Preparation device of polymer-grade 1, 4-butanediol

Abstract

The utility model relates to a preparation device of polymer-grade 1, 4-butanediol, which comprises a feed chute, a hydrolysis hydrogenation reactor, a reaction discharge separator and a dehydrating tower, and the feed chute is connected with an external storage tank for crude 1, 4-butanediol products; the hydrolysis hydrogenation reactor is used for catalytic hydrogenation of the crude 1, 4-butanediol product, so that acetal in the crude 1, 4-butanediol product is converted into the 1, 4-butanediol product; the reaction discharge separator is connected with the post-reaction product discharge port and is used for gas-liquid separation of the product after catalytic hydrogenation of the hydrolysis hydrogenation reactor; the dehydrating tower is connected with a liquid outlet of the reaction discharge separator, and the dehydrating tower is used for separating residual water in the reacted 1, 4-butanediol product. Compared with the prior art, the device disclosed by the utility model is suitable for converting a crude 1, 4-butanediol product into a polymer-grade product, effectively converting acetal through a catalytic hydrogenation reaction, and removing residual moisture through the dehydrating tower, so that the final product is ensured to reach a high-purity standard.

Description

TECHNICAL FIELD

[0001] The utility model relates to a kind of 1,4-butanediol production device, especially a kind of preparation device of polymeric grade 1,4-butanediol. BACKGROUND

[0002] 1,4-butanediol, English name 1,4-Butanediol, is a colorless, viscous organic compound, chemical formula C4H 10 O2. Due to its special structure, 1,4-butanediol is widely used in organic synthesis, industrial solvent and polymer raw material intermediate, generating tetrahydrofuran (THF), gamma-butyrolactone (GBL), polybutylene terephthalate (PBT), polyurethane, thermoplastic polyurethane (TPU) and other derivatives. These high value-added derivatives are widely used in automobile, spandex fiber, engineering plastic and pharmaceutical industries. In addition, it is a precursor of synthetic chemicals such as 1,4-butanediol dimethyl acrylate (BDDMA) and N-methyl-2-pyrrolidone (NMP). These chemicals can be used to produce adhesives, coatings and specialty chemicals. With the rise of new energy industry, it is also widely used in lithium ion batteries, and can also be used in the field of semiconductor chip flushing.

[0003] According to "Contemporary Chemical Industry" (May 2024, Vol. 53, No. 5), "BDO refining technology research report", acetal is the main color-developing impurity in BDO product, and the difference between polymeric grade BDO product and industrial grade BDO lies in the special requirement for acetal content. Acetal, English abbreviation HBTHF, is an oxide impurity produced in the hydrogenation process of BDO. This substance is easy to oxidize and develop color, thereby affecting the quality of BDO downstream polymerization products. Controlling the content of acetal impurity is the key to producing polymeric grade BDO. Therefore, domestic manufacturers and research institutes have conducted research on this problem. At present, there are mainly two methods to solve it:

[0004] 1) Increase the purity of BDO by physical separation means, such as changing the rectification conditions, increasing the packing height of rectification tower and extremely high reflux ratio to reduce the content of acetal, and increasing the discharge amount. However, due to the special physical system of HBTHF and BDO, the boiling points are similar and form azeotrope. This method not only increases equipment investment and energy consumption, but also reduces the yield of BDO, and the separation effect of acetal is not obvious. CN11571678A discloses a low-temperature purification crystallization purification method, which can obtain BDO with high purity by means of multi-stage melt crystallization. However, it requires multiple melt crystallization, which increases energy consumption.

[0005] 2) By chemical means, for the property of acetal and BDO difficult to separate, acetal is converted into other easily separated components by catalytic reaction, and high quality BDO product is obtained by further rectification. CN117645586A discloses a method for refining and removing acetal from BDO, which generates THF by dehydration and cyclization of BDO, and then separates acetal from THF. Although the acetal is separated from the system, the yield of BDO is reduced. The methods disclosed in CN1216973A, CN106622393A and CN110833862A use catalytic hydrogenation method, and acetal is hydrolyzed and hydrogenated to generate BDO under the action of Ni-based catalyst. The yield of BDO is improved while the acetal is removed. Such method has high requirements for the performance and mechanical properties of the catalyst. The catalyst has suitable pore structure, acidity and mechanical strength. If the surface acidity of the catalyst is too strong, the dehydration and cyclization side reaction of BDO will occur, the content of THF will increase, and the yield of BDO will decrease. Since the reaction needs to be hydrolyzed first, a certain proportion of water needs to be added, which requires the catalyst to have good hydrothermal stability at high temperature and high pressure. However, good hydrothermal stability will reduce the pore volume and specific surface area of the catalyst, which is difficult to balance and is only suitable for raw materials with low acetal content. According to the acetal content in the BDO disclosed in the published patents, the acetal content is usually ≤2000ppm. The removal capacity is limited for raw materials with high content.

[0006] From the perspective of engineering implementation, water needs to be added to complete the hydrolysis in the liquid phase reaction of catalytic hydrogenation. The large viscosity difference between water and butanediol makes it difficult to mix and dissolve. In the liquid phase reaction system, hydrogen is difficult to dissolve fully. In order to ensure complete hydrogenation in industry, a large amount of hydrogen needs to be added, but this will cause the residence time of the reactor to be short, thereby causing the reaction performance to decrease and the hydrogen consumption to increase.

[0007] Due to the limitations of the existing production process, the quality of BDO products is uneven, and most of them cannot meet the special requirements of polymerization grade BDO quality. Therefore, it is of great significance to develop a new polymerization grade BDO preparation device to simplify the process, reduce production cost, reduce environmental pollution and improve the product upgrading of existing BDO devices in China. It is an important research direction in the field of chemical industry. Practical new type content

[0008] The purpose of the present application is to overcome the defects of the prior art and provide a preparation device for polymerization grade 1,4-butanediol, which is suitable for converting crude 1,4-butanediol product into polymerization grade product, effectively converting acetal by catalytic hydrogenation reaction, and removing residual water by dehydration tower to ensure that the final product meets the high purity standard.

[0009] The purpose of the present application can be achieved by the following technical solutions:

[0010] The utility model provides a kind of preparation device of polymeric grade 1,4-butanediol, including feed tank, hydrolysis hydrogenation reactor, reaction discharge separator, dehydration tower, and wherein specifically:

[0011] Feed tank is connected with the storage tank of external coarse 1,4-butanediol product;

[0012] Hydrolysis hydrogenation reactor is used for the catalytic hydrogenation of coarse 1,4-butanediol product, so that acetal in coarse 1,4-butanediol product is converted into 1,4-butanediol product, hydrogen inlet, coarse 1,4-butanediol product inlet and post-reaction 1,4-butanediol product discharge port are equipped on the hydrolysis hydrogenation reactor, and the coarse 1,4-butanediol product inlet is connected with the feed tank;

[0013] Reaction discharge separator is connected with the post-reaction product discharge port, and is used for the gas-liquid separation of product after catalytic hydrogenation of hydrolysis hydrogenation reactor;

[0014] Dehydration tower is connected with the liquid outlet of reaction discharge separator, and the dehydration tower is used for separating residual water in post-reaction 1,4-butanediol product.

[0015] Further, the hydrolysis hydrogenation reactor is a trickle bed reactor.

[0016] Further, the hydrolysis hydrogenation reactor is filled with a hydrogenation catalyst.

[0017] Further, the hydrogen inlet and coarse 1,4-butanediol product inlet on the hydrolysis hydrogenation reactor are arranged at the top of the hydrolysis hydrogenation reactor.

[0018] Further, the preparation device of polymeric grade 1,4-butanediol further includes a coarse 1,4-butanediol product feed pump and a reactor feed cooler connected with each other, the coarse 1,4-butanediol product feed pump is connected with the feed tank, and the coarse 1,4-butanediol product feed pump is connected with the coarse 1,4-butanediol product inlet.

[0019] Further, the preparation device of polymeric grade 1,4-butanediol further includes a reaction liquid circulating pump, and the reaction liquid circulating pump is connected with the reactor feed cooler and the reaction discharge separator respectively.

[0020] Further, the preparation device of polymeric grade 1,4-butanediol further includes a 1,4-butanediol product filter and a dehydration tower feed pump connected in sequence, the 1,4-butanediol product filter is connected with the reaction discharge separator, and the dehydration tower feed pump is connected with the dehydration tower.

[0021] Further, the top of the dehydration tower is matched with a dehydration tower reflux pump and a dehydration tower overhead condenser connected with each other, and the dehydration tower reflux pump and the dehydration tower overhead condenser are connected with the top of the dehydration tower.

[0022] Further, the middle part of the dehydration tower is provided with a 1,4-butanediol to be dehydrated feeding port and a polymerization grade 1,4-butanediol product discharging port.

[0023] The 1,4-butanediol to be dehydrated feeding port is connected with the dehydration tower feeding pump, and the polymerization grade 1,4-butanediol product discharging port is used to output the polymerization grade 1,4-butanediol product.

[0024] Further, the bottom of the dehydration tower is matched with a dehydration tower bottom reboiler and a dehydration tower bottom pump.

[0025] Compared with the prior art, the polymeric 1,4-butanediol preparation device has the following beneficial effects:

[0026] 1) The polymeric 1,4-butanediol preparation device can improve the production efficiency and product quality of 1,4-butanediol, and is particularly suitable for converting crude 1,4-butanediol product into polymerization grade product, effectively converting acetal through catalytic hydrogenation reaction, and removing residual moisture through the dehydration tower to ensure that the final product meets high-purity standards and meets the strict requirements of downstream high-molecular material production.

[0027] 2) The design of the preparation device also includes a series of auxiliary equipment such as a feeding pump, a cooler, a circulating pump and a filter, which cooperate with each other to form an efficient and energy-saving production system. The integrated design not only simplifies the operation process, reduces energy consumption and maintenance cost, but also improves the automation level of the entire device and reduces the possibility of human operation errors, thereby ensuring product quality while improving production safety and economic benefits. BRIEF DESCRIPTION OF DRAWINGS

[0028] Figure 1 The figure is a structural schematic view of the polymeric 1,4-butanediol preparation device in the utility model.

[0029] In the figure: 1-hydrolysis hydrogenation reactor; 2-dehydration tower; 3-feeding tank; 4-reaction discharge separator; 5-dehydration tower feeding pump; 6-crude 1,4-butanediol cooler; 7-reactor feeding cooler; 8-dehydration tower overhead condenser; 9-dehydration tower bottom reboiler; 10-1,4-butanediol product filter; 11-crude 1,4-butanediol conveying pump; 12-reaction liquid circulating pump; 13-dehydration tower bottom pump; 14-dehydration tower reflux pump. DETAILED DESCRIPTION

[0030] The utility model will be explained in detail below in combination with the drawings and specific embodiments. In the technical scheme, the components, material names, connection structures, control methods, algorithms and other features not explicitly described are considered as common technical features disclosed in the prior art and are considered as contents not described in the utility model.

[0031] Embodiment 1

[0032] The preparation device of the polymerization-grade 1,4-butanediol in the embodiment comprises a feed tank 3, a hydrolysis hydrogenation reactor 1, a reaction discharge separator 4 and a dehydration tower 2. For details, refer to Figure 1 .

[0033] The feed tank 3 is connected with an external crude 1,4-butanediol product storage tank. Non-condensable gas at the top of the feed tank 3 can be discharged for combustion.

[0034] The hydrolysis hydrogenation reactor 1 is used for catalytic hydrogenation of the crude 1,4-butanediol product, so that the acetal in the crude 1,4-butanediol product is converted into the 1,4-butanediol product. The hydrolysis hydrogenation reactor 1 is provided with a hydrogen inlet, a crude 1,4-butanediol product inlet and a post-reaction 1,4-butanediol product outlet. The crude 1,4-butanediol product inlet is connected with the feed tank 3. The hydrolysis hydrogenation reactor 1 is a trickle bed reactor. The hydrogen inlet and the crude 1,4-butanediol product inlet of the hydrolysis hydrogenation reactor 1 are both arranged at the top of the hydrolysis hydrogenation reactor 1. The hydrolysis hydrogenation reactor 1 is filled with a hydrogenation catalyst. The specific catalyst is selected from existing industrial hydrogenation catalysts that can be used to convert the acetal in the crude 1,4-butanediol product into the 1,4-butanediol product according to a specific process.

[0035] The reaction discharge separator 4 is connected with the post-reaction product outlet and is used for gas-liquid separation of the product after catalytic hydrogenation in the hydrolysis hydrogenation reactor 1. Non-condensable gas at the top of the reaction discharge separator 4 can be discharged for combustion.

[0036] The dehydration tower 2 is connected with the liquid outlet of the reaction discharge separator 4 and is used for separating residual water in the post-reaction 1,4-butanediol product.

[0037] The preparation device of the polymerization-grade 1,4-butanediol further comprises a crude 1,4-butanediol product feed pump 11 and a reactor feed cooler 7 connected with each other. The crude 1,4-butanediol product feed pump 11 is connected with the feed tank 3. The crude 1,4-butanediol product feed pump 11 is connected with the crude 1,4-butanediol product inlet.

[0038] The device for preparing polymer-grade 1,4-butanediol further comprises a reaction liquid circulating pump 12, which is connected with the reactor feed cooler 7 and the reaction discharge separator 4 respectively.

[0039] The device for preparing polymer-grade 1,4-butanediol further comprises a 1,4-butanediol product filter 10 and a dehydration column feed pump 5 connected in sequence, wherein the 1,4-butanediol product filter 10 is connected with the reaction discharge separator 4, and the dehydration column feed pump 5 is connected with the dehydration column 2. The 1,4-butanediol product filter 10 is used for filtering impurities in the product.

[0040] The top of the dehydration column 2 is matched with a dehydration column reflux pump 14 and a dehydration column overhead condenser 8 connected with each other, both of which are connected with the top of the dehydration column 2. The middle part of the dehydration column 2 is provided with a 1,4-butanediol to be dehydrated feed port and a polymer-grade 1,4-butanediol product discharge port; the 1,4-butanediol to be dehydrated feed port is connected with the dehydration column feed pump 5, and the polymer-grade 1,4-butanediol product discharge port is used for outputting polymer-grade 1,4-butanediol product. The bottom of the dehydration column 2 is matched with a dehydration column bottom reboiler 9 and a dehydration column bottom pump.

[0041] In specific implementation, the salt water as cooling water is transported through a pipeline to realize heat exchange of the feed tank 3 and the dehydration column overhead condenser 8. The structure of the heat exchange pipeline is a prior art, which will not be described here.

[0042] A crude 1,4-butanediol cooler 6 can also be provided, which is connected with the feed tank 3 and the dehydration column feed pump 5 respectively, and is used for cooling the crude 1,4-butanediol from the dehydration column feed pump 5 and returning to the feed tank 3.

[0043] The operation process of the device for preparing polymer-grade 1,4-butanediol is as follows:

[0044] The feed stage: the crude 1,4-butanediol product is transported from an external storage tank to the device through the feed tank 3. The non-condensable gas at the top of the feed tank 3 can be discharged and sent to combustion.

[0045] The catalytic hydrogenation reaction stage: the crude 1,4-butanediol product is transported from the feed tank 3 to the hydrolysis hydrogenation reactor 1 through the crude 1,4-butanediol product feed pump 11.

[0046] In the hydrolysis hydrogenation reactor 1, the crude 1,4-butanediol product is mixed with hydrogen, and under the action of the hydrogenation catalyst, the acetal is converted into the 1,4-butanediol product. The hydrogen enters the reactor through a hydrogen feed port.

[0047] Gas-liquid separation stage: the reacted product flows out from the outlet of the hydrolysis hydrogenation reactor 1, enters the reaction outlet separator 4 for gas-liquid separation. The non-condensable gas at the top of the separator can be discharged and sent to combustion.

[0048] Dehydration stage: the separated liquid product is filtered through the 1,4-butanediol product filter 10 to remove impurities, and then is sent to the dehydration column 2 by the dehydration column feed pump 5. In the dehydration column 2, the residual water in the 1,4-butanediol product is separated by a distillation process.

[0049] Cooling and reflux stage: the dehydration column 2 is provided with a dehydration column reflux pump 14 and a dehydration column overhead condenser 8 at the top of the column, for condensing the vapor at the top of the column and partially refluxing into the column to improve the dehydration efficiency.

[0050] Product output stage: the polymerization grade 1,4-butanediol product after dehydration treatment is output from the polymerization grade 1,4-butanediol product outlet of the dehydration column 2.

