CN112457160A - Preparation system and process of 1, 4-butanediol - Google Patents
Preparation system and process of 1, 4-butanediol Download PDFInfo
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Abstract
The invention is suitable for the technical field of preparation of 1, 4-butanediol, and provides a preparation system and a preparation process of 1, 4-butanediol, wherein the preparation system comprises a formaldehyde production device, an acetylene generation device, a micro-interface generator, a deionization system and a hydrogenation system; the output ends of the formaldehyde production device and the acetylene generation device are connected with the ethynylation reaction device through the first micro-interface generator; the output end of the separation subsystem is connected with the hydrogenation system through the second micro-interface generator, the formaldehyde production device comprises a heating system, a reaction system and a product collecting system which are connected with each other, and the reaction system comprises a fire retardant filter, a reactor and an absorption tower; the heater includes a first heater and a second heater. Therefore, the invention improves the traditional 1, 4-butanediol production process, reduces the upgrading cost of enterprise equipment and improves the reaction efficiency.
Description
Technical Field
The invention relates to the technical field of preparation of 1, 4-butanediol, in particular to a preparation system and a preparation process of 1, 4-butanediol.
Background
1, 4-butanediol is an important basic organic chemical and fine chemical raw material. The derivatives of the compound are widely used, and particularly the derivatives of the compound are fine chemical products with high added value and widely used in the aspects of solvents, medicines, cosmetics, plasticizers, curing agents, pesticides, herbicides, artificial leather, fibers, engineering plastics and the like. 1, 4-butanediol is also used for the production of Tetrahydrofuran (THF), γ -butyrolactone (GBL), N-methyl pyrrolidone (NMP), and the like. In recent years, PBT (polybutylene terephthalate, which is mainly used in the fields of PBT modification, PBT drawing, film drawing, optical fiber sheathing, and the like, and can be widely used in the fields of automobile manufacturing, electronics and electrics, instruments, lighting, home appliances, textiles, machinery, communications, and the like after being reinforced and modified) engineering plastics and PBT fibers are widely used in the industries of automobiles, machinery, electronics, electrical and the like because of their easy processing and excellent electrical properties, mechanical properties, and heat resistance. The PBT fiber has excellent elasticity (superior to nylon), good dyeing property and water absorption and plump hand feeling, is mainly used for high-grade sportswear, women's underwear, tights and the like, and has a larger potential market.
The production process routes of the 1, 4-butanediol are more than ten kinds, mainly including a Reppe method, an n-butane/maleic anhydride method, a butadiene method, a propylene oxide method and the like, wherein the Reppe method and the n-butane/maleic anhydride method are the most main processes for producing the 1, 4-butanediol at present. In addition, a biotransformation method and a new method for directly preparing 1, 4-butanediol by selectively hydrolyzing 1, 2-epoxy-3-butene [ acetylene and formaldehyde are used as raw materials, 1, 4-butynediol is generated under the catalysis of copper, and then 1, 4-butanediol is generated by hydrogenation. Among them, the Reppe method is the most widely used process method.
The Reppe method is classified into a classical method and an improved method. In the classical method, under the operation conditions of 13.8-27.6MPa and 350 ℃ of 250-.
In the improved Reppe process, a Cu-Bi silica gel catalyst is adopted, the temperature is 90-100 ℃, the pressure is 0.1-0.2MPa, and the 1, 4-butynediol is synthesized in a suspension bed or a slurry bed, so that the acetylene partial pressure in the reaction process is reduced.
In China, a plurality of routes are available for synthesizing the 1, 4-butanediol, but in recent years, with the development of a 1, 4-butanediol synthesis technology, the preparation of the 1, 4-butanediol is mainly completed by an alkyne aldehyde method. In the process flow of synthesizing 1, 4-butanediol by utilizing the alkynal method, particularly in the process of mixing acetylene and formaldehyde and synthesizing 1, 4-butanediol by utilizing the 1, 4-butynediol for hydrogenation, because two gases with different densities are directly mixed, the reaction rate is low, a large amount of derivative substances are inevitably generated, and the cost of later-stage separation is increased.
In view of the above, the prior art is obviously inconvenient and disadvantageous in practical use, and needs to be improved.
Disclosure of Invention
In view of the above-mentioned drawbacks, the present invention aims to provide a system and a process for preparing 1, 4-butanediol, which improve the conventional 1, 4-butanediol production system, reduce the upgrade cost of enterprise equipment, and improve the reaction efficiency.
In order to achieve the aim, the invention provides a preparation system of 1, 4-butanediol, which comprises a formaldehyde production device, an acetylene generation device, a micro-interface generator, a deionization system and a hydrogenation system; the micro-interface generator is used for crushing gas to form micron-sized bubbles with the diameter being more than or equal to 1 mu m and less than 1mm, and comprises a first micro-interface generator and a second micro-interface generator; the output ends of the formaldehyde production device and the acetylene generation device are connected with the ethynylation reaction device through the first micro-interface generator; the output end of the separation subsystem is connected with the hydrogenation system through the second micro-interface generator, and the hydrogenation system is a multistage hydrogenation system; the formaldehyde production device comprises a heating system, a reaction system and a product collecting system which are connected with each other, wherein the heating system comprises a heater, a reboiler and a superheater; the heater comprises a first heater and a second heater, the first heater is located at the output end of the tail gas fan, and the second heater is connected with the outside air and the mixer respectively.
According to the preparation system of the 1, 4-butanediol, the rear end of the ethynylation reaction device is also connected with a rectifying device, the rectifying device is a 1, 4-butynediol rectifying device, and the output end of the 1, 4-butynediol rectifying device is connected with the separation subsystem.
According to the preparation system of the 1, 4-butanediol, the multistage hydrogenation system comprises a low-pressure hydrogenation system and a high-pressure hydrogenation system, the input ends of the low-pressure hydrogenation system and the high-pressure hydrogenation system are both connected with the second micro-interface generator, and the input end of the second micro-interface generator is connected with the separation subsystem.
According to the 1, 4-butanediol preparation system, a steam drum for pressure stabilization balance is also connected between the reactor and the superheater.
According to the 1, 4-butanediol preparation system, the number of the absorption towers is two, the absorption towers comprise a first absorption tower and a second absorption tower, the output end of the first absorption tower is connected with a circulating pump, the output end of the circulating pump is connected with the preparation tank and the product tank, the output end of the second absorption tower is connected with a tail gas fan and a burner, and the output end of the tail gas fan is connected with the first heater.
According to the preparation system of the 1, 4-butanediol, the acetylene generating device sequentially comprises a hydrolysis system, an acetylene generator and a cooler, and the output end of the cooler is connected with the hydrolysis tank and the gas holder.
According to the 1, 4-butanediol preparation system, an external reactor is arranged in the hydrogenation system, and the external reactor comprises one or more of a slurry bed, a fixed bed, a trickle bed or a capillary reactor.
According to the system for preparing 1, 4-butanediol of the present invention, the capillary reactor has an upper end opening diameter smaller than a lower end opening diameter.
According to the preparation system of the 1, 4-butanediol, the capillary tube reactor is formed by uniformly combining a plurality of single capillary tubes, the inner diameter of each single capillary tube is 2-4mm, the inner diameter of the bottom of the integral capillary tube is 10-16cm, and the diameter of the upper part of the integral capillary tube is 5-8 cm.
A preparation process of 1, 4-butanediol comprises the following steps:
the method comprises the following steps: preparing formaldehyde and acetylene by using a formaldehyde production device and an acetylene generating device respectively;
step two: carrying out alkyne-aldehyde reaction on the formaldehyde prepared in the step one and acetylene in a reaction kettle, and adding a catalyst in the alkyne-aldehyde reaction to generate 1, 4-butynediol; the catalyst in the reaction of alkynal is Cu2C2-Bi2O3Or SiO2The reaction temperature is 80-120 ℃, and the reaction pressure in the reaction kettle is less than or equal to 2 MPa;
step three: carrying out hydrogenation reaction on the 1, 4-butynediol prepared in the step two in an external reactor, wherein the hydrogenation reaction is two-stage hydrogenation, the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system, the adopted catalyst is a Ni-based catalyst, and the reaction pressure is 1-5 MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, the adopted catalyst is a Pd-based catalyst, and the reaction pressure is 10-30 MPa; after the two-stage hydrogenation process is finished, 1, 4-butanediol produced by the first-stage hydrogenation reaction and the second-stage hydrogenation reaction is refined in a rectifying tower to produce a 1, 4-butanediol product.
