CN216910238U - Device for synthesizing ethylene carbonate or propylene carbonate - Google Patents

Abstract

The utility model discloses a device for synthesizing ethylene carbonate or propylene carbonate, Ethylene Oxide (EO) or Propylene Oxide (PO) and CO₂Mixing the materials by a material mixer, then feeding the mixture into a tubular reactor, reacting under the catalytic action of a catalyst to generate a crude product of Ethylene Carbonate (EC) or Propylene Carbonate (PC), and sequentially removing light components, heavy components and refining the crude product of Ethylene Carbonate (EC) or Propylene Carbonate (PC) to obtain an electronic grade product of Ethylene Carbonate (EC) or Propylene Carbonate (PC). The catalyst adopted by the utility model is a resin catalyst, is insoluble in water, organic solvent or inorganic solvent, does not decompose metal ions, does not react with raw materials in a reaction system such as carbon dioxide or EO/PO, and is used for catalyzing and synthesizing EO/PO and CO₂The chemical reaction is efficient, environment-friendly, safe and reliable.

Description

Device for synthesizing ethylene carbonate or propylene carbonate

Technical Field

The utility model relates to a device for synthesizing ethylene carbonate or propylene carbonate, belonging to the technical field of chemical synthesis.

Background

Ethylene Carbonate (EC) or Propylene Carbonate (PC) is two basic materials of a carbonate family, namely an electronic chemical family, is mainly used as a chemical solvent in a new energy automobile battery, and is the best known chemical solvent with green environmental protection concept. The current main methods for synthesizing the two esters include phosgene method, urea alcoholysis method and halogenated alcohol method:

the phosgene method has high cost and high toxicity and is gradually eliminated; the urea alcoholysis method is difficult to recycle and is not popular because of large amount of ammonia gas; the halohydrin method also produces a byproduct of halide, is not an environment-friendly process, and is gradually eliminated.

At present, the direct synthesis of ethylene carbonate or propylene carbonate, which is a single product, has many advantages, and the direct synthesis process includes potassium methoxide and sodium methoxide (including potassium ethoxide, sodium ethoxide and ionic liquid methods thereof) and solid alkali methods. However, when an EC/PC is directly synthesized from an epoxy substance such as EO/PO and carbon dioxide, and a catalyst thereof is potassium methoxide or potassium ethoxide or an ionic liquid thereof, these metal ions directly react with carbon dioxide to produce carbonate to cause precipitation, and the pipe is clogged during the operation of the apparatus to cause a safety accident, and the solid alkali method also decomposes the metal ions when it comes into contact with water, and the same problems as above occur.

The utility model uses carbon dioxide and ethylene oxide or propylene oxide to directly synthesize a single product, namely ethylene carbonate or propylene carbonate, by adopting a tube array fixed bed technology under the action of a resin catalyst, the material distