WO2021042579A1 - Preparation system and process for 1,4-butanediol - Google Patents

Preparation system and process for 1,4-butanediol Download PDF

Info

Publication number
WO2021042579A1
WO2021042579A1 PCT/CN2019/120090 CN2019120090W WO2021042579A1 WO 2021042579 A1 WO2021042579 A1 WO 2021042579A1 CN 2019120090 W CN2019120090 W CN 2019120090W WO 2021042579 A1 WO2021042579 A1 WO 2021042579A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
hydrogenation
acetylene
butanediol
micro
Prior art date
Application number
PCT/CN2019/120090
Other languages
French (fr)
Chinese (zh)
Inventor
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
南京延长反应技术研究院有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 南京延长反应技术研究院有限公司 filed Critical 南京延长反应技术研究院有限公司
Publication of WO2021042579A1 publication Critical patent/WO2021042579A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0046—Sequential or parallel reactions, e.g. for the synthesis of polypeptides or polynucleotides; Apparatus and devices for combinatorial chemistry or for making molecular arrays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0242—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid flow within the bed being predominantly vertical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C07C29/82—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/04—Acyclic alcohols with carbon-to-carbon triple bonds
    • C07C33/042—Acyclic alcohols with carbon-to-carbon triple bonds with only one triple bond
    • C07C33/044—Alkynediols
    • C07C33/046—Butynediols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group

Definitions

  • the present invention relates to the technical field of preparation of 1,4-butanediol, in particular to a preparation system and process of 1,4-butanediol.
  • 1,4-Butanediol is an important basic organic chemical and fine chemical raw material. It has a wide range of uses, especially its derivatives are fine chemical products with high added value, which are widely used as solvents, medicines, cosmetics, plasticizers, curing agents, pesticides, herbicides, artificial leather, fibers, engineering plastics, etc. 1,4-Butanediol is also used to produce tetrahydrofuran (THF), gamma-butyrolactone (GBL), N-methylpyrrolidone (NMP), etc.
  • PBT polybutylene terephthalate
  • PBT polybutylene terephthalate
  • 1,4-butanediol There are more than a dozen production process routes of 1,4-butanediol, mainly including Reppe method, n-butane/maleic anhydride method, butadiene method and propylene oxide method, among which Reppe method and n-butane/maleic anhydride
  • the method is currently the most important process for producing 1,4-butanediol.
  • Reppe method is divided into classic method and modified method.
  • classical method under the operating conditions of 13.8-27.6 MPa and 250-350°C, the partial pressure of acetylene is high and there is a danger of explosion.
  • polymerization of acetylene will generate polyacetylene, which leads to the deactivation of the catalyst.
  • the Cu-Bi silica gel catalyst is used, the temperature is 90-100°C, the pressure is 0.1-0.2MPa, and the synthesis of 1,4-butynediol is carried out in a suspended bed or a slurry bed to reduce the reaction process of acetylene. Partial pressure.
  • the purpose of the present invention is to provide a 1,4-butanediol preparation system and process, which improves the traditional 1,4-butanediol production system, while reducing the cost of enterprise equipment upgrades, Improve reaction efficiency.
  • the present invention provides a 1,4-butanediol preparation system, including a formaldehyde production device, an acetylene generation device, a micro-interface generator, a disengagement subsystem, and a hydrogenation system; the micro-interface generator is used for The gas is crushed to form micron-level bubbles with a diameter of ⁇ 1 ⁇ m and ⁇ 1mm, which includes a first micro-interface generator and a second micro-interface generator; the output ends of the formaldehyde production device and the acetylene generation device pass through the first micro-interface generator and the second micro-interface generator.
  • a micro-interface generator is connected to the acetylene reaction device; the output end of the disengagement subsystem is connected to the hydrogenation system through the second micro-interface generator, and the hydrogenation system is a multi-stage hydrogenation system;
  • the formaldehyde production device includes a heating system, a reaction system, and a product collection system connected to each other.
  • the heating system includes a heater, a reboiler and a superheater; the heater includes a first heater and a second heater.
  • a heater is located at the output end of the exhaust fan, and the second heater is connected to the outside air and the mixer respectively.
  • the back end of the acetylene reaction device is also connected to a rectification device, and the rectification device is a 1,4-butynediol rectification device.
  • the output end of the 4-butynediol rectification device is connected to the disengagement subsystem.
  • the multi-stage hydrogenation system includes a low-pressure hydrogenation system and a high-pressure hydrogenation system, and the input ends of the low-pressure hydrogenation system and the high-pressure hydrogenation system are both
  • the second micro-interface generator is connected, and the input end of the second micro-interface generator is connected to the decoupling subsystem.
  • a steam drum for pressure stabilization and balance is also connected between the reactor and the superheater.
  • the number of the absorption towers is two, including a first absorption tower and a second absorption tower, the output end of the first absorption tower is connected with a circulating pump, and 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 an exhaust fan and a burner, and the output end of the exhaust fan is connected with the first heater.
  • the acetylene generating device sequentially includes a hydrolysis system, an acetylene generator and a cooler, and the output end of the cooler is connected to the hydrolysis tank and the gas tank.
  • an external reactor is provided in the hydrogenation system, and the external reactor includes a slurry bed, a fixed bed, a trickle bed or a capillary reactor.
  • the external reactor includes a slurry bed, a fixed bed, a trickle bed or a capillary reactor.
  • the capillary reactor has an upper opening diameter smaller than a lower opening diameter.
  • the capillary reactor is formed by a uniform combination of a plurality of single capillaries, the inner diameter of the single capillary is 2-4mm, the inner diameter of the bottom of the monolithic capillary is 10-16cm, and the upper part The diameter is 5-8cm.
  • a preparation process of 1,4-butanediol includes the following steps:
  • Step 1 Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
  • Step 2 The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reaction kettle, and a catalyst is added to the acetylene reaction to produce 1,4-butynediol; the catalyst in the acetylene reaction is Cu 2 C 2 -Bi 2 O 3 or SiO 2 , the reaction temperature is 80-120°C, and the reaction pressure in the reactor is ⁇ 2MPa;
  • Step 3 Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor.
  • the hydrogenation reaction is a two-stage hydrogenation.
  • the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system.
  • the catalyst used is It is a Ni-based catalyst with a reaction pressure of 1-5MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, and the catalyst used is a Pd-based catalyst with a reaction pressure of 10-30MPa; after the two-stage hydrogenation process is completed, the first stage
  • the 1,4-butanediol produced by the hydrogenation reaction and the second stage of hydrogenation is refined in a rectifying tower to produce 1,4-butanediol products.
  • the purpose of the present invention is to provide a 1,4-butanediol preparation system, including a formaldehyde production device, an acetylene generating device, a micro-interface generator, a disengagement subsystem, and a hydrogenation system;
  • the micro-interface generator includes a first A micro-interface generator and a second micro-interface generator; the output ends of the formaldehyde production device and the acetylene generating device are connected through the first micro-interface generator and quickly mixed to perform the acetylene aldehyde reaction to generate 1,4-butane Acetylene glycol.
  • the output end of the separation subsystem is connected to the hydrogenation system through the second micro-interface generator, and the hydrogenation system is a multi-stage hydrogenation system; because the hydrogenation reaction is a strong exothermic reaction, industrially 1 , 4-Butynediol hydrogenation process is prone to local overheating, high temperature easily deactivates the catalyst, and reduces the life of the catalyst. Therefore, the general hydrogenation system uses a multi-stage hydrogenation system, which can greatly improve the use of equipment. Life, to prevent local overheating.
  • the formaldehyde production device includes a heating system, a reaction system, and a product collection system connected to each other.
  • the heating system is located at the front end of the reaction system and includes a heater, a reboiler, and a superheater; the reaction system includes a flame retardant filter , Reactor and absorption tower; the product collection system includes a preparation tank and a product tank; the heater includes a first heater and a second heater, the first heater is located at the output end of the exhaust fan, and the second heater The device is connected to the outside air and the mixer respectively.
  • the micro-interface generator can break the hydrogen into micron-sized bubbles with a diameter of ⁇ 1 ⁇ m and ⁇ 1mm, and at the same time fully mix the micron-sized bubbles with 1,4-butynediol to form a gas-liquid Emulsions increase the contact area between gas and liquid, but the chemical properties are inconvenient, which can greatly improve the chemical reaction efficiency during the reaction process.
  • Figure 1 is a schematic diagram of the structure of the present invention
  • Figure 2 is a schematic diagram of the structure of the formaldehyde production device of the present invention.
  • Figure 3 is a production flow chart of acetylene of the present invention.
  • Figure 4 is a schematic diagram of the structure of a capillary reactor
  • Figure 5 is a schematic diagram of the process flow of the present invention.
  • the terms “installed”, “connected”, and “connected” should be understood in a broad sense. For example, they can be fixed or fixed. It is a detachable connection or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication between two components.
  • installed e.g., they can be fixed or fixed. It is a detachable connection or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication between two components.
  • the specific meaning of the above-mentioned terms in the present invention can be understood according to specific circumstances.
  • the purpose of the present invention is to provide a 1,4-butanediol preparation system, including a formaldehyde production device, an acetylene generation device, a micro-interface generator, a separation subsystem, and a hydrogenation system; micro-interface
  • the generator includes a first micro-interface generator and a second micro-interface generator; the output ends of the formaldehyde production device and the acetylene generating device are connected through the first micro-interface generator and quickly mixed to perform the acetylene aldehyde reaction to generate 1,4-butyne Glycol.
  • the output end of the disengagement subsystem is connected to the hydrogenation system through the second micro-interface generator, and the hydrogenation system is a multi-stage hydrogenation system; because the hydrogenation reaction is a strong exothermic reaction, 1,4-butyne two is industrially In the alcohol hydrogenation process, local overheating is easy to occur, and high temperature can easily deactivate the catalyst and reduce the life of the catalyst. Therefore, the multi-stage hydrogenation system is generally used in the hydrogenation system, which can greatly increase the service life of the equipment and prevent local overheating.
  • the micro-interface enhanced reactor is suitable for most reaction processes controlled by mass transfer and heat transfer, such as gas-liquid, gas-liquid-solid, liquid-liquid, liquid-liquid-solid, gas-liquid-liquid-solid reaction systems and many more.
  • the basic scientific principle is to break the gas or liquid particle diameter at the gas-liquid, liquid-liquid, gas-liquid-liquid interface of the reaction system into a micron range (30-900 ⁇ m), while the traditional bubbling reactor
  • the diameter of gas and liquid particles is generally millimeter/cm (3mm-30mm). In this way, the mass transfer area and total mass transfer rate between gas-liquid and liquid-liquid can be doubled, thereby greatly increasing the reaction speed, effectively controlling side reactions and improving product yield, and significantly reducing the energy and material consumption of the reaction process. , And improve the safety of the reaction section.
  • the reaction rate can be increased by 3-5 times or more compared with traditional stirred reactors.
  • the energy consumption can generally be saved by 30-50% or more, and the material consumption can be saved by 5%-20%.
  • the micro-interface enhanced reactor is a universal technology, suitable for petrochemical, coal chemical, fine chemical, pharmaceutical (medicine, pesticide, veterinary) production, new material production, daily chemical production, electronics and biological chemicals, marine chemical, environmental Chemical reactions in multiple industries and fields, such as gas-liquid, gas-liquid-solid, liquid-liquid, liquid-liquid-solid, gas-liquid-liquid-solid and other chemical reactions, can greatly improve reaction efficiency and reduce pollutant emissions And reduce energy consumption.
  • the formaldehyde production device includes a heating system, a reaction system, and a product collection system that are connected to each other.
  • the heating system is located at the front end of the reaction system and includes a heater, a mixer 5, a reboiler 4, and a superheater 6;
  • the reaction system includes a flame retardant filter 7, a reactor 9 and an absorption tower;
  • the product collection system includes a preparation tank 13 and a product tank 14;
  • the heater includes a first heater 2 and a second heater 3, and the first heater is located in the exhaust fan
  • the output end of 1, the second heater 3 is connected to the outside air and the mixer 5, respectively.
  • the required temperature is relatively high.
  • the number of absorption towers should be at least two, including the first absorption tower 10 and the second absorption tower 11.
  • the second absorption tower still generates a lot of waste heat.
  • the waste heat quickly enters the first heater 2 after passing through the exhaust fan 1, and is heated again and put into the reaction, which can better improve the reaction efficiency.
  • the back end of the acetylene reaction device of the present invention is also connected to a rectification device, the rectification device is a 1,4-butynediol rectification device, and the output end of the 1,4-butynediol rectification device is connected to the disengagement subsystem.
  • the rectification device is a 1,4-butynediol rectification device
  • the output end of the 1,4-butynediol rectification device is connected to the disengagement subsystem.
  • the multi-stage hydrogenation system of the present invention includes 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 to the second micro-interface generator, and the second micro-interface generator The input terminal is disconnected from the subsystem.
  • the hydrogenation reaction is a strong exothermic reaction, the process of removing reaction heat in the industrial 1,4-butynediol hydrogenation process is complicated, and local overheating is prone to occur. High temperature can easily deactivate the catalyst and reduce the life of the catalyst.
  • the main reason for the local reaction temperature being too high is that the 1,4-butynediol hydrogenation process is a series of reactions. 1,4-butynediol is first hydrogenated to form 1,4-butenediol and then hydrogenated to form 1,4-Butanediol.
  • the main reaction formula of 1,4-butynediol hydrogenation process is:
  • the 1,4-butynediol two-stage hydrogenation process can reduce the direct one-stage hydrogenation pressure of 1,4-butynediol, and the yield of 1,4-butynediol can be increased to over 96%, which can greatly Improve the quality of 1,4-butanediol products.
  • a steam drum 8 for voltage stabilization and balance is also connected between the reactor 9 and the superheater 6.
  • the steam drum 8 has a certain amount of water stored in the steam drum, and has a certain amount of heat and working fluid storage. It can slow down the steam pressure change speed when the working conditions change, and play a certain buffering effect when the water supply and the load are not coordinated for a short time.
  • the number of absorption towers in the present invention is two, including the first absorption tower 10 and the second absorption tower 11.
  • the output end is connected to the circulating pump 12, the output end of the circulating pump 12 is connected to the preparation tank 13 and the product tank 14, the output end of the second absorption tower 11 is connected to the exhaust fan 1 and the burner 15, and the output end of the exhaust fan 1 is connected to the first One heater 2.
  • the formaldehyde generated by the first absorption tower 10 enters the storage link under the action of the circulating pump 12 or directly enters the next production process.
  • the acetylene generating device sequentially includes a hydrolysis system, an acetylene generator and a cooler, and the output end of the cooler is connected to the hydrolysis tank and the gas tank.
  • the main production processes using calcium carbide hydrolysis are: raw material processing; batching; adding the mixture into the electric furnace through the inlet or pipeline at the upper end of the electric furnace, and heating it to about 2000 °C in an open or closed electric furnace, according to the following formula
  • the reaction generates calcium carbide: GaO+3C ⁇ CaC 2 +CO.
  • the molten calcium carbide is taken out from the bottom of the furnace, cooled and broken, and then packaged as a finished product.
  • Another method is wet acetylene generation, which uses 17 times more than the theoretical amount of water to decompose calcium carbide, and the resulting calcium carbide slag slurry has a water content of 90%.
  • the reaction heat is taken away by the slurry water, and there is a dissolution loss of nearly 1%.
  • Each feeding needs to be replaced, which will drain the acetylene in the hopper and cause additional losses.
  • 15 tons of sewage containing a large amount of sulfur and phosphorus are produced, and only a small part can be reused.
  • the calcium carbide slag slurry is filtered into a filter cake with a water content of about 35%, and the ultimate yield of acetylene is 96%.
  • the hydrogenation system of the present invention is provided with an external reactor, and the external reactor includes one or more of a slurry bed, a fixed bed, a trickle bed or a capillary reactor. Since the hydrogenation reaction is a strong exothermic reaction, in order to improve the service life of the equipment, the hydrogenation system needs to select a suitable external reactor, and the heat dissipation performance is better for the slurry bed, fixed bed, trickle bed or capillary reaction. Device.
  • the external reactor of the present invention is a capillary reactor.
  • the capillary reactor is formed by a uniform combination of a plurality of single capillaries.
  • the inner diameter of a single capillary is 2-4mm, and the inner diameter of the bottom of the monolithic capillary is 10- 16cm, the diameter of the upper part is 5-8cm.
  • External reactors generally prefer capillary reactors.
  • the capillary reactor includes a pump body and a reactor body.
  • the bottom of the reactor body has a diameter of 6-10 cm and an upper diameter of 3-6 cm.
  • the catalyst is supported on the inner wall of the reaction tube, and the reaction section is located In the lower half of the reactor body, a micro-interface generator is added, and gas and liquid flow down through the capillary tube.
  • the capillary reactor has low cost, good heat dissipation effect, and is easy to install.
  • a capillary reactor is generally formed by a uniform combination of multiple single capillaries.
  • the inner diameter of a single capillary is 2mm.
  • the inner diameter of the bottom of the monolithic capillary is 10cm and the upper part is 5cm.
  • the catalyst is supported on the inner wall of the reaction tube. The reaction takes place on the catalyst. Studies have shown that the temperature at 24°C-54°C, the pressure at 100-300kPa, and the flow state (single-phase flow, low gas holdup two-phase flow, high gas hold-up two-phase flow) compared to 1,4-butynediol The impact of the hydrogenation process.
  • the slurry bed can also effectively remove the heat of reaction and keep the catalyst active, but the product and the catalyst need to be separated.
  • the product and the catalyst in the fixed bed and trickle bed are easy to separate.
  • the reactor adopts the external circulation of the reaction material to cool down and then returns to the reactor, the heat exchange between sections and the excess cold hydrogen circulation to remove the reaction heat, the fixed bed and the trickle bed
  • the internal diffusion resistance is large, and the operation under high pressure causes problems such as high equipment investment.
  • the production system of 1,4-butanediol includes the following steps:
  • Step 1 Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
  • Step 2 The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reaction kettle, and a catalyst is added to the acetylene reaction to produce 1,4-butynediol; the catalyst in the acetylene reaction is Cu 2 C 2 -Bi 2 O 3 or SiO 2 , the reaction temperature is 80-120°C, and the reaction pressure in the reactor is ⁇ 2MPa;
  • Step 3 Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor.
  • the hydrogenation reaction is a two-stage hydrogenation.
  • the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system.
  • the catalyst used is It is a Ni-based catalyst with a reaction pressure of 1-5MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, and the catalyst used is a Pd-based catalyst with a reaction pressure of 10-30MPa; after the two-stage hydrogenation process is completed, the first stage
  • the 1,4-butanediol produced by the hydrogenation reaction and the second stage of hydrogenation is refined in a rectifying tower to produce 1,4-butanediol products.
  • Step 1 Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
  • Step 2 The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reactor, and a catalyst is added to the acetylene reaction to generate 1,4-butynediol; the catalyst in the acetylene reaction is SiO 2 , and the reaction The temperature is 80°C, and the reaction pressure in the reactor is 1MPa;
  • Step 3 Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor.
  • the hydrogenation reaction is a two-stage hydrogenation.
  • the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system.
  • the catalyst used is It is a Ni-based catalyst with a reaction pressure of 2MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, and the catalyst used is a Pd-based catalyst with a reaction pressure of 10MPa; after the two-stage hydrogenation process is completed, the first-stage hydrogenation reaction is carried out with
  • the 1,4-butanediol produced in the second stage of hydrogenation is refined in a rectification tower to produce 1,4-butanediol products.
  • the hydrogenation process of this embodiment uses one-step hydrogenation.
  • Raney nickel is used as a catalyst in a fixed bed and the reaction is carried out at 30 MPa.
  • the ratio of 1,4-butynediol to hydrogen in the 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°C.
  • the main difference between the above embodiment and the control group is the use of a capillary reactor. Compared with a slurry bed, the capillary reactor can keep the catalyst active and has better heat dissipation, which can greatly increase the service life of the equipment.
  • Step 1 Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
  • Step 2 The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reaction kettle, and a catalyst is added to the acetylene reaction to generate 1,4-butynediol; the catalyst in the acetylene reaction is SiO 2 , and the reaction The temperature is 80°C, and the reaction pressure in the reactor is 1MPa;
  • Step 3 Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor.
  • the hydrogenation reaction is a two-stage hydrogenation.
  • the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system.
  • the catalyst used is It is a Ni-based catalyst with a reaction pressure of 2MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, and the catalyst used is a Pd-based catalyst with a reaction pressure of 10MPa; after the two-stage hydrogenation process is completed, the first-stage hydrogenation reaction is carried out with
  • the 1,4-butanediol produced in the second stage of hydrogenation is refined in a rectification tower to produce 1,4-butanediol products.
  • the hydrogenation process of this embodiment uses one-step hydrogenation.
  • Raney nickel is used as a catalyst in a fixed bed and the reaction is carried out at 30 MPa.
  • the ratio of 1,4-butynediol to hydrogen in the 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°C.
  • the reaction is carried out in a slurry bed.
  • the catalyst is selected as Ni-based catalyst, the reaction pressure is 112MPa, and the reaction temperature is 30°C.
  • the test found that the total conversion rate of 1,4-butynediol was 97.6%, and the selectivity of 1,4-butanediol was 95.6%.
  • Step 1 Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
  • Step 2 The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reactor, and a catalyst is added to the acetylene reaction to generate 1,4-butynediol; the catalyst in the acetylene reaction is SiO 2 , and the reaction The temperature is 80°C, and the reaction pressure in the reactor is 1MPa;
  • Step 3 Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor.
  • the hydrogenation reaction is a two-stage hydrogenation.
  • the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system.
  • the catalyst used is It is a Ni-based catalyst with a reaction pressure of 2MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, and the catalyst used is a Pd-based catalyst with a reaction pressure of 10MPa; after the two-stage hydrogenation process is completed, the first-stage hydrogenation reaction is carried out with
  • the 1,4-butanediol produced in the second stage of hydrogenation is refined in a rectification tower to produce 1,4-butanediol products.
  • the hydrogenation process of this embodiment uses one-step hydrogenation.
  • Raney nickel is used as a catalyst in a fixed bed and the reaction is carried out at 30 MPa.
  • the ratio of 1,4-butynediol to hydrogen in the 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°C.
  • the reaction is carried out in a slurry bed.
  • the selected catalyst is a Ni-based catalyst, the reaction pressure is 12MPa, and the reaction temperature is 30°C.
  • the test found that the total conversion rate of 1,4-butynediol was 100%, and the selectivity of 1,4-butanediol was 98.1%.
  • Step 1 Preparation of formaldehyde and acetylene
  • Step 2 Acetylene and formaldehyde react under the action of a catalyst to produce 1,4-butynediol;
  • Step 3 Under the action of a catalyst, in the reactor, 1,4-butynediol is hydrogenated to produce 1,4-butanediol;
  • step two and step three both the connecting end of acetylene and formaldehyde and the 1,4-butynediol hydrogenation input end are connected with a micro-interface generator.
  • 1,4-butynediol hydrogenation adopts two-step hydrogenation, the catalyst is Pd,
  • the hydrogenation process in this embodiment uses two-step hydrogenation.
  • Pd is used in a fixed bed and the reaction is carried out at 10 MPa.
  • the gas-to-gas ratio of 1,4-butynediol to hydrogen in the micro-interface generator is 200: 1;
  • the third step is to react in a slurry bed, and the catalyst is selected as a Ni-based catalyst, the reaction pressure is 12 MPa, and the reaction temperature is 24-30°C.
  • the test found that the total conversion rate of 1,4-butynediol was 100%, and the selectivity of 1,4-butanediol was 98.1%.
  • Step 1 Preparation of formaldehyde and acetylene
  • Step 2 Acetylene and formaldehyde react under the action of a catalyst to produce 1,4-butynediol;
  • Step 3 Under the action of a catalyst, in the reactor, 1,4-butynediol is hydrogenated to produce 1,4-butanediol;
  • step two and step three both the connecting end of acetylene and formaldehyde and the 1,4-butynediol hydrogenation input end are connected with a gas-gas type micro-interface generator.
  • the hydrogenation process of this embodiment uses one-step hydrogenation.
  • a nickel-based catalyst generally Raney nickel
  • alumina or silica gel is used in a fixed bed, and the reaction is carried out at 30-32MPa.
  • the micro-interface generator is The gas-gas ratio of 1,4-butynediol to hydrogen is 100:1;
  • the third step is the reaction in the capillary reactor.
  • the catalyst is Al 2 O 3 , the reaction pressure is 20 MPa, and the reaction temperature is 45°C.
  • the test found that the total conversion rate of 1,4-butynediol was 99.1%, and the selectivity of 1,4-butanediol was 96.7%.
  • the main difference between the above embodiment and the control group is the use of a capillary reactor.
  • the capillary reactor can keep the catalyst active and has better heat dissipation, which can greatly improve the service life of the equipment.
  • Step 1 Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
  • Step 2 The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reaction kettle, and a catalyst is added to the acetylene reaction to produce 1,4-butynediol; the catalyst in the acetylene reaction is Cu 2 C 2 -Bi 2 O 3 or SiO 2 , the reaction temperature is 80-120°C, and the reaction pressure in the reactor is 1 MPa;
  • Step 3 Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor.
  • the hydrogenation reaction is one-stage hydrogenation.
  • the first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system.
  • the catalyst used is Ni-based catalyst, the reaction pressure is 1-5MPa;
  • the second stage hydrogenation reaction is carried out in a high-pressure system, the catalyst used is a Pd-based catalyst, and the reaction pressure is 10-30MPa; after the two-stage hydrogenation process is completed, the first stage is added
  • the 1,4-butanediol produced by the hydrogen reaction and the second stage of hydrogenation is refined in a rectifying tower to produce 1,4-butanediol products.
  • the reaction is carried out in a capillary reactor.
  • the catalyst is Al 2 O 3
  • the reaction pressure is 20 MPa
  • the reaction temperature is 30°C.
  • the third step is carried out in a capillary reactor.
  • two-step hydrogenation or three-step hydrogenation is preferred.
  • 1,4-butynediol can be completely converted, and 1,4- The selectivity of butanediol is extremely high.
  • the main difference between the above embodiment and the control group is the use of a capillary reactor.
  • the capillary reactor can keep the catalyst active and has better heat dissipation, which can greatly improve the service life of the equipment

Abstract

The present invention is suitable for use in the technical field of 1,4 -butanediol preparation, and provides a preparation system and process for 1,4-butanediol, comprising a formaldehyde generating apparatus, an acetylene generating apparatus, microinterface generators, a deionising system, and hydrogenation systems; output ends of the formaldehyde generating apparatus and the acetylene generating apparatus are connected to an alkylation reaction apparatus by means of a first microinterface generator; an output end of the deionising system is connected to the hydrogenation systems by means of second microinterface generators; the formaldehyde generating apparatus comprises a heating system, a reaction system, and a product collection system connected to one another, the reaction system comprising a flame retardant filter, a reactor, and an absorption tower; and the heater comprises a first heater and a second heater. Thus, by means of improving the traditional 1,4-butanediol production process, the present invention reduces enterprise equipment upgrade costs and increases reaction efficiency.

Description

一种1，4-丁二醇的制备系统及工艺A preparation system and process for 1,4-butanediol 技术领域Technical field
本发明涉及1，4-丁二醇的制备技术领域，尤其涉及一种1，4-丁二醇的制备系统及工艺。The present invention relates to the technical field of preparation of 1,4-butanediol, in particular to a preparation system and process of 1,4-butanediol.
背景技术Background technique
1，4-丁二醇是一种重要的基本有机化工和精细化工原料。其用途广泛，尤其它的衍生物更是附加价值高的精细化工产品，广泛用作溶剂、医药、化妆品、增塑剂、固化剂、农药、除莠剂、人造革、纤维、工程塑料等方面。1，4-丁二醇还用作制造四氢呋喃(THF)、γ-丁内酯(GBL)、N-甲基呲咯烷酮(NMP)等。近年来PBT(聚对苯二甲酸丁二醇酯，主要用于PBT改性、PBT抽丝、拉膜、光纤护套等领域，在增强改性后可广泛应用于汽车制造、电子电气、仪表仪器、照明用具、家电、纺织、机械和通讯等领域)工程塑料和PBT纤维，因其易加工，优异的电性能、机械及耐热性能，而被广泛应用于汽车、机械、电子和电气等工业。PBT纤维具有优异的弹性(优于尼龙)，染色性和吸水性好，手感丰满，主要用于高档运动服，妇女内衣和紧身衣等，具有较大潜在市场。1,4-Butanediol is an important basic organic chemical and fine chemical raw material. It has a wide range of uses, especially its derivatives are fine chemical products with high added value, which are widely used as solvents, medicines, cosmetics, plasticizers, curing agents, pesticides, herbicides, artificial leather, fibers, engineering plastics, etc. 1,4-Butanediol is also used to produce tetrahydrofuran (THF), gamma-butyrolactone (GBL), N-methylpyrrolidone (NMP), etc. In recent years, PBT (polybutylene terephthalate) is mainly used in the fields of PBT modification, PBT spinning, film drawing, optical fiber sheath, etc. After being enhanced and modified, it can be widely used in automobile manufacturing, electronic and electrical, and instrumentation. Instruments, lighting appliances, home appliances, textiles, machinery and communications, etc.) Engineering plastics and PBT fibers are widely used in automobiles, machinery, electronics, and electrical due to their easy processing, excellent electrical properties, mechanical and heat resistance properties. industry. PBT fiber has excellent elasticity (better than nylon), good dyeability and water absorption, and full hand feeling. It is mainly used in high-end sportswear, women's underwear and tights, etc., and has a large potential market.
1，4-丁二醇的生产工艺路线多达十几种，主要有Reppe法、正丁烷/顺酐法、丁二烯法和环氧丙烷法等，其中Reppe法和正丁烷/顺酐法是目前生产1，4-丁二醇的最主要工艺。此外还有生物转化法和1,2-环氧-3-丁烯选择性水解直接制1，4-丁二醇等新方法[以乙炔和甲醛为原料，在铜催化作用下生成1，4-丁炔二醇，再加氢生成1，4-丁二醇。其中Reppe法是使用最广泛的工艺方法。There are more than a dozen production process routes of 1,4-butanediol, mainly including Reppe method, n-butane/maleic anhydride method, butadiene method and propylene oxide method, among which Reppe method and n-butane/maleic anhydride The method is currently the most important process for producing 1,4-butanediol. In addition, there are new methods such as the bioconversion method and the selective hydrolysis of 1,2-epoxy-3-butene to directly produce 1,4-butanediol [using acetylene and formaldehyde as raw materials, under the catalysis of copper, 1,4 -Butynediol, which is then hydrogenated to produce 1,4-butanediol. The Reppe method is the most widely used process method.
Reppe法分为经典法和改良法。经典法中，在13.8-27.6MPa和250-350℃的操作条件下，导致乙炔分压较高，有爆炸危险，另外，乙炔聚合会生成聚乙炔， 导致催化剂失活。Reppe method is divided into classic method and modified method. In the classical method, under the operating conditions of 13.8-27.6 MPa and 250-350°C, the partial pressure of acetylene is high and there is a danger of explosion. In addition, the polymerization of acetylene will generate polyacetylene, which leads to the deactivation of the catalyst.
改良后的Reppe法工艺中，采用Cu-Bi硅胶催化剂，温度90-100℃，压力0.1-0.2MPa，在悬浮床或者淤浆床中进行1，4-丁炔二醇合成，降低反应过程乙炔分压。In the improved Reppe process, the Cu-Bi silica gel catalyst is used, the temperature is 90-100℃, the pressure is 0.1-0.2MPa, and the synthesis of 1,4-butynediol is carried out in a suspended bed or a slurry bed to reduce the reaction process of acetylene. Partial pressure.
以前我国合成1，4-丁二醇有多种路线，但是最近几年，随着1，4-丁二醇合成技术的发展，现在制备1，4-丁二醇主要是通过炔醛法来完成的。在利用炔醛法合成1，4-丁二醇的工艺流程中，特别是将乙炔、甲醛混合和利用1，4-丁炔二醇加氢合成1，4-丁二醇过程中，由于直接将两种密度不同的气体直接进行混合，反应率较低，反应率较低，不可避免的会产生大量衍生物质，增加后期分离的成本。In the past, there were many routes for synthesizing 1,4-butanediol in my country, but in recent years, with the development of 1,4-butanediol synthesis technology, the preparation of 1,4-butanediol is mainly through the alkynal method. Finished. In the process of synthesizing 1,4-butanediol by the acetylene aldehyde method, especially in the process of mixing acetylene and formaldehyde and hydrogenating 1,4-butynediol to synthesize 1,4-butanediol, it is directly Mixing two gases with different densities directly has a low reaction rate and a low reaction rate, which will inevitably produce a large amount of derivative substances and increase the cost of later separation.
综上可知，现有技术在实际使用上显然存在不便与缺陷，所以有必要加以改进。In summary, the existing technology obviously has inconvenience and defects in actual use, so it is necessary to improve it.
发明内容Summary of the invention
针对上述的缺陷，本发明的目的在于提供一种1，4-丁二醇的制备系统及工艺，其对传统1，4-丁二醇生产系统进行改进，在降低企业设备升级成本的同时，提高反应效率。In view of the above-mentioned drawbacks, the purpose of the present invention is to provide a 1,4-butanediol preparation system and process, which improves the traditional 1,4-butanediol production system, while reducing the cost of enterprise equipment upgrades, Improve reaction efficiency.
为了实现上述目的，本发明提供一种1，4-丁二醇的制备系统，包括甲醛生产装置、乙炔发生装置、微界面发生器、脱离子系统和加氢系统；所述微界面发生器用于将气体破碎形成直径≥1μm、且＜1mm的微米级气泡，其包括第一微界面发生器和第二微界面发生器；所述甲醛生产装置和所述乙炔发生装置的输出端通过所述第一微界面发生器连接炔化反应装置；所述脱离子系统的输出端通过所述第二微界面发生器连接所述加氢系统，且所述加氢系统为多级加氢系统；所述甲醛生产装置包括相互连接的加热系统、反应系统和产品收集系统，所述加热系包括加热器、再沸器和过热器；所述加热器包括第一加热器和第二 加热器，所述第一加热器位于尾气风机的输出端，第二加热器连接分别连接外界空气和混合器。In order to achieve the above objective, the present invention provides a 1,4-butanediol preparation system, including a formaldehyde production device, an acetylene generation device, a micro-interface generator, a disengagement subsystem, and a hydrogenation system; the micro-interface generator is used for The gas is crushed to form micron-level bubbles with a diameter of ≥1μm and <1mm, which includes a first micro-interface generator and a second micro-interface generator; the output ends of the formaldehyde production device and the acetylene generation device pass through the first micro-interface generator and the second micro-interface generator. A micro-interface generator is connected to the acetylene reaction device; the output end of the disengagement subsystem is connected to the hydrogenation system through the second micro-interface generator, and the hydrogenation system is a multi-stage hydrogenation system; The formaldehyde production device includes a heating system, a reaction system, and a product collection system connected to each other. The heating system includes a heater, a reboiler and a superheater; the heater includes a first heater and a second heater. A heater is located at the output end of the exhaust fan, and the second heater is connected to the outside air and the mixer respectively.
根据本发明的1，4-丁二醇的制备系统，所述炔化反应装置后端还连接精馏装置，所述精馏装置为1，4-丁炔二醇精馏装置，所述1，4-丁炔二醇精馏装置的输出端连接所述脱离子系统。According to the 1,4-butanediol preparation system of the present invention, the back end of the acetylene reaction device is also connected to a rectification device, and the rectification device is a 1,4-butynediol rectification device. , The output end of the 4-butynediol rectification device is connected to the disengagement subsystem.
根据本发明的1，4-丁二醇的制备系统，所述多级加氢系统包括低压加氢系统和高压加氢系统，所述低压加氢系统与所述高压加氢系统的输入端均连接第二微界面发生器，所述第二微界面发生器的输入端连接所述脱离子系统。According to the 1,4-butanediol preparation system of the present invention, the multi-stage hydrogenation system includes a low-pressure hydrogenation system and a high-pressure hydrogenation system, and the input ends of the low-pressure hydrogenation system and the high-pressure hydrogenation system are both The second micro-interface generator is connected, and the input end of the second micro-interface generator is connected to the decoupling subsystem.
根据本发明的1，4-丁二醇的制备系统，所述反应器与过热器之间还连接有用于稳压平衡的汽包。According to the 1,4-butanediol preparation system of the present invention, a steam drum for pressure stabilization and balance is also connected between the reactor and the superheater.
根据本发明的1，4-丁二醇的制备系统，所述吸收塔的数量为两个，包括第一吸收塔和第二吸收塔，第一吸收塔的输出端连接有循环泵，所述循环泵的输出端连接配制槽与产品槽，所述第二吸收塔的输出端连接有尾气风机和燃烧器，且所述尾气风机的输出端连接所述第一加热器。According to the 1,4-butanediol preparation system of the present invention, the number of the absorption towers is two, including a first absorption tower and a second absorption tower, the output end of the first absorption tower is connected with a circulating pump, and 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 an exhaust fan and a burner, and the output end of the exhaust fan is connected with the first heater.
根据本发明的1，4-丁二醇的制备系统，所述乙炔发生装置依次包括水解系统、乙炔发生器和冷却器，所述冷却器的输出端连接水解槽和气柜。According to the 1,4-butanediol preparation system of the present invention, the acetylene generating device sequentially includes a hydrolysis system, an acetylene generator and a cooler, and the output end of the cooler is connected to the hydrolysis tank and the gas tank.
根据本发明的1，4-丁二醇的制备系统，所述加氢系统内设有外式反应器，所述外式反应器包括淤浆床、固定床、滴流床或毛细管反应器中的一种或多种。According to the 1,4-butanediol preparation system of the present invention, an external reactor is provided in the hydrogenation system, and the external reactor includes a slurry bed, a fixed bed, a trickle bed or a capillary reactor. One or more of.
根据本发明的1，4-丁二醇的制备系统，所述毛细管反应器呈上端开口直径小于下端开口直径。According to the 1,4-butanediol preparation system of the present invention, the capillary reactor has an upper opening diameter smaller than a lower opening diameter.
根据本发明的1，4-丁二醇的制备系统，所述毛细管反应器由多个单个毛细管均匀组合成型，单个毛细管的内径为2-4mm，整体式毛细管的底部内径为10-16cm，上部直径为5-8cm。According to the 1,4-butanediol preparation system of the present invention, the capillary reactor is formed by a uniform combination of a plurality of single capillaries, the inner diameter of the single capillary is 2-4mm, the inner diameter of the bottom of the monolithic capillary is 10-16cm, and the upper part The diameter is 5-8cm.
一种1，4-丁二醇的制备工艺，包括如下步骤：A preparation process of 1,4-butanediol includes the following steps:
步骤一：利用甲醛生产装置和乙炔发生装置分别制备甲醛和乙炔；Step 1: Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
步骤二：将步骤一制备的甲醛和乙炔在反应釜中进行炔醛反应，并在炔醛反应中加入催化剂，生成1，4-丁炔二醇；炔醛反应中的催化剂为Cu 2C 2-Bi 2O 3或SiO 2，反应温度为80-120℃，反应釜中的反应压力≤2MPa； Step 2: The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reaction kettle, and a catalyst is added to the acetylene reaction to produce 1,4-butynediol; the catalyst in the acetylene reaction is Cu 2 C 2 -Bi 2 O 3 or SiO 2 , the reaction temperature is 80-120℃, and the reaction pressure in the reactor is ≤2MPa;
步骤三：将步骤二制备的1，4-丁炔二醇在外反应器中加氢反应，加氢反应为两段加氢，第一段加氢反应在低压加氢系统中进行，采用的催化剂为Ni基催化剂，反应压力1-5MPa；第二段加氢反应在高压系统中进行，采用的催化剂为Pd基催化剂的，反应压力10-30MPa；两段加氢工艺完成后，将第一段加氢反应与第二段加氢产生的1，4-丁二醇在精馏塔中进行精制生成1，4-丁二醇产品。Step 3: Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor. The hydrogenation reaction is a two-stage hydrogenation. The first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system. The catalyst used is It is a Ni-based catalyst with a reaction pressure of 1-5MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, and the catalyst used is a Pd-based catalyst with a reaction pressure of 10-30MPa; after the two-stage hydrogenation process is completed, the first stage The 1,4-butanediol produced by the hydrogenation reaction and the second stage of hydrogenation is refined in a rectifying tower to produce 1,4-butanediol products.
本发明的目的在于提供一种1，4-丁二醇的制备系统，包括甲醛生产装置、乙炔发生装置、微界面发生器、脱离子系统和加氢系统；所述微界面发生器包括第一微界面发生器和第二微界面发生器；所述甲醛生产装置和所述乙炔发生装置的输出端通过所述第一微界面发生器连接并快速混合进行炔醛反应，生成1，4-丁炔二醇。脱离子系统的输出端通过所述第二微界面发生器连接所述加氢系统，且所述加氢系统为多级加氢系统；由于加氢反应是较强的放热反应，工业上1，4-丁炔二醇加氢过程中易出现局部过热，高温易使催化剂失活，降低催化剂的寿命的现象，因此一般加氢系统选用多级加氢系统，可以极大的提高设备的使用寿命，防止局部过热。所述甲醛生产装置包括相互连接的加热系统、反应系统和产品收集系统，所述加热系统位于所述反应系统前端，包括加热器、再沸器和过热器；所述反应系统包括阻火过滤器、反应器和吸收塔；所述产品收集系统包括配制槽和产品槽；所述加热器包括第一加热器和第二加热器，所述第一加热器位于尾气风机的输出端，第二加热器连接分别连接外界空气和混合器，微界面发生器能够将氢气破碎成直径≥1μm、且＜1mm的微米级气泡，同时将微米级气泡与1,4-丁炔二醇充分混合形成气液乳化物，提高气体与液体之间的接触面积，而化学性质不便，在反应过程中可以极大的提高化学反应效率。The purpose of the present invention is to provide a 1,4-butanediol preparation system, including a formaldehyde production device, an acetylene generating device, a micro-interface generator, a disengagement subsystem, and a hydrogenation system; the micro-interface generator includes a first A micro-interface generator and a second micro-interface generator; the output ends of the formaldehyde production device and the acetylene generating device are connected through the first micro-interface generator and quickly mixed to perform the acetylene aldehyde reaction to generate 1,4-butane Acetylene glycol. The output end of the separation subsystem is connected to the hydrogenation system through the second micro-interface generator, and the hydrogenation system is a multi-stage hydrogenation system; because the hydrogenation reaction is a strong exothermic reaction, industrially 1 , 4-Butynediol hydrogenation process is prone to local overheating, high temperature easily deactivates the catalyst, and reduces the life of the catalyst. Therefore, the general hydrogenation system uses a multi-stage hydrogenation system, which can greatly improve the use of equipment. Life, to prevent local overheating. The formaldehyde production device includes a heating system, a reaction system, and a product collection system connected to each other. The heating system is located at the front end of the reaction system and includes a heater, a reboiler, and a superheater; the reaction system includes a flame retardant filter , Reactor and absorption tower; the product collection system includes a preparation tank and a product tank; the heater includes a first heater and a second heater, the first heater is located at the output end of the exhaust fan, and the second heater The device is connected to the outside air and the mixer respectively. The micro-interface generator can break the hydrogen into micron-sized bubbles with a diameter of ≥1μm and <1mm, and at the same time fully mix the micron-sized bubbles with 1,4-butynediol to form a gas-liquid Emulsions increase the contact area between gas and liquid, but the chemical properties are inconvenient, which can greatly improve the chemical reaction efficiency during the reaction process.
附图说明Description of the drawings
图1是本发明的结构示意图；Figure 1 is a schematic diagram of the structure of the present invention;
图2是本发明的甲醛生产装置结构示意图；Figure 2 is a schematic diagram of the structure of the formaldehyde production device of the present invention;
图3是本发明乙炔的生产流程图；Figure 3 is a production flow chart of acetylene of the present invention;
图4是毛细管反应器结构示意图；Figure 4 is a schematic diagram of the structure of a capillary reactor;
图5是本发明的工艺流程示意图；Figure 5 is a schematic diagram of the process flow of the present invention;
在图中，1-尾气风机，2-第一加热器，3-第二加热器，4-再沸器，5-混合器，6-过热器，7-阻火过滤器，8-汽包，9-反应器，10-第一吸收塔，11-第二吸收塔，12-循环泵，13-配制槽，14-产品槽，15-焚烧器，BDO-1，4-丁二醇，BYD-1，4-丁炔二醇，BED-1,4-丁烯二醇。In the figure, 1-exhaust fan, 2-first heater, 3-second heater, 4-reboiler, 5-mixer, 6-superheater, 7-flame retardant filter, 8-steam drum , 9-reactor, 10-first absorption tower, 11-second absorption tower, 12-circulation pump, 13-preparation tank, 14-product tank, 15-incinerator, BDO-1,4-butanediol, BYD-1,4-butynediol, BED-1,4-butenediol.
具体实施方式detailed description
下面参照附图来描述本发明的优选实施方式。本领域技术人员应当理解的是，这些实施方式仅仅用于解释本发明的技术原理，并非在限制本发明的保护范围。The preferred embodiments of the present invention will be described below with reference to the drawings. Those skilled in the art should understand that these embodiments are only used to explain the technical principles of the present invention, and are not intended to limit the protection scope of the present invention.
需要说明的是，在本发明的描述中，术语“上”、“下”、“左”、“右”、“内”、“外”等指示的方向或位置关系的术语是基于附图所示的方向或位置关系，这仅仅是为了便于描述，而不是指示或暗示所述装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。It should be noted that in the description of the present invention, the terms "upper", "lower", "left", "right", "inner", "outer" and other terms indicating directions or positional relationships are based on the attached drawings. The direction or position relationship shown is only for ease of description, and does not indicate or imply that the device or element must have a specific orientation, be configured and operated in a specific orientation, and therefore cannot be understood as a limitation of the present invention.
此外，还需要说明的是，在本发明的描述中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域技术人员而言，可根据具体情况理解上述术语在本发明中的具体含义。In addition, it should be noted that, in the description of the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense. For example, they can be fixed or fixed. It is a detachable connection or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the internal communication between two components. For those skilled in the art, the specific meaning of the above-mentioned terms in the present invention can be understood according to specific circumstances.
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明，应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the objectives, technical solutions, and advantages of the present invention clearer, the following further describes the present invention in detail with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described here are only used to explain the present invention and are not intended to Limit the present invention.
参见图1、图5，本发明的目的在于提供一种1，4-丁二醇的制备系统，包括甲醛生产装置、乙炔发生装置、微界面发生器、脱离子系统和加氢系统；微界面发生器包括第一微界面发生器和第二微界面发生器；甲醛生产装置和乙炔发生装置的输出端通过第一微界面发生器连接并快速混合进行炔醛反应，生成1，4-丁炔二醇。Referring to Figures 1 and 5, the purpose of the present invention is to provide a 1,4-butanediol preparation system, including a formaldehyde production device, an acetylene generation device, a micro-interface generator, a separation subsystem, and a hydrogenation system; micro-interface The generator includes a first micro-interface generator and a second micro-interface generator; the output ends of the formaldehyde production device and the acetylene generating device are connected through the first micro-interface generator and quickly mixed to perform the acetylene aldehyde reaction to generate 1,4-butyne Glycol.
脱离子系统的输出端通过第二微界面发生器连接加氢系统，且加氢系统为多级加氢系统；由于加氢反应是较强的放热反应，工业上1，4-丁炔二醇加氢过程中易出现局部过热，高温易使催化剂失活，降低催化剂的寿命的现象，因此一般加氢系统选用多级加氢系统，可以极大的提高设备的使用寿命，防止局部过热。The output end of the disengagement subsystem is connected to the hydrogenation system through the second micro-interface generator, and the hydrogenation system is a multi-stage hydrogenation system; because the hydrogenation reaction is a strong exothermic reaction, 1,4-butyne two is industrially In the alcohol hydrogenation process, local overheating is easy to occur, and high temperature can easily deactivate the catalyst and reduce the life of the catalyst. Therefore, the multi-stage hydrogenation system is generally used in the hydrogenation system, which can greatly increase the service life of the equipment and prevent local overheating.
微界面强化反应器适用于绝大多数受传质和传热控制反应过程，如气-液、气-液-固、液-液、液-液-固、气-液-液-固反应体系等等。其基本科学原理是将反应体系的气－液、液－液、气－液－液相界面的气体或液相颗粒直径破碎成微米级(30－900μm)范围，而传统的鼓泡反应器内气、液相颗粒直径一般为毫米/厘米级(3mm－30mm)。这样可成倍地提高气－液、液－液之间的传质面积和总传质速率，从而大幅提高反应速度、有效控制副反应和提高产品收率、显著降低反应过程的能耗和物耗、以及反应工段的提高安全性等。The micro-interface enhanced reactor is suitable for most reaction processes controlled by mass transfer and heat transfer, such as gas-liquid, gas-liquid-solid, liquid-liquid, liquid-liquid-solid, gas-liquid-liquid-solid reaction systems and many more. The basic scientific principle is to break the gas or liquid particle diameter at the gas-liquid, liquid-liquid, gas-liquid-liquid interface of the reaction system into a micron range (30-900μm), while the traditional bubbling reactor The diameter of gas and liquid particles is generally millimeter/cm (3mm-30mm). In this way, the mass transfer area and total mass transfer rate between gas-liquid and liquid-liquid can be doubled, thereby greatly increasing the reaction speed, effectively controlling side reactions and improving product yield, and significantly reducing the energy and material consumption of the reaction process. , And improve the safety of the reaction section.
一般地，对于氧化、过氧化、加氢、苯环氯化、等气-液、气-液-固等反应体系，与传统的搅拌反应釜相比，反应速率可提高3-5倍或更多，能耗一般可节省30-50％或更多，物耗节省5％-20％不等。Generally, for oxidation, peroxidation, hydrogenation, benzene ring chlorination, and other gas-liquid, gas-liquid-solid reaction systems, the reaction rate can be increased by 3-5 times or more compared with traditional stirred reactors. The energy consumption can generally be saved by 30-50% or more, and the material consumption can be saved by 5%-20%.
微界面强化反应器是一种通用性技术，适合于石化、煤化工、精细化工、制药(医药、农药、兽药)生产、新材料生产、日化生产、电子与生物化学品、 海洋化工、环境化工等多行业多领域具有气-液、气-液-固、液-液、液-液-固、气-液-液-固等化学反应的场合，可大幅提高反应效率、减少污染物排放和降低能耗。The micro-interface enhanced reactor is a universal technology, suitable for petrochemical, coal chemical, fine chemical, pharmaceutical (medicine, pesticide, veterinary) production, new material production, daily chemical production, electronics and biological chemicals, marine chemical, environmental Chemical reactions in multiple industries and fields, such as gas-liquid, gas-liquid-solid, liquid-liquid, liquid-liquid-solid, gas-liquid-liquid-solid and other chemical reactions, can greatly improve reaction efficiency and reduce pollutant emissions And reduce energy consumption.
参见图2，生产甲醛的过程，甲醛生产装置包括相互连接的加热系统、反应系统和产品收集系统，加热系统位于反应系统前端，包括加热器、混合器5、再沸器4和过热器6；反应系统包括阻火过滤器7、反应器9和吸收塔；产品收集系统包括配制槽13和产品槽14；加热器包括第一加热器2和第二加热器3，第一加热器位于尾气风机1的输出端，第二加热器3连接分别连接外界空气和混合器5。在生产甲醛的过程中，一般所需的温度较高，为了充分反映，吸收塔的数量至少为两个，包括第一吸收塔10和第二吸收塔11，第二吸收塔依然会产生大量余热，而余热经由尾气风机1后，快速进入第一加热器2中，再次加热并投入反映中，可以更好地提高反应效率。Refer to Figure 2, the process of producing formaldehyde. The formaldehyde production device includes a heating system, a reaction system, and a product collection system that are connected to each other. The heating system is located at the front end of the reaction system and includes a heater, a mixer 5, a reboiler 4, and a superheater 6; The reaction system includes a flame retardant filter 7, a reactor 9 and an absorption tower; the product collection system includes a preparation tank 13 and a product tank 14; the heater includes a first heater 2 and a second heater 3, and the first heater is located in the exhaust fan The output end of 1, the second heater 3 is connected to the outside air and the mixer 5, respectively. In the process of producing formaldehyde, generally the required temperature is relatively high. In order to fully reflect, the number of absorption towers should be at least two, including the first absorption tower 10 and the second absorption tower 11. The second absorption tower still generates a lot of waste heat. , And the waste heat quickly enters the first heater 2 after passing through the exhaust fan 1, and is heated again and put into the reaction, which can better improve the reaction efficiency.
本发明炔化反应装置后端还连接精馏装置，精馏装置为1，4-丁炔二醇精馏装置，1，4-丁炔二醇精馏装置的输出端连接脱离子系统，1，4-丁二醇在制备过程中，会产生大量的1，4-丁炔二醇中间产物，利用精馏装置，可以更好地去除其他杂质，如水汽等，方便进行下一个加工步骤。The back end of the acetylene reaction device of the present invention is also connected to a rectification device, the rectification device is a 1,4-butynediol rectification device, and the output end of the 1,4-butynediol rectification device is connected to the disengagement subsystem. During the preparation process of 4-butanediol, a large amount of 1,4-butynediol intermediate products will be produced. The use of rectification equipment can better remove other impurities, such as water vapor, and facilitate the next processing step.
更进一步的，本发明的多级加氢系统包括低压加氢系统和高压加氢系统，低压加氢系统与高压加氢系统的输入端均连接第二微界面发生器，第二微界面发生器的输入端连接脱离子系统。由于加氢反应是较强的放热反应，工业上1，4-丁炔二醇加氢过程中反应热移除过程复杂，易出现局部过热，高温易使催化剂失活，降低催化剂的寿命。局部反应过温度过高的主要原因是1，4-丁炔二醇加氢过程是连串反应，1，4-丁炔二醇先加氢生成1,4-丁烯二醇再加氢生成1，4-丁二醇。1，4-丁炔二醇加氢过程的主反应式为：Furthermore, the multi-stage hydrogenation system of the present invention includes 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 to the second micro-interface generator, and the second micro-interface generator The input terminal is disconnected from the subsystem. Since the hydrogenation reaction is a strong exothermic reaction, the process of removing reaction heat in the industrial 1,4-butynediol hydrogenation process is complicated, and local overheating is prone to occur. High temperature can easily deactivate the catalyst and reduce the life of the catalyst. The main reason for the local reaction temperature being too high is that the 1,4-butynediol hydrogenation process is a series of reactions. 1,4-butynediol is first hydrogenated to form 1,4-butenediol and then hydrogenated to form 1,4-Butanediol. The main reaction formula of 1,4-butynediol hydrogenation process is:
CH 2OH—C≡≡C—CH 2OH+H 2—→CH 2OH—CH＝CH—CH 2OH  ΔH＝–154.8kJ/mol(1) CH 2 OH—C≡≡C—CH 2 OH+H 2 —→CH 2 OH—CH=CH—CH 2 OH ΔH=–154.8kJ/mol(1)
CH 2OH—CH＝CH—CH 2OH+H 2—→CH 2OH—CH 2—CH 2—CH 2OH  ΔH＝–96.3kJ/mol(2) CH 2 OH—CH=CH—CH 2 OH+H 2 —→CH 2 OH—CH 2 —CH 2 —CH 2 OH ΔH=–96.3kJ/mol(2)
1，4-丁炔二醇二段加氢工艺，可以降低1，4-丁炔二醇直接一段加氢压力，1，4-丁二醇的收率可以提高到96％以上，可以极大提高1，4-丁二醇产品质量。The 1,4-butynediol two-stage hydrogenation process can reduce the direct one-stage hydrogenation pressure of 1,4-butynediol, and the yield of 1,4-butynediol can be increased to over 96%, which can greatly Improve the quality of 1,4-butanediol products.
在实际生产甲醛的过程中，反应器9与过热器6之间还连接有用于稳压平衡的汽包8，汽包8汽包中存有一定水量，具有一定的热量及工质的储蓄，在工况变动时可减缓汽压变化速度，当给水与负荷短时间不协调时起一定的缓冲作用。In the actual production of formaldehyde, a steam drum 8 for voltage stabilization and balance is also connected between the reactor 9 and the superheater 6. The steam drum 8 has a certain amount of water stored in the steam drum, and has a certain amount of heat and working fluid storage. It can slow down the steam pressure change speed when the working conditions change, and play a certain buffering effect when the water supply and the load are not coordinated for a short time.
更好地，在生产甲醛的过程中，一般需要设置多个吸收塔，本发明中的吸收塔的数量为两个，包括第一吸收塔10和第二吸收塔11，第一吸收塔10的输出端连接有循环泵12，循环泵12的输出端连接配制槽13与产品槽14，第二吸收塔11的输出端连接有尾气风机1和燃烧器15，且尾气风机1的输出端连接第一加热器2。第一吸收塔10产生的甲醛在循环泵12的作用下进入存储环节或直接进入下一个生产工序。Preferably, in the process of producing formaldehyde, it is generally necessary to set up multiple absorption towers. The number of absorption towers in the present invention is two, including the first absorption tower 10 and the second absorption tower 11. The output end is connected to the circulating pump 12, the output end of the circulating pump 12 is connected to the preparation tank 13 and the product tank 14, the output end of the second absorption tower 11 is connected to the exhaust fan 1 and the burner 15, and the output end of the exhaust fan 1 is connected to the first One heater 2. The formaldehyde generated by the first absorption tower 10 enters the storage link under the action of the circulating pump 12 or directly enters the next production process.
参见图3，乙炔发生装置依次包括水解系统、乙炔发生器和冷却器，冷却器的输出端连接水解槽和气柜。在实际使用过程中，利用电石水解的主要生产过程是：原料加工；配料；通过电炉上端的入口或管道将混合料加入电炉内，在开放或密闭的电炉中加热至2000℃左右，依下式反应生成电石：GaO+3C→CaC 2+CO。熔化了的碳化钙从炉底取出后，经冷却、破碎后作为成品包装。 Referring to Figure 3, the acetylene generating device sequentially includes a hydrolysis system, an acetylene generator and a cooler, and the output end of the cooler is connected to the hydrolysis tank and the gas tank. In the actual use process, the main production processes using calcium carbide hydrolysis are: raw material processing; batching; adding the mixture into the electric furnace through the inlet or pipeline at the upper end of the electric furnace, and heating it to about 2000 ℃ in an open or closed electric furnace, according to the following formula The reaction generates calcium carbide: GaO+3C→CaC 2 +CO. The molten calcium carbide is taken out from the bottom of the furnace, cooled and broken, and then packaged as a finished product.
另一种方法是湿法乙炔发生是用多于理论量17倍的水分解电石，产生的电石渣浆含水量为90％。反应热由渣浆水带走，有将近1％的溶解损失。每次加料都需要置换，会排掉斗内的乙炔从而造成额外损失。每生产1吨1，4-丁二醇就要产生15吨含有大量硫、磷的污水，只有一小部分能够回用。电石渣浆经过压滤成为含水量约35％的滤饼，乙炔的极限收率为96％。Another method is wet acetylene generation, which uses 17 times more than the theoretical amount of water to decompose calcium carbide, and the resulting calcium carbide slag slurry has a water content of 90%. The reaction heat is taken away by the slurry water, and there is a dissolution loss of nearly 1%. Each feeding needs to be replaced, which will drain the acetylene in the hopper and cause additional losses. For every ton of 1,4-butanediol produced, 15 tons of sewage containing a large amount of sulfur and phosphorus are produced, and only a small part can be reused. The calcium carbide slag slurry is filtered into a filter cake with a water content of about 35%, and the ultimate yield of acetylene is 96%.
本发明的加氢系统内设有外式反应器，外式反应器包括淤浆床、固定床、滴流床或毛细管反应器中的一种或多种。由于加氢反应是较强的放热反应，为 提高设备的使用寿命，加氢系统需要选择合适的外式反应器，散热性能较好的为淤浆床、固定床、滴流床或毛细管反应器。The hydrogenation system of the present invention is provided with an external reactor, and the external reactor includes one or more of a slurry bed, a fixed bed, a trickle bed or a capillary reactor. Since the hydrogenation reaction is a strong exothermic reaction, in order to improve the service life of the equipment, the hydrogenation system needs to select a suitable external reactor, and the heat dissipation performance is better for the slurry bed, fixed bed, trickle bed or capillary reaction. Device.
参见图4，更好地，本发明的外式反应器为毛细管反应器，毛细管反应器由多个单个毛细管均匀组合成型，单个毛细管的内径为2-4mm，整体式毛细管的底部内径为10-16cm，上部直径为5-8cm。外式反应器一般优先选用毛细管反应器，毛细管反应器包括泵体和反应器本体，反应器本体底部直径为6-10cm，上部直径为3-6cm，催化剂负载在反应管的内壁，反应段位于反应器本体下半段，增加微界面发生器，采用气液并流向下通过毛细管，毛细管反应器成本较低，散热效果好，便于安装是用。毛细管反应器一般由多个单个毛细管均匀组合成型，单个毛细管的内径为2mm，整体式毛细管的底部内径为10cm，上部为5cm，催化剂负载在反应管的内壁，采用气液并流向下通过毛细管并在催化剂上发生反应。研究表明，温度在24℃-54℃、压力在100-300kPa，及流动状态(单相流、低气含率两相流、高气含率两相流)对1，4-丁炔二醇加氢过程的影响。实验结果表明，在单个毛细管和多个毛细管下，1，4-丁炔二醇的转化率为100％，1,4-丁烯二醇选择性达到98％。在相同的温度和压力下，多个毛细管反应器催化剂表面活性氢的浓度要高于单个毛细管，且随着温度的升高而降低。毛细管反应器中气液接触效率高，强化了气液传质，提高了催化剂表面活性氢的浓度，从而提高了1,4-丁烯二醇的选择性。4, it is better that the external reactor of the present invention is a capillary reactor. The capillary reactor is formed by a uniform combination of a plurality of single capillaries. The inner diameter of a single capillary is 2-4mm, and the inner diameter of the bottom of the monolithic capillary is 10- 16cm, the diameter of the upper part is 5-8cm. External reactors generally prefer capillary reactors. The capillary reactor includes a pump body and a reactor body. The bottom of the reactor body has a diameter of 6-10 cm and an upper diameter of 3-6 cm. The catalyst is supported on the inner wall of the reaction tube, and the reaction section is located In the lower half of the reactor body, a micro-interface generator is added, and gas and liquid flow down through the capillary tube. The capillary reactor has low cost, good heat dissipation effect, and is easy to install. A capillary reactor is generally formed by a uniform combination of multiple single capillaries. The inner diameter of a single capillary is 2mm. The inner diameter of the bottom of the monolithic capillary is 10cm and the upper part is 5cm. The catalyst is supported on the inner wall of the reaction tube. The reaction takes place on the catalyst. Studies have shown that the temperature at 24℃-54℃, the pressure at 100-300kPa, and the flow state (single-phase flow, low gas holdup two-phase flow, high gas hold-up two-phase flow) compared to 1,4-butynediol The impact of the hydrogenation process. Experimental results show that under a single capillary tube and multiple capillary tubes, the conversion rate of 1,4-butynediol is 100%, and the selectivity of 1,4-butenediol reaches 98%. Under the same temperature and pressure, the concentration of active hydrogen on the catalyst surface of multiple capillary reactors is higher than that of a single capillary, and decreases with the increase of temperature. The high gas-liquid contact efficiency in the capillary reactor enhances the gas-liquid mass transfer and increases the concentration of active hydrogen on the catalyst surface, thereby increasing the selectivity of 1,4-butenediol.
淤浆床也可以有效地移除反应热，使催化剂保持较好的活性，但需要对产品和催化剂进行分离。固定床和滴流床中产品与催化剂易于分离，反应器采用反应物料外循环进行冷却降温后返回反应器、段间换热和过量冷氢循环进行反应热的移除，固定床与滴流床中内扩散阻力大，在高压下操作，造成设备投资高等问题。The slurry bed can also effectively remove the heat of reaction and keep the catalyst active, but the product and the catalyst need to be separated. The product and the catalyst in the fixed bed and trickle bed are easy to separate. The reactor adopts the external circulation of the reaction material to cool down and then returns to the reactor, the heat exchange between sections and the excess cold hydrogen circulation to remove the reaction heat, the fixed bed and the trickle bed The internal diffusion resistance is large, and the operation under high pressure causes problems such as high equipment investment.
1，4-丁二醇的制备系统，包括如下操作步骤，The production system of 1,4-butanediol includes the following steps:
步骤一：利用甲醛生产装置和乙炔发生装置分别制备甲醛和乙炔；Step 1: Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
步骤二：将步骤一制备的甲醛和乙炔在反应釜中进行炔醛反应，并在炔醛反应中加入催化剂，生成1，4-丁炔二醇；炔醛反应中的催化剂为Cu 2C 2-Bi 2O 3或SiO 2，反应温度为80-120℃，反应釜中的反应压力≤2MPa； Step 2: The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reaction kettle, and a catalyst is added to the acetylene reaction to produce 1,4-butynediol; the catalyst in the acetylene reaction is Cu 2 C 2 -Bi 2 O 3 or SiO 2 , the reaction temperature is 80-120℃, and the reaction pressure in the reactor is ≤2MPa;
步骤三：将步骤二制备的1，4-丁炔二醇在外反应器中加氢反应，加氢反应为两段加氢，第一段加氢反应在低压加氢系统中进行，采用的催化剂为Ni基催化剂，反应压力1-5MPa；第二段加氢反应在高压系统中进行，采用的催化剂为Pd基催化剂的，反应压力10-30MPa；两段加氢工艺完成后，将第一段加氢反应与第二段加氢产生的1，4-丁二醇在精馏塔中进行精制生成1，4-丁二醇产品。Step 3: Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor. The hydrogenation reaction is a two-stage hydrogenation. The first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system. The catalyst used is It is a Ni-based catalyst with a reaction pressure of 1-5MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, and the catalyst used is a Pd-based catalyst with a reaction pressure of 10-30MPa; after the two-stage hydrogenation process is completed, the first stage The 1,4-butanediol produced by the hydrogenation reaction and the second stage of hydrogenation is refined in a rectifying tower to produce 1,4-butanediol products.
实施例1Example 1
步骤一：利用甲醛生产装置和乙炔发生装置分别制备甲醛和乙炔；Step 1: Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
步骤二：将步骤一制备的甲醛和乙炔在反应釜中进行炔醛反应，并在炔醛反应中加入催化剂，生成1，4-丁炔二醇；炔醛反应中的催化剂为SiO 2，反应温度为80℃，反应釜中的反应压力1MPa； Step 2: The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reactor, and a catalyst is added to the acetylene reaction to generate 1,4-butynediol; the catalyst in the acetylene reaction is SiO 2 , and the reaction The temperature is 80°C, and the reaction pressure in the reactor is 1MPa;
步骤三：将步骤二制备的1，4-丁炔二醇在外反应器中加氢反应，加氢反应为两段加氢，第一段加氢反应在低压加氢系统中进行，采用的催化剂为Ni基催化剂，反应压力2MPa；第二段加氢反应在高压系统中进行，采用的催化剂为Pd基催化剂的，反应压力10MPa；两段加氢工艺完成后，将第一段加氢反应与第二段加氢产生的1，4-丁二醇在精馏塔中进行精制生成1，4-丁二醇产品。Step 3: Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor. The hydrogenation reaction is a two-stage hydrogenation. The first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system. The catalyst used is It is a Ni-based catalyst with a reaction pressure of 2MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, and the catalyst used is a Pd-based catalyst with a reaction pressure of 10MPa; after the two-stage hydrogenation process is completed, the first-stage hydrogenation reaction is carried out with The 1,4-butanediol produced in the second stage of hydrogenation is refined in a rectification tower to produce 1,4-butanediol products.
本实施例的加氢工艺选用的是一步加氢，在固定床中采用雷尼镍为催化剂，于30MPa下进行反应，微界面发生器中1，4-丁炔二醇与氢气的比例采用100:1；外式反应器为毛细管反应器，选用催化剂为Ni基催化剂，反应压力10MPa，反应温度为30℃。The hydrogenation process of this embodiment uses one-step hydrogenation. Raney nickel is used as a catalyst in a fixed bed and the reaction is carried out at 30 MPa. The ratio of 1,4-butynediol to hydrogen in the 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°C.
测试发现，1，4-丁炔二醇的总转化率为98.5％，1，4-丁二醇的选择性为95％。上述实施例与对照组主要区别为采用毛细管反应器，毛细管反应器相比于淤浆 床，可以让催化剂保持持久的活性，且散热性较好，可以极大的提高设备的使用寿命。The test found that the total conversion rate of 1,4-butynediol was 98.5%, and the selectivity of 1,4-butanediol was 95%. The main difference between the above embodiment and the control group is the use of a capillary reactor. Compared with a slurry bed, the capillary reactor can keep the catalyst active and has better heat dissipation, which can greatly increase the service life of the equipment.
实施例2Example 2
步骤一：利用甲醛生产装置和乙炔发生装置分别制备甲醛和乙炔；Step 1: Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
步骤二：将步骤一制备的甲醛和乙炔在反应釜中进行炔醛反应，并在炔醛反应中加入催化剂，生成1，4-丁炔二醇；炔醛反应中的催化剂为SiO 2，反应温度为80℃，反应釜中的反应压力1MPa； Step 2: The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reaction kettle, and a catalyst is added to the acetylene reaction to generate 1,4-butynediol; the catalyst in the acetylene reaction is SiO 2 , and the reaction The temperature is 80°C, and the reaction pressure in the reactor is 1MPa;
步骤三：将步骤二制备的1，4-丁炔二醇在外反应器中加氢反应，加氢反应为两段加氢，第一段加氢反应在低压加氢系统中进行，采用的催化剂为Ni基催化剂，反应压力2MPa；第二段加氢反应在高压系统中进行，采用的催化剂为Pd基催化剂的，反应压力10MPa；两段加氢工艺完成后，将第一段加氢反应与第二段加氢产生的1，4-丁二醇在精馏塔中进行精制生成1，4-丁二醇产品。Step 3: Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor. The hydrogenation reaction is a two-stage hydrogenation. The first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system. The catalyst used is It is a Ni-based catalyst with a reaction pressure of 2MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, and the catalyst used is a Pd-based catalyst with a reaction pressure of 10MPa; after the two-stage hydrogenation process is completed, the first-stage hydrogenation reaction is carried out with The 1,4-butanediol produced in the second stage of hydrogenation is refined in a rectification tower to produce 1,4-butanediol products.
本实施例的加氢工艺选用的是一步加氢，在固定床中采用雷尼镍为催化剂，于30MPa下进行反应，微界面发生器中1，4-丁炔二醇与氢气的比例采用100:1；外式反应器为毛细管反应器，选用催化剂为Ni基催化剂，反应压力10MPa，反应温度为30℃。The hydrogenation process of this embodiment uses one-step hydrogenation. Raney nickel is used as a catalyst in a fixed bed and the reaction is carried out at 30 MPa. The ratio of 1,4-butynediol to hydrogen in the 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°C.
第三步在淤浆床中反应，选用催化剂为Ni基催化剂，反应压力112MPa，反应温度为30℃。测试发现，1，4-丁炔二醇的总转化率为97.6％，1，4-丁二醇的选择性为95.6％。In the third step, the reaction is carried out in a slurry bed. The catalyst is selected as Ni-based catalyst, the reaction pressure is 112MPa, and the reaction temperature is 30°C. The test found that the total conversion rate of 1,4-butynediol was 97.6%, and the selectivity of 1,4-butanediol was 95.6%.
实施例3Example 3
步骤一：利用甲醛生产装置和乙炔发生装置分别制备甲醛和乙炔；Step 1: Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
步骤二：将步骤一制备的甲醛和乙炔在反应釜中进行炔醛反应，并在炔醛反应中加入催化剂，生成1，4-丁炔二醇；炔醛反应中的催化剂为SiO 2，反应温度为80℃，反应釜中的反应压力1MPa； Step 2: The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reactor, and a catalyst is added to the acetylene reaction to generate 1,4-butynediol; the catalyst in the acetylene reaction is SiO 2 , and the reaction The temperature is 80°C, and the reaction pressure in the reactor is 1MPa;
步骤三：将步骤二制备的1，4-丁炔二醇在外反应器中加氢反应，加氢反应 为两段加氢，第一段加氢反应在低压加氢系统中进行，采用的催化剂为Ni基催化剂，反应压力2MPa；第二段加氢反应在高压系统中进行，采用的催化剂为Pd基催化剂的，反应压力10MPa；两段加氢工艺完成后，将第一段加氢反应与第二段加氢产生的1，4-丁二醇在精馏塔中进行精制生成1，4-丁二醇产品。Step 3: Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor. The hydrogenation reaction is a two-stage hydrogenation. The first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system. The catalyst used is It is a Ni-based catalyst with a reaction pressure of 2MPa; the second-stage hydrogenation reaction is carried out in a high-pressure system, and the catalyst used is a Pd-based catalyst with a reaction pressure of 10MPa; after the two-stage hydrogenation process is completed, the first-stage hydrogenation reaction is carried out with The 1,4-butanediol produced in the second stage of hydrogenation is refined in a rectification tower to produce 1,4-butanediol products.
本实施例的加氢工艺选用的是一步加氢，在固定床中采用雷尼镍为催化剂，于30MPa下进行反应，微界面发生器中1，4-丁炔二醇与氢气的比例采用100:1；外式反应器为毛细管反应器，选用催化剂为Ni基催化剂，反应压力10MPa，反应温度为30℃。The hydrogenation process of this embodiment uses one-step hydrogenation. Raney nickel is used as a catalyst in a fixed bed and the reaction is carried out at 30 MPa. The ratio of 1,4-butynediol to hydrogen in the 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°C.
第三步在淤浆床中反应，选用的催化剂为Ni基催化剂，反应压力12MPa，反应温度为30℃。测试发现，1，4-丁炔二醇的总转化率为100％，1，4-丁二醇的选择性为98.1％。In the third step, the reaction is carried out in a slurry bed. The selected catalyst is a Ni-based catalyst, the reaction pressure is 12MPa, and the reaction temperature is 30°C. The test found that the total conversion rate of 1,4-butynediol was 100%, and the selectivity of 1,4-butanediol was 98.1%.
实施例4Example 4
步骤一：制备甲醛和乙炔；Step 1: Preparation of formaldehyde and acetylene;
步骤二：乙炔和甲醛在催化剂的作用下进行炔醛反应生产1，4-丁炔二醇；Step 2: Acetylene and formaldehyde react under the action of a catalyst to produce 1,4-butynediol;
步骤三：在催化剂的作用下，在反应器中，1，4-丁炔二醇加氢生产1，4-丁二醇；Step 3: Under the action of a catalyst, in the reactor, 1,4-butynediol is hydrogenated to produce 1,4-butanediol;
步骤二与步骤三中，乙炔与甲醛的连接端与1，4-丁炔二醇加氢输入端均连接有微界面发生器。In step two and step three, both the connecting end of acetylene and formaldehyde and the 1,4-butynediol hydrogenation input end are connected with a micro-interface generator.
1，4-丁炔二醇加氢采用两步加氢，催化剂为Pd，1,4-butynediol hydrogenation adopts two-step hydrogenation, the catalyst is Pd,
本实施例的加氢工艺选用的是两步加氢，在固定床中采用Pd，于10MPa下进行反应，微界面发生器中1，4-丁炔二醇与氢气的气气比选用200:1；The hydrogenation process in this embodiment uses two-step hydrogenation. Pd is used in a fixed bed and the reaction is carried out at 10 MPa. The gas-to-gas ratio of 1,4-butynediol to hydrogen in the micro-interface generator is 200: 1;
第三步在淤浆床中反应，选用催化剂为Ni基催化剂，反应压力12MPa，反应温度为24-30℃。测试发现，1，4-丁炔二醇的总转化率为100％，1，4-丁二醇的选择性为98.1％。The third step is to react in a slurry bed, and the catalyst is selected as a Ni-based catalyst, the reaction pressure is 12 MPa, and the reaction temperature is 24-30°C. The test found that the total conversion rate of 1,4-butynediol was 100%, and the selectivity of 1,4-butanediol was 98.1%.
实施例5Example 5
步骤一：制备甲醛和乙炔；Step 1: Preparation of formaldehyde and acetylene;
步骤二：乙炔和甲醛在催化剂的作用下进行炔醛反应生产1，4-丁炔二醇；Step 2: Acetylene and formaldehyde react under the action of a catalyst to produce 1,4-butynediol;
步骤三：在催化剂的作用下，在反应器中，1，4-丁炔二醇加氢生产1，4-丁二醇；Step 3: Under the action of a catalyst, in the reactor, 1,4-butynediol is hydrogenated to produce 1,4-butanediol;
步骤二与步骤三中，乙炔与甲醛的连接端与1，4-丁炔二醇加氢输入端均连接有气气型微界面发生器。In step two and step three, both the connecting end of acetylene and formaldehyde and the 1,4-butynediol hydrogenation input end are connected with a gas-gas type micro-interface generator.
本实施例的加氢工艺选用的是一步加氢，在固定床中采用氧化铝或硅胶为载体的镍系催化剂(一般为雷尼镍)，于30-32MPa下进行反应，微界面发生器中1，4-丁炔二醇与氢气的气气比选用100:1；The hydrogenation process of this embodiment uses one-step hydrogenation. A nickel-based catalyst (generally Raney nickel) supported by alumina or silica gel is used in a fixed bed, and the reaction is carried out at 30-32MPa. The micro-interface generator is The gas-gas ratio of 1,4-butynediol to hydrogen is 100:1;
第三步在毛细管反应器反应，选用催化剂为Al 2O 3，反应压力20MPa，反应温度为45℃。测试发现，1，4-丁炔二醇的总转化率为99.1％，1，4-丁二醇的选择性为96.7％。 The third step is the reaction in the capillary reactor. The catalyst is Al 2 O 3 , the reaction pressure is 20 MPa, and the reaction temperature is 45°C. The test found that the total conversion rate of 1,4-butynediol was 99.1%, and the selectivity of 1,4-butanediol was 96.7%.
上述实施例与对照组主要区别为采用毛细管反应器，毛细管反应器相比于淤浆床，可以让催化剂保持持久的活性，且散热性较好，可以极大的提高设备的使用寿命。The main difference between the above embodiment and the control group is the use of a capillary reactor. Compared with a slurry bed, the capillary reactor can keep the catalyst active and has better heat dissipation, which can greatly improve the service life of the equipment.
实施例6Example 6
步骤一：利用甲醛生产装置和乙炔发生装置分别制备甲醛和乙炔；Step 1: Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
步骤二：将步骤一制备的甲醛和乙炔在反应釜中进行炔醛反应，并在炔醛反应中加入催化剂，生成1，4-丁炔二醇；炔醛反应中的催化剂为Cu 2C 2-Bi 2O 3或SiO 2，反应温度为80-120℃，反应釜中的反应压力1MPa； Step 2: The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reaction kettle, and a catalyst is added to the acetylene reaction to produce 1,4-butynediol; the catalyst in the acetylene reaction is Cu 2 C 2 -Bi 2 O 3 or SiO 2 , the reaction temperature is 80-120°C, and the reaction pressure in the reactor is 1 MPa;
步骤三：将步骤二制备的1，4-丁炔二醇在外反应器中加氢反应，加氢反应为一段加氢，第一段加氢反应在低压加氢系统中进行，采用的催化剂为Ni基催化剂，反应压力1-5MPa；第二段加氢反应在高压系统中进行，采用的催化剂为Pd基催化剂的，反应压力10-30MPa；两段加氢工艺完成后，将第一段加氢反应与第二段加氢产生的1，4-丁二醇在精馏塔中进行精制生成1，4-丁二醇产品。Step 3: Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor. The hydrogenation reaction is one-stage hydrogenation. The first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system. The catalyst used is Ni-based catalyst, the reaction pressure is 1-5MPa; the second stage hydrogenation reaction is carried out in a high-pressure system, the catalyst used is a Pd-based catalyst, and the reaction pressure is 10-30MPa; after the two-stage hydrogenation process is completed, the first stage is added The 1,4-butanediol produced by the hydrogen reaction and the second stage of hydrogenation is refined in a rectifying tower to produce 1,4-butanediol products.
第三步在毛细管反应器反应，选用催化剂为Al 2O 3，反应压力20MPa，反应温度为30℃。测试发现，1，4-丁炔二醇的总转化率为100％，1，4-丁二醇的选择性为99.7％。 In the third step, the reaction is carried out in a capillary reactor. The catalyst is Al 2 O 3 , the reaction pressure is 20 MPa, and the reaction temperature is 30°C. The test found that the total conversion rate of 1,4-butynediol was 100%, and the selectivity of 1,4-butanediol was 99.7%.
实施例1-6汇总Summary of Examples 1-6
Figure PCTCN2019120090-appb-000001
Figure PCTCN2019120090-appb-000001
综上所述，第三步在毛细管反应器中进行，同时，加氢方式中，优先选用两步加氢或三步加氢，1，4-丁炔二醇可以全部转化，1，4-丁二醇的选择性极高。In summary, the third step is carried out in a capillary reactor. At the same time, in the hydrogenation mode, two-step hydrogenation or three-step hydrogenation is preferred. 1,4-butynediol can be completely converted, and 1,4- The selectivity of butanediol is extremely high.
上述实施例与对照组主要区别为采用毛细管反应器，毛细管反应器相比于淤浆床，可以让催化剂保持持久的活性，且散热性较好，可以极大的提高设备 的使用寿命The main difference between the above embodiment and the control group is the use of a capillary reactor. Compared with a slurry bed, the capillary reactor can keep the catalyst active and has better heat dissipation, which can greatly improve the service life of the equipment
至此，已经结合附图所示的优选实施方式描述了本发明的技术方案，但是，本领域技术人员容易理解的是，本发明的保护范围显然不局限于这些具体实施方式。在不偏离本发明的原理的前提下，本领域技术人员可以对相关技术特征做出等同的更改或替换，这些更改或替换之后的技术方案都将落入本发明的保护范围之内。So far, the technical solutions of the present invention have been described in conjunction with the preferred embodiments shown in the drawings. However, it is easy for those skilled in the art to understand that the protection scope of the present invention is obviously not limited to these specific embodiments. Without departing from the principle of the present invention, those skilled in the art can make equivalent changes or substitutions to the relevant technical features, and the technical solutions after these changes or substitutions will fall within the protection scope of the present invention.