The invention aims to provide a preparation system of 1, 4-butanediol, which comprises a formaldehyde production device, an acetylene generation device, a micro-interface generator, a deionization system and a hydrogenation system; the micro-interface generator comprises a first micro-interface generator and a second micro-interface generator; the output ends of the formaldehyde production device and the acetylene generation device are connected through the first micro-interface generator and are rapidly mixed for alkyne-aldehyde reaction to generate 1, 4-butynediol. The output end of the separation subsystem is connected with the hydrogenation system through the second micro-interface generator, and the hydrogenation system is a multistage hydrogenation system; as the hydrogenation reaction is a strong exothermic reaction, local overheating is easy to occur in the industrial hydrogenation process of the 1, 4-butynediol, the catalyst is easy to inactivate at high temperature, and the service life of the catalyst is reduced, so that a multistage hydrogenation system is adopted in a general hydrogenation system, the service life of equipment can be greatly prolonged, and local overheating is prevented. The formaldehyde production device comprises a heating system, a reaction system and a product collecting system which are connected with each other, wherein the heating system is positioned at the front end of the reaction system and comprises a heater, a reboiler and a superheater; the reaction system comprises a fire retardant filter, a reactor and an absorption tower; the product collection system comprises a preparation tank and a product tank; the heater comprises a first heater and a second heater, the first heater is located at the output end of the tail gas fan, the second heater is connected with the outside air and the mixer respectively, the micro-interface generator can crush hydrogen into micron-sized bubbles with the diameter being more than or equal to 1 mu m and less than 1mm, and the micron-sized bubbles and 1, 4-butynediol are fully mixed to form a gas-liquid emulsion, so that the contact area between gas and liquid is increased, the chemical property is inconvenient, and the chemical reaction efficiency can be greatly improved in the reaction process.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a schematic view of the structure of a formaldehyde production apparatus of the present invention;
FIG. 3 is a flow diagram of the production of acetylene according to the invention;
FIG. 4 is a schematic diagram of a capillary reactor configuration;
FIG. 5 is a schematic process flow diagram of the present invention;
in the figure, 1-tail gas fan, 2-first heater, 3-second heater, 4-reboiler, 5-mixer, 6-superheater, 7-fire retardant filter, 8-steam drum, 9-reactor, 10-first absorption tower, 11-second absorption tower, 12-circulating pump, 13-preparation tank, 14-product tank, 15-incinerator, BDO-1, 4-butanediol, BYD-1, 4-butynediol, BED-1, 4-butenediol.
Detailed Description
Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the present invention, and do not limit the scope of the present 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 in a specific orientation, and be operated, 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 meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail with reference to the accompanying drawings and embodiments, it being understood that the specific embodiments described herein are merely illustrative of the present invention and are not intended to limit the present invention.
Referring to fig. 1 and 5, the invention aims to provide a system for preparing 1, 4-butanediol, which comprises a formaldehyde production device, an acetylene generation device, a micro-interface generator, a deionization system and a hydrogenation system; the micro-interface generator comprises a first micro-interface generator and a second micro-interface generator; the output ends of the formaldehyde production device and the acetylene generation device are connected through a first micro-interface generator and are rapidly mixed for acetylene aldehyde reaction to generate 1, 4-butynediol.
The output end of the separation subsystem is connected with a hydrogenation system through a second micro-interface generator, and the hydrogenation system is a multistage hydrogenation system; as the hydrogenation reaction is a strong exothermic reaction, local overheating is easy to occur in the industrial hydrogenation process of the 1, 4-butynediol, the catalyst is easy to inactivate at high temperature, and the service life of the catalyst is reduced, so that a multistage hydrogenation system is adopted in a general hydrogenation system, the service life of equipment can be greatly prolonged, and local overheating is prevented.
The micro-interface strengthening reactor is suitable for most reaction processes controlled by mass transfer and heat transfer, such as gas-liquid, gas-liquid-solid, liquid-solid, gas-liquid-solid reaction systems and the like. The basic scientific principle is that the diameters of gas or liquid phase particles at gas-liquid, liquid-liquid and gas-liquid phase interfaces of a reaction system are crushed into micron-sized (30-900 mu m) ranges, while the diameters of the gas and liquid phase particles in the traditional bubble reactor are generally millimeter/centimeter-sized (3-30 mm). Therefore, the mass transfer area and the total mass transfer rate between gas-liquid and liquid-liquid can be increased by times, so that the reaction speed is greatly increased, side reactions are effectively controlled, the product yield is increased, the energy consumption and material consumption in the reaction process are obviously reduced, the safety of the reaction section is improved, and the like.
Generally, for reaction systems such as oxidation, peroxidation, hydrogenation, benzene ring chlorination, and the like, gas-liquid-solid, and the like, compared with a traditional stirred reaction kettle, the reaction rate can be improved by 3-5 times or more, the energy consumption can be saved by 30-50% or more generally, and the material consumption can be saved by 5% -20% or more.
The micro-interface strengthening reactor is a general technology, is suitable for the occasions of chemical reactions such as gas-liquid, gas-liquid-solid, liquid-solid, gas-liquid-solid and the like in multiple industries and multiple fields such as petrifaction, coal chemical industry, fine chemical industry, pharmacy (medicines, pesticides and veterinary drugs), new material production, daily chemical production, electronics and biochemical products, marine chemical industry, environmental chemical industry and the like, and can greatly improve the reaction efficiency, reduce the pollutant emission and reduce the energy consumption.
Referring to fig. 2, in the process of producing formaldehyde, the formaldehyde production device comprises a heating system, a reaction system and a product collecting system which are connected with each other, wherein the heating system is positioned at the front end of the reaction system and comprises a heater, a mixer 5, a reboiler 4 and a superheater 6; the reaction system comprises a fire retardant filter 7, a reactor 9 and an absorption tower; the product collection system comprises a preparation tank 13 and a product tank 14; the heater includes first heater 2 and second heater 3, and first heater is located the output of tail gas fan 1, and second heater 3 connects and connects outside air and blender 5 respectively. In the process of producing formaldehyde, generally the required temperature is higher, in order to fully reflect, the number of absorption towers is at least two, including first absorption tower 10 and second absorption tower 11, the second absorption tower still can produce a large amount of waste heat, and the waste heat passes through tail gas fan 1, and then enters first heater 2 fast, heats again and puts into the reaction, can improve reaction efficiency better.
The rear end of the ethynylation reaction device is also connected with a rectifying device, the rectifying device is a 1, 4-butynediol rectifying device, the output end of the 1, 4-butynediol rectifying device is connected with the separation subsystem, 1, 4-butanediol can generate a large amount of 1, 4-butynediol intermediate products in the preparation process, and other impurities such as water vapor and the like can be better removed by utilizing the rectifying device, so that the next processing step is convenient to carry out.
Furthermore, the multistage hydrogenation system comprises a low-pressure hydrogenation system and a high-pressure hydrogenation system, wherein the input ends of the low-pressure hydrogenation system and the high-pressure hydrogenation system are both connected with the second micro-interface generator, and the input end of the second micro-interface generator is connected with the separation subsystem. As the hydrogenation reaction is a strong exothermic reaction, the removal process of reaction heat in the industrial hydrogenation process of the 1, 4-butynediol is complex, local overheating is easy to occur, the catalyst is easy to inactivate at high temperature, and the service life of the catalyst is shortened. The main reason for the over-high temperature of the local reaction is that the hydrogenation process of the 1, 4-butynediol is a serial reaction, and the 1, 4-butynediol is firstly hydrogenated to generate the 1, 4-butylene glycol and then hydrogenated to generate the 1, 4-butylene glycol. The main reaction formula of the 1, 4-butynediol hydrogenation process is as follows:
CH2OH—C≡≡C—CH2OH+H2—→CH2OH—CH＝CH—CH2OH ΔH＝–154.8kJ/mol(1)
CH2OH—CH＝CH—CH2OH+H2—→CH2OH—CH2—CH2—CH2OH ΔH＝–96.3kJ/mol(2)
the 1, 4-butynediol two-stage hydrogenation process can reduce the direct one-stage hydrogenation pressure of the 1, 4-butynediol, improve the yield of the 1, 4-butanediol to more than 96 percent and greatly improve the product quality of the 1, 4-butanediol.
In the actual formaldehyde production process, a steam pocket 8 for pressure stabilization and balance is connected between the reactor 9 and the superheater 6, a certain amount of water exists in the steam pocket 8, certain heat and working medium are stored, the steam pressure change speed can be slowed down when the working condition changes, and a certain buffering effect is achieved when water supply and load are out of harmony in a short time.
Preferably, in the process of producing formaldehyde, a plurality of absorption towers are generally required to be arranged, the number of the absorption towers in the invention is two, the absorption towers comprise a first absorption tower 10 and a second absorption tower 11, the output end of the first absorption tower 10 is connected with a circulating pump 12, the output end of the circulating pump 12 is connected with a preparation tank 13 and a product tank 14, the output end of the second absorption tower 11 is connected with a tail gas fan 1 and a burner 15, and the output end of the tail gas fan 1 is connected with a first heater 2. The formaldehyde generated by the first absorption tower 10 enters a storage link or directly enters the next production process under the action of a circulating pump 12.
Referring to fig. 3, the acetylene generating device comprises a hydrolysis system, an acetylene generator and a cooler in sequence, wherein the output end of the cooler is connected with the hydrolysis tank and the gas holder. In the actual use process, the main production process of calcium carbide hydrolysis is utilizedThe method comprises the following steps: processing raw materials; preparing materials; the mixture is added into an electric furnace through an inlet or a pipeline at the upper end of the electric furnace, and is heated to about 2000 ℃ in an open or closed electric furnace, and calcium carbide is generated by the following reaction: GaO +3C → CaC2+ CO. And taking out the molten calcium carbide from the furnace bottom, cooling and crushing the calcium carbide to obtain a finished product, and packaging the finished product.
The other method is that the wet acetylene generation is to decompose calcium carbide by using water which is 17 times more than the theoretical amount, and the water content of the generated calcium carbide slurry is 90 percent. The heat of reaction is carried away by the slurry water with nearly 1% dissolution loss. Each charge requires replacement and can result in additional loss of acetylene from the hopper. 15 tons of sewage containing a large amount of sulfur and phosphorus are generated when 1 ton of 1, 4-butanediol is produced, and only a small part of sewage can be recycled. The carbide slag slurry is pressed and filtered into a filter cake with the water content of about 35 percent, and the ultimate yield of the acetylene is 96 percent.
The hydrogenation system is internally provided with an external reactor, and the external reactor comprises one or more of a slurry bed, a fixed bed, a trickle bed or a capillary reactor. As the hydrogenation reaction is a stronger exothermic reaction, in order to prolong the service life of equipment, a hydrogenation system needs to select a proper external reactor, and the hydrogenation system with better heat dissipation performance is a slurry bed, a fixed bed, a trickle bed or a capillary reactor.
Referring to fig. 4, preferably, the external reactor of the present invention is a capillary reactor, the capillary reactor is formed by uniformly combining a plurality of single capillaries, the inner diameter of the single capillary is 2-4mm, the inner diameter of the bottom of the integral capillary is 10-16cm, and the diameter of the upper part is 5-8 cm. The external reactor is preferably a capillary reactor generally, the capillary reactor comprises a pump body and a reactor body, the diameter of the bottom of the reactor body is 6-10cm, the diameter of the upper part of the reactor body is 3-6cm, a catalyst is loaded on the inner wall of the reactor, the reaction section is positioned on the lower half section of the reactor body, a micro-interface generator is added, gas-liquid parallel flow downwards passes through the capillary, and the capillary reactor is low in cost, good in heat dissipation effect and convenient to install. The capillary reactor is generally formed by uniformly combining a plurality of single capillaries, the inner diameter of each capillary is 2mm, the inner diameter of the bottom of the integral capillary is 10cm, the inner diameter of the upper part of the integral capillary is 5cm, the catalyst is loaded on the inner wall of the reaction tube, and gas-liquid co-current flows downwards through the capillaries and reacts on the catalyst. Research shows that the temperature is 24-54 ℃, the pressure is 100-300kPa, and the flow state (single-phase flow, two-phase flow with low gas content and two-phase flow with high gas content) has influence on the hydrogenation process of 1, 4-butynediol. The experimental result shows that under the condition of a single capillary tube and a plurality of capillary tubes, the conversion rate of 1, 4-butynediol is 100 percent, and the selectivity of 1, 4-butylene glycol reaches 98 percent. Under the same temperature and pressure, the concentration of active hydrogen on the surface of the catalyst of the plurality of capillary reactors is higher than that of a single capillary, and decreases with the increase of the temperature. The gas-liquid contact efficiency in the capillary reactor is high, the gas-liquid mass transfer is enhanced, and the concentration of active hydrogen on the surface of the catalyst is improved, so that the selectivity of the 1, 4-butylene glycol is improved.
The slurry bed also effectively removes the heat of reaction and keeps the catalyst active, but requires separation of the product from the catalyst. Products and catalysts in the fixed bed and the trickle bed are easy to separate, the reactor returns to the reactor after cooling by adopting reaction material external circulation, intersegment heat exchange and excessive cold hydrogen circulation are used for removing reaction heat, the internal diffusion resistance in the fixed bed and the trickle bed is large, and the operation under high pressure causes the problems of high equipment investment and the like.
A system for preparing 1, 4-butanediol comprises the following operation steps,
the method comprises the following steps: preparing formaldehyde and acetylene by using a formaldehyde production device and an acetylene generating device respectively;
step two: carrying out alkyne-aldehyde reaction on the formaldehyde prepared in the step one and acetylene in a reaction kettle, and adding a catalyst in the alkyne-aldehyde reaction to generate 1, 4-butynediol; the catalyst in the reaction of alkynal is Cu2C2-Bi2O3Or SiO2The reaction temperature is 80-120 ℃, and the reaction pressure in the reaction kettle is less than or equal to 2 MPa;
step three: carrying out hydrogenation reaction on the 1, 4-butynediol prepared in the step two in an external reactor, wherein the hydrogenation reaction is two-stage hydrogenation, the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system, the adopted catalyst is a Ni-based catalyst, and the reaction pressure is 1-5 MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, the adopted catalyst is a Pd-based catalyst, and the reaction pressure is 10-30 MPa; after the two-stage hydrogenation process is finished, 1, 4-butanediol produced by the first-stage hydrogenation reaction and the second-stage hydrogenation reaction is refined in a rectifying tower to produce a 1, 4-butanediol product.
Example 1
The method comprises the following steps: preparing formaldehyde and acetylene by using a formaldehyde production device and an acetylene generating device respectively;
step two: carrying out alkyne-aldehyde reaction on the formaldehyde prepared in the step one and acetylene in a reaction kettle, and adding a catalyst in the alkyne-aldehyde reaction to generate 1, 4-butynediol; the catalyst in the reaction of alkynal is SiO2The reaction temperature is 80 ℃, and the reaction pressure in the reaction kettle is 1 MPa;
step three: carrying out hydrogenation reaction on the 1, 4-butynediol prepared in the step two in an external reactor, wherein the hydrogenation reaction is two-stage hydrogenation, the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system, the adopted catalyst is a Ni-based catalyst, and the reaction pressure is 2 MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, the adopted catalyst is a Pd-based catalyst, and the reaction pressure is 10 MPa; after the two-stage hydrogenation process is finished, 1, 4-butanediol produced by the first-stage hydrogenation reaction and the second-stage hydrogenation reaction is refined in a rectifying tower to produce a 1, 4-butanediol product.
The hydrogenation process of the embodiment adopts one-step hydrogenation, Raney nickel is adopted as a catalyst in a fixed bed, the reaction is carried out under 30MPa, and the ratio of 1, 4-butynediol to hydrogen in a micro-interface generator is 100: 1; the external reactor is a capillary reactor, the catalyst is selected as Ni-based catalyst, the reaction pressure is 10MPa, and the reaction temperature is 30 ℃.
The overall conversion of 1, 4-butynediol was found to be 98.5% and the selectivity for 1, 4-butanediol was found to be 95%. The embodiment is mainly different from the control group in that a capillary reactor is adopted, and compared with a slurry bed, the capillary reactor can keep the lasting activity of the catalyst, has better heat dissipation performance and can greatly prolong the service life of equipment.
Example 2
The method comprises the following steps: preparing formaldehyde and acetylene by using a formaldehyde production device and an acetylene generating device respectively;
step two: carrying out alkyne-aldehyde reaction on the formaldehyde prepared in the step one and acetylene in a reaction kettle, and adding a catalyst in the alkyne-aldehyde reaction to generate 1, 4-butynediol; the catalyst in the reaction of alkynal is SiO2The reaction temperature is 80 ℃, and the reaction pressure in the reaction kettle is 1 MPa;
step three: carrying out hydrogenation reaction on the 1, 4-butynediol prepared in the step two in an external reactor, wherein the hydrogenation reaction is two-stage hydrogenation, the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system, the adopted catalyst is a Ni-based catalyst, and the reaction pressure is 2 MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, the adopted catalyst is a Pd-based catalyst, and the reaction pressure is 10 MPa; after the two-stage hydrogenation process is finished, 1, 4-butanediol produced by the first-stage hydrogenation reaction and the second-stage hydrogenation reaction is refined in a rectifying tower to produce a 1, 4-butanediol product.
The hydrogenation process of the embodiment adopts one-step hydrogenation, Raney nickel is adopted as a catalyst in a fixed bed, the reaction is carried out under 30MPa, and the ratio of 1, 4-butynediol to hydrogen in a micro-interface generator is 100: 1; the external reactor is a capillary reactor, the catalyst is selected as Ni-based catalyst, the reaction pressure is 10MPa, and the reaction temperature is 30 ℃.
The third step is to react in a slurry bed, the catalyst is selected to be Ni-based catalyst, the reaction pressure is 112MPa, and the reaction temperature is 30 ℃. The overall conversion of 1, 4-butynediol was found to be 97.6% and the selectivity for 1, 4-butanediol was 95.6%.
Example 3
The method comprises the following steps: preparing formaldehyde and acetylene by using a formaldehyde production device and an acetylene generating device respectively;
step two: carrying out alkyne-aldehyde reaction on the formaldehyde prepared in the step one and acetylene in a reaction kettle, and adding a catalyst in the alkyne-aldehyde reaction to generate 1, 4-butynediol; the catalyst in the reaction of alkynal is SiO2The reaction temperature is 80 ℃, and the reaction pressure in the reaction kettle is 1 MPa;
step three: carrying out hydrogenation reaction on the 1, 4-butynediol prepared in the step two in an external reactor, wherein the hydrogenation reaction is two-stage hydrogenation, the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system, the adopted catalyst is a Ni-based catalyst, and the reaction pressure is 2 MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, the adopted catalyst is a Pd-based catalyst, and the reaction pressure is 10 MPa; after the two-stage hydrogenation process is finished, 1, 4-butanediol produced by the first-stage hydrogenation reaction and the second-stage hydrogenation reaction is refined in a rectifying tower to produce a 1, 4-butanediol product.
The hydrogenation process of the embodiment adopts one-step hydrogenation, Raney nickel is adopted as a catalyst in a fixed bed, the reaction is carried out under 30MPa, and the ratio of 1, 4-butynediol to hydrogen in a micro-interface generator is 100: 1; the external reactor is a capillary reactor, the catalyst is selected as Ni-based catalyst, the reaction pressure is 10MPa, and the reaction temperature is 30 ℃.
The third step is reaction in a slurry bed, the selected catalyst is Ni-based catalyst, the reaction pressure is 12MPa, and the reaction temperature is 30 ℃. The overall conversion of 1, 4-butynediol was found to be 100% and the selectivity for 1, 4-butanediol was found to be 98.1%.
Example 4
The method comprises the following steps: preparing formaldehyde and acetylene;
step two: acetylene and formaldehyde are subjected to acetylenic aldehyde reaction under the action of a catalyst to produce 1, 4-butynediol;
step three: under the action of a catalyst, 1, 4-butynediol is hydrogenated in a reactor to produce 1, 4-butanediol;
in the second step and the third step, the connecting end of the acetylene and the formaldehyde and the hydrogenation input end of the 1, 4-butynediol are both connected with a micro-interface generator.
The hydrogenation of 1, 4-butynediol adopts two-step hydrogenation, the catalyst is Pd,
the hydrogenation process of the embodiment adopts two-step hydrogenation, Pd is adopted in a fixed bed to react under 10MPa, and the gas-gas ratio of 1, 4-butynediol to hydrogen in a micro-interface generator is 200: 1;
the third step is reaction in a slurry bed, the catalyst is selected as Ni-based catalyst, the reaction pressure is 12MPa, and the reaction temperature is 24-30 ℃. The overall conversion of 1, 4-butynediol was found to be 100% and the selectivity for 1, 4-butanediol was found to be 98.1%.
Example 5
The method comprises the following steps: preparing formaldehyde and acetylene;
step two: acetylene and formaldehyde are subjected to acetylenic aldehyde reaction under the action of a catalyst to produce 1, 4-butynediol;
step three: under the action of a catalyst, 1, 4-butynediol is hydrogenated in a reactor to produce 1, 4-butanediol;
in the second step and the third step, the connecting end of the acetylene and the formaldehyde and the hydrogenation input end of the 1, 4-butynediol are both connected with a gas-gas type micro-interface generator.
The hydrogenation process of the embodiment adopts one-step hydrogenation, a nickel-based catalyst (generally Raney nickel) with alumina or silica gel as a carrier is adopted in a fixed bed to react under 30-32MPa, and the gas-gas ratio of 1, 4-butynediol to hydrogen in a micro-interface generator is 100: 1;
the third step is reaction in a capillary reactor, and Al is selected as a catalyst2O3The reaction pressure is 20MPa, and the reaction temperature is 45 ℃. The overall conversion of 1, 4-butynediol was found to be 99.1% and the selectivity for 1, 4-butanediol was 96.7%.
The embodiment is mainly different from the control group in that a capillary reactor is adopted, and compared with a slurry bed, the capillary reactor can keep the lasting activity of the catalyst, has better heat dissipation performance and can greatly prolong the service life of equipment.
Example 6
The method comprises the following steps: preparing formaldehyde and acetylene by using a formaldehyde production device and an acetylene generating device respectively;
step two: carrying out alkyne-aldehyde reaction on the formaldehyde prepared in the step one and acetylene in a reaction kettle, and adding a catalyst in the alkyne-aldehyde reaction to generate 1, 4-butynediol; the catalyst in the reaction of alkynal is Cu2C2-Bi2O3Or SiO2The reaction temperature is 80-120 ℃, and the reaction pressure in the reaction kettle is 1 MPa;
step three: carrying out hydrogenation reaction on the 1, 4-butynediol prepared in the step two in an external reactor, wherein the hydrogenation reaction is first-stage hydrogenation, the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system, the adopted catalyst is a Ni-based catalyst, and the reaction pressure is 1-5 MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, the adopted catalyst is a Pd-based catalyst, and the reaction pressure is 10-30 MPa; after the two-stage hydrogenation process is finished, 1, 4-butanediol produced by the first-stage hydrogenation reaction and the second-stage hydrogenation reaction is refined in a rectifying tower to produce a 1, 4-butanediol product.
The third step is reaction in a capillary reactor, and Al is selected as a catalyst2O3The reaction pressure is 20MPa, and the reaction temperature is 30 ℃. The overall conversion of 1, 4-butynediol was found to be 100% and the selectivity for 1, 4-butanediol was found to be 99.7%.
EXAMPLES 1 to 6
In conclusion, the third step is carried out in a capillary reactor, and in the hydrogenation mode, two-step hydrogenation or three-step hydrogenation is preferably adopted, so that the 1, 4-butynediol can be completely converted, and the selectivity of the 1, 4-butanediol is extremely high.
The embodiment is mainly different from a control group in that a capillary reactor is adopted, and compared with a slurry bed, the capillary reactor can keep the lasting activity of the catalyst, has better heat dissipation performance and can greatly prolong the service life of equipment
So far, the technical solutions of the present invention have been described in connection with the preferred embodiments shown in the drawings, but it is easily understood by those skilled in the art that the scope of the present invention is obviously not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.
Claims (10)
1. A preparation system of 1, 4-butanediol is characterized by comprising a formaldehyde production device, an acetylene generation device, a micro-interface generator, a deionization system and a hydrogenation system; the micro-interface generator is used for crushing gas to form micron-sized bubbles with the diameter being more than or equal to 1 mu m and less than 1mm, and comprises a first micro-interface generator and a second micro-interface generator;
the output ends of the formaldehyde production device and the acetylene generation device are connected with the ethynylation reaction device through the first micro-interface generator; the output end of the separation subsystem is connected with the hydrogenation system through the second micro-interface generator, and the hydrogenation system is a multistage hydrogenation system;
the formaldehyde production device comprises a heating system, a reaction system and a product collecting system which are sequentially connected, wherein the heating system comprises a heater, a reboiler and a superheater; the heater comprises a first heater and a second heater, the first heater is located at the output end of the tail gas fan, and the second heater is connected with the outside air and the mixer respectively.