[0051] The above description of the embodiments is for the purpose of enabling a person of ordinary skill in the art to understand and use the utility model. Those skilled in the art can obviously make various modifications to these embodiments, and apply the general principles described herein to other embodiments without having to go through creative labor. Therefore, the utility model is not limited to the above embodiments, and the improvements and modifications made by those skilled in the art based on the disclosure of the utility model without departing from the scope of the utility model should be within the protection scope of the utility model.

Claims

1. An apparatus for the production of polymer grade 1,4-butanediol, characterized in that The application relates to a preparation device for polymerization-grade 1,4-butanediol. The preparation device comprises the following components: a feed tank (3) connected with an external crude 1,4-butanediol product storage tank; a hydrolysis hydrogenation reactor (1) for catalytic hydrogenation of the crude 1,4-butanediol product, so that acetal in the crude 1,4-butanediol product is converted into 1,4-butanediol product, wherein a hydrogen inlet, a crude 1,4-butanediol product inlet and a post-reaction 1,4-butanediol product outlet are arranged on the hydrolysis hydrogenation reactor (1), and the crude 1,4-butanediol product inlet is connected with the feed tank (3); a reaction discharge separator (4) connected with the post-reaction 1,4-butanediol product outlet, used for gas-liquid separation of the product after catalytic hydrogenation in the hydrolysis hydrogenation reactor (1); 2. A device for the preparation of polymer grade 1,4-butanediol according to claim 1, characterized in that a dehydration tower (2) connected with a liquid outlet of the reaction discharge separator (4), used for separating residual water in the post-reaction 1,4-butanediol product.

3. A device for the preparation of polymer grade 1,4-butanediol according to claim 1, characterized in that The hydrolysis hydrogenation reactor (1) is a trickle bed reactor.

4. The apparatus for producing polymer grade 1,4-butanediol according to claim 1, wherein The hydrolysis hydrogenation reactor (1) is filled with a hydrogenation catalyst.

5. The apparatus for producing polymer grade 1,4-butanediol according to claim 1, wherein The hydrogen inlet and the crude 1,4-butanediol product inlet of the hydrolysis hydrogenation reactor (1) are arranged on the top of the hydrolysis hydrogenation reactor (1).

6. A device for the production of polymer grade 1,4-butanediol according to claim 5, characterized in that The preparation device for polymerization-grade 1,4-butanediol further comprises a crude 1,4-butanediol product feed pump (11) and a reactor feed cooler (7) connected with each other, the crude 1,4-butanediol product feed pump (11) is connected with the feed tank (3), and the crude 1,4-butanediol product feed pump (11) is connected with the crude 1,4-butanediol product inlet.

7. The apparatus of claim 1, wherein the apparatus is configured to produce polymeric grade 1,4-butanediol. The preparation device for polymerization-grade 1,4-butanediol further comprises a reaction liquid circulating pump (12), and the reaction liquid circulating pump (12) is connected with the reactor feed cooler (7) and the reaction discharge separator (4) respectively.

8. The apparatus of claim 1, wherein the apparatus is configured to produce polymeric grade 1,4-butanediol. The preparation device for polymerization-grade 1,4-butanediol further comprises a 1,4-butanediol product filter (10) and a dehydration tower feed pump (5) connected in sequence, the 1,4-butanediol product filter (10) is connected with the reaction discharge separator (4), and the dehydration tower feed pump (5) is connected with the dehydration tower (2).

9. The apparatus for producing polymer grade 1,4-butanediol according to claim 7, wherein A dehydration tower reflux pump (14) and a dehydration tower overhead condenser (8) are arranged on the top of the dehydration tower (2) in a matched mode and are connected with the top of the dehydration tower (2). A 1,4-butanediol feed inlet for dehydration and a polymerization-grade 1,4-butanediol product outlet are arranged in the middle of the dehydration tower (2).

10. The apparatus for producing polymer grade 1,4-butanediol according to claim 1, wherein The 1,4-butanediol feed inlet for dehydration is connected with the dehydration tower feed pump (5), and the polymerization-grade 1,4-butanediol product outlet is used for outputting polymerization-grade 1,4-butanediol product. A dehydration tower kettle reboiler (9) and a dehydration tower kettle pump are arranged on the kettle of the dehydration tower (2).

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