Claims (10)

  1. 一种1，4-丁二醇的制备系统，其特征在于，包括甲醛生产装置、乙炔发生装置、微界面发生器、脱离子系统和加氢系统；所述微界面发生器用于将气体破碎形成直径≥1μm、且＜1mm的微米级气泡，所述微界面发生器包括第一微界面发生器和第二微界面发生器；A preparation system of 1,4-butanediol, which is characterized in that it comprises a formaldehyde production device, an acetylene generating device, a micro-interface generator, a disengagement subsystem, and a hydrogenation system; the micro-interface generator is used to crush the gas to form Micron-level bubbles with a diameter of ≥1μm and <1mm, the micro-interface generator includes a first micro-interface generator and a second micro-interface generator;
    所述甲醛生产装置和所述乙炔发生装置的输出端通过所述第一微界面发生器连接炔化反应装置；所述脱离子系统的输出端通过所述第二微界面发生器连接所述加氢系统，且所述加氢系统为多级加氢系统；The output ends of the formaldehyde production device and the acetylene generating device are connected to the acetylene reaction device through the first micro-interface generator; the output end of the disengagement subsystem is connected to the adding device through the second micro-interface generator A hydrogen system, and the hydrogenation system is a multi-stage hydrogenation system;
    所述甲醛生产装置包括依次连接的加热系统、反应系统和产品收集系统，所述加热系包括加热器、再沸器和过热器；所述加热器包括第一加热器和第二加热器，所述第一加热器位于尾气风机的输出端，第二加热器连接分别连接外界空气和混合器。The formaldehyde production device includes a heating system, a reaction system, and a product collection system that are connected in sequence. The heating system includes a heater, a reboiler, and a superheater; the heater includes a first heater and a second heater. The first heater is located at the output end of the exhaust fan, and the second heater is connected to the outside air and the mixer respectively.
  2. 根据权利要求1所述的1，4-丁二醇的制备系统，其特征在于，所述炔化反应装置后端还连接精馏装置，所述精馏装置为1，4-丁炔二醇精馏装置，所述1，4-丁炔二醇精馏装置的输出端连接所述脱离子系统。The 1,4-butanediol preparation system according to claim 1, wherein the back end of the acetylene reaction device is also connected to a rectification device, and the rectification device is 1,4-butynediol The rectification device, the output end of the 1,4-butynediol rectification device is connected to the disengagement subsystem.
  3. 根据权利要求1所述的1，4-丁二醇的制备系统，其特征在于，所述多级加氢系统包括低压加氢系统和高压加氢系统，所述低压加氢系统与所述高压加氢系统的输入端均连接第二微界面发生器，所述第二微界面发生器的输入端连接所述脱离子系统。The 1,4-butanediol preparation system according to claim 1, wherein the multi-stage hydrogenation system includes a low-pressure hydrogenation system and a high-pressure hydrogenation system, and the low-pressure hydrogenation system is connected to the high-pressure hydrogenation system. The input ends of the hydrogenation system are all connected to the second micro-interface generator, and the input end of the second micro-interface generator is connected to the separation subsystem.
  4. 根据权利要求1所述的1，4-丁二醇的制备系统，其特征在于，所述反应器与过热器之间还连接有用于稳压平衡的汽包。The production system of 1,4-butanediol according to claim 1, wherein a steam drum for pressure stabilization and balance is also connected between the reactor and the superheater.
  5. 根据权利要求1所述的1，4-丁二醇的制备系统，其特征在于，所述吸收塔的数量为两个，包括第一吸收塔和第二吸收塔，第一吸收塔的输出端连接有循环泵，所述循环泵的输出端连接配制槽与产品槽，所述第二吸收塔的输出端连接有尾气风机和燃烧器，且所述尾气风机的输出端连接所述第一加热器。The 1,4-butanediol preparation system according to claim 1, wherein the number of the absorption tower is two, including a first absorption tower and a second absorption tower, and the output end of the first absorption tower A circulating pump is connected, the output end of the circulating pump is connected to the preparation tank and the product tank, the output end of the second absorption tower is connected to an exhaust fan and a burner, and the output end of the exhaust fan is connected to the first heating Device.
  6. 根据权利要求1所述的1，4-丁二醇的制备系统，其特征在于，所述乙 炔发生装置依次包括水解系统、乙炔发生器和冷却器，所述冷却器的输出端连接水解槽和气柜。The 1,4-butanediol preparation system according to claim 1, wherein the acetylene generating device includes a hydrolysis system, an acetylene generator, and a cooler in sequence, and the output end of the cooler is connected to the hydrolysis tank and the gas. cabinet.
  7. 根据权利要求1所述的1，4-丁二醇的制备系统，其特征在于，所述加氢系统内设有外式反应器，所述外式反应器包括淤浆床、固定床、滴流床或毛细管反应器中的一种或多种。The 1,4-butanediol preparation system according to claim 1, wherein the hydrogenation system is provided with an external reactor, and the external reactor includes a slurry bed, a fixed bed, and a drip bed. One or more of fluidized bed or capillary reactors.
  8. 根据权利要求7所述的1，4-丁二醇的制备系统，其特征在于，所述毛细管反应器呈上端开口直径小于下端开口直径。The 1,4-butanediol preparation system according to claim 7, wherein the capillary reactor has an upper opening diameter smaller than a lower opening diameter.
  9. 根据权利要求8所述的1，4-丁二醇的制备系统，其特征在于，所述毛细管反应器由多个单个毛细管均匀组合成型，单个毛细管的内径为2-4mm，整体式毛细管的底部内径为10-16cm，上部直径为5-8cm。The 1,4-butanediol preparation system according to claim 8, wherein the capillary reactor is formed by a uniform combination of a plurality of single capillaries, the inner diameter of the single capillary is 2-4mm, and the bottom of the integral capillary The inner diameter is 10-16cm, and the upper diameter is 5-8cm.
  10. 一种1，4-丁二醇的制备工艺，其特征在于，包括如下步骤：A preparation process of 1,4-butanediol, which is characterized in that it comprises the following steps:
    步骤一：利用甲醛生产装置和乙炔发生装置分别制备甲醛和乙炔；Step 1: Use the formaldehyde production device and the acetylene generation device to prepare formaldehyde and acetylene respectively;
    步骤二：将步骤一制备的甲醛和乙炔在反应釜中进行炔醛反应，并在炔醛反应中加入催化剂，生成1，4-丁炔二醇；炔醛反应中的催化剂为Cu 2C 2-Bi 2O 3或SiO 2，反应温度为80-120℃，反应釜中的反应压力≤2MPa； Step 2: The formaldehyde and acetylene prepared in step 1 are reacted with acetylene in a reaction kettle, and a catalyst is added to the acetylene reaction to produce 1,4-butynediol; the catalyst in the acetylene reaction is Cu 2 C 2 -Bi 2 O 3 or SiO 2 , the reaction temperature is 80-120℃, and the reaction pressure in the reactor is ≤2MPa;
    步骤三：将步骤二制备的1，4-丁炔二醇在外反应器中加氢反应，加氢反应为两段加氢，第一段加氢反应在低压加氢系统中进行，采用的催化剂为Ni基催化剂，反应压力1-5MPa；第二段加氢反应在高压系统中进行，采用的催化剂为Pd基催化剂的，反应压力10-30MPa；两段加氢工艺完成后，将第一段加氢反应与第二段加氢产生的1，4-丁二醇在精馏塔中进行精制生成1，4-丁二醇产品。Step 3: Hydrogenate the 1,4-butynediol prepared in step 2 in an external reactor. The hydrogenation reaction is a two-stage hydrogenation. The first-stage hydrogenation reaction is carried out in a low-pressure hydrogenation system. The catalyst used is It is a Ni-based catalyst with a reaction pressure of 1-5MPa; the second stage hydrogenation reaction is carried out in a high-pressure system, and the catalyst used is a Pd-based catalyst with a reaction pressure of 10-30MPa; after the two-stage hydrogenation process is completed, the first stage The 1,4-butanediol produced by the hydrogenation reaction and the second stage of hydrogenation is refined in a rectifying tower to produce 1,4-butanediol products.
PCT/CN2019/120090 2019-09-06 2019-11-22 Preparation system and process for 1,4-butanediol WO2021042579A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201910839878.7 2019-09-06
CN201910839878.7A CN112457160A (en) 2019-09-06 2019-09-06 Preparation system and process of 1, 4-butanediol