2. The system for preparing 1, 4-butanediol as defined in claim 1, wherein the rear end of the ethynylation reaction device is further connected with a rectifying device, the rectifying device is a 1, 4-butynediol rectifying device, and the output end of the 1, 4-butynediol rectifying device is connected with the separation subsystem.
3. The system for preparing 1, 4-butanediol of claim 1, wherein the multistage hydrogenation system comprises a low-pressure hydrogenation system and a high-pressure hydrogenation system, the input ends of the low-pressure hydrogenation system and the high-pressure hydrogenation system are both connected with a second micro-interface generator, and the input end of the second micro-interface generator is connected with the disengagement subsystem.
4. The system for preparing 1, 4-butanediol as set forth in claim 1, wherein a steam drum for pressure stabilization and equalization is further connected between the reactor and the superheater.
5. The system for preparing 1, 4-butanediol as defined in claim 1, wherein the number of the absorption towers is two, and the absorption towers comprise a first absorption tower and a second absorption tower, the output end of the first absorption tower is connected with a circulating pump, the output end of the circulating pump is connected with the preparation tank and the product tank, the output end of the second absorption tower is connected with a tail gas fan and a burner, and the output end of the tail gas fan is connected with the first heater.
6. The system for preparing 1, 4-butanediol as defined in claim 1, wherein the acetylene generating device comprises a hydrolysis system, an acetylene generator and a cooler in sequence, and the output end of the cooler is connected with the hydrolysis tank and the gas holder.
7. The system for preparing 1, 4-butanediol of claim 1, wherein an external reactor is arranged in the hydrogenation system, and the external reactor comprises one or more of a slurry bed, a fixed bed, a trickle bed or a capillary reactor.
8. The system for producing 1, 4-butanediol of claim 7, wherein the capillary reactor has an upper end opening diameter smaller than a lower end opening diameter.
9. The system for preparing 1, 4-butanediol of claim 8, wherein the capillary reactor is formed by uniformly combining a plurality of single capillaries, the inner diameter of each single capillary is 2-4mm, the inner diameter of the bottom of the integral capillary is 10-16cm, and the diameter of the upper part of the integral capillary is 5-8 cm.
10. A preparation process of 1, 4-butanediol is characterized by comprising the following steps:
the method comprises the following steps: preparing formaldehyde and acetylene by using a formaldehyde production device and an acetylene generating device respectively;
step two: carrying out alkyne-aldehyde reaction on the formaldehyde prepared in the step one and acetylene in a reaction kettle, and adding a catalyst in the alkyne-aldehyde reaction to generate 1, 4-butynediol; catalyst in alkyne aldehyde reactionIs Cu2C2-Bi2O3Or SiO2The reaction temperature is 80-120 ℃, and the reaction pressure in the reaction kettle is less than or equal to 2 MPa;
step three: carrying out hydrogenation reaction on the 1, 4-butynediol prepared in the step two in an external reactor, wherein the hydrogenation reaction is two-stage hydrogenation, the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system, the adopted catalyst is a Ni-based catalyst, and the reaction pressure is 1-5 MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, the adopted catalyst is a Pd-based catalyst, and the reaction pressure is 10-30 MPa; after the two-stage hydrogenation process is finished, 1, 4-butanediol produced by the first-stage hydrogenation reaction and the second-stage hydrogenation reaction is refined in a rectifying tower to produce a 1, 4-butanediol product.
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| CN107141196A (en) * | 2017-06-27 | 2017-09-08 | 查都（上海）科技有限公司 | A kind of 1,4 butynediols two-stage hydrogenation systems |
| CN109651110A (en) * | 2019-01-17 | 2019-04-19 | 新疆天智辰业化工有限公司 | A kind of production method of high-purity 1,4- butanediol |
| CN109678660A (en) * | 2019-02-15 | 2019-04-26 | 陕西陕化煤化工集团有限公司 | A kind of improvement technique producing 1,4-butanediol |
| CN109734556A (en) * | 2019-01-04 | 2019-05-10 | 内蒙古东景生物环保科技有限公司 | A kind of preparation method of 1,4 butanediol composition |
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| CN107141196A (en) * | 2017-06-27 | 2017-09-08 | 查都（上海）科技有限公司 | A kind of 1,4 butynediols two-stage hydrogenation systems |
| CN109734556A (en) * | 2019-01-04 | 2019-05-10 | 内蒙古东景生物环保科技有限公司 | A kind of preparation method of 1,4 butanediol composition |
| CN109651110A (en) * | 2019-01-17 | 2019-04-19 | 新疆天智辰业化工有限公司 | A kind of production method of high-purity 1,4- butanediol |
| CN109678660A (en) * | 2019-02-15 | 2019-04-26 | 陕西陕化煤化工集团有限公司 | A kind of improvement technique producing 1,4-butanediol |
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