acetic acid is characterized by comprising a diacetoxy reactor, a first rectifying tower, a hydrogenation reaction device, a hydrolysis reactor and a second rectifying tower which are sequentially and correspondingly connected; the intelligent control device is also included;

the hydrogenation reaction device comprises a hydrogenation reaction kettle, and the hydrogenation reaction kettle comprises a main reaction kettle and an auxiliary reaction kettle which are connected with each other; the outlet end of the secondary reaction kettle is connected with a catalyst recoverer, and the catalyst recoverer is connected with the hydrolysis reactor;

the micro-interface generator is arranged at the bottom end inside the main reaction kettle and is used for crushing reactant hydrogen, so that the diameter of the micro-scale bubbles formed by crushing is more than or equal to 1 mu m and less than 1 mm;

the inlet end of the main reaction kettle is respectively connected with a feeding pump, a catalyst feeding structure and a hydrogen tank, the hydrogen tank is connected with the micro-interface generator, and the feeding pump is connected with the first rectifying tower;

2. The strengthening system for preparing 1, 4-butanediol from butadiene and acetic acid according to claim 1, wherein the catalyst feeding structure comprises a feeding hopper, support plates are arranged on two opposite sides of the middle lower part of the feeding hopper, air cylinders are arranged on the support plates, and the air cylinders are connected with feeding baffle plates extending into the feeding hopper.

3. The strengthening system for preparing 1, 4-butanediol by using butadiene and acetic acid as claimed in claim 1, wherein the catalyst recoverer comprises a thrust plate and a compression plate which are connected with two ends of a frame, a filtering structure is connected between the thrust plate and the compression plate, and the compression plate is connected with the compression structure.

4. The enhanced system for preparing 1, 4-butanediol from butadiene and acetic acid as claimed in claim 3, wherein the filter structure comprises a plurality of filter plates, the middle parts of the filter plates are recessed inwards, and a filter chamber is formed between every two filter plates.

5. The enhancement system for preparing 1, 4-butanediol from butadiene and acetic acid as claimed in claim 1, wherein the top of each of the first rectifying tower and the second rectifying tower is provided with a cooler for controlling the temperature of the top of the tower.

6. The enhancement system for preparing 1, 4-butanediol from butadiene and acetic acid according to claim 1, wherein reflux pumps for controlling reflux amount at the top of the tower are arranged on the top reflux lines of the first rectifying tower and the second rectifying tower.

7. The enhancement system for preparing 1, 4-butanediol from butadiene and acetic acid according to claim 1, wherein the catalyst recoverer is connected with an intelligent control device.

8. The enhanced system for preparing 1, 4-butanediol from butadiene and acetic acid as claimed in claim 1, wherein the diacetation oxidation reactor is provided with a stirring device for accelerating the reaction speed of the acetylation reaction.

9. The enhancement system for preparing 1, 4-butanediol by using butadiene and acetic acid as claimed in claim 1, wherein temperature sensors are arranged in the main reaction kettle and the secondary reaction kettle.