Publications (1)

Publication Number Publication Date
WO2021042579A1 true WO2021042579A1 (en) 2021-03-11

Family

ID=74806816

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/120090 WO2021042579A1 (en) 2019-09-06 2019-11-22 Preparation system and process for 1,4-butanediol

Country Status (2)

Country Link
CN (1) CN112457160A (en)
WO (1) WO2021042579A1 (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101244984A (en) * 2007-02-15 2008-08-20 巴斯福股份公司 Method for the production of 1,4-butanediol
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101244984A (en) * 2007-02-15 2008-08-20 巴斯福股份公司 Method for the production of 1,4-butanediol
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

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
LI YU-FANG ,LI MING: "Production Technology and Market Analysis of 1,4-butanediol in China", CHEMICAL INDUSTRY, vol. 30, no. 10, 21 October 2012 (2012-10-21), pages 39 - 44, XP009526632, ISSN: 1673-9647 *
LIU XIANG ,LIAO QIJIANG ,ZHANG MINQING: "Research progress of 1,4-butynediol hydrogenation process", CHEMICAL INDUSTRY AND ENGINEERING PROGRESS, vol. 36, no. 8, 12 May 2017 (2017-05-12), pages 2787 - 2797, XP009526636, ISSN: 1000-6613, DOI: 10.16085/j.issn.1000-6613.2017-0320 *
ZHANG ZHIBING; TIAN HONGZHOU; ZHANG FENG; ZHOU ZHENG: "Overview of Microinterface Intensification in Multiphase Reaction Systems", JOURNAL OF CHEMICAL INDUSTRY AND ENGINEERING, vol. 69, no. 1, 6 November 2007 (2007-11-06), pages 44 - 49, XP009526633, ISSN: 0438-1157, DOI: 10.11949/j.issn.0438-1157.20171400 *

Also Published As

Publication number Publication date
CN112457160A (en) 2021-03-09

Similar Documents

Publication Publication Date Title
CN101437750B (en) Hydrogen generator and hydrogenation apparatus
US5762658A (en) Self-sustaining hydrogene generator
CN101139242B (en) Method for liquid phase selective hydrogenation of C3 hydrocarbons
CN106518608B (en) The continuous preparation method and device of cyclohexanedimethanol
CN101774928B (en) Method for preparing m-xylylenediamine
JP4388000B2 (en) Method for ring hydrogenation of methylenedianiline
WO2023071938A1 (en) Maleic anhydride hydrogenation method and succinic acid production method comprising same
CN113563201A (en) Method for continuously and efficiently synthesizing 3, 4-dichloroaniline based on fixed bed microreactor
CN111689849B (en) Method for producing succinic acid by liquid-phase two-stage hydrogenation
CN101735182A (en) Process for continuously producing succinic anhydride through hydrogenation of maleic anhydride
CN102875500A (en) Continuous production method of 2-MeTHF (2-methyltetrahydrofuran)
WO2021042579A1 (en) Preparation system and process for 1,4-butanediol
WO2021227136A1 (en) Enhanced reaction system and method for preparing cyclohexanone by selective hydrogenation of benzene
CN102190582A (en) Method of simultaneously producing dimethyl succinate and 1,4-butyl glycol
CN109748791A (en) Produce the power-economizing method of dimethyl adipate
CN107673952A (en) The method that 1,2 propane diols and normal propyl alcohol are prepared using biological glycerol
CN213506661U (en) Preparation system of 1, 4-butanediol
CN108285417A (en) The method that liquid phase continuous catalytic hydrogenation reduction nitrotoleune prepares methylaniline
CN111116335A (en) Method and device for preparing acrolein or methacrolein
CN102432418B (en) Method for preparing cyclohexane by performing two-section benzene hydrogenation in automatic liquid level control way
CN112011366A (en) Micro-interface reaction system and method for petroleum resin hydrogenation
CN112759505A (en) Method and system for preparing ethylene glycol
CN103357355A (en) High-temperature reactor and chemical engineering system using the same
CN113200875B (en) Micro-reaction system and method for continuously preparing 2-amino-1, 3-diol compound
CN116023350A (en) System and method for preparing succinic anhydride

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19944126

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19944126

Country of ref document: EP

Kind code of ref document: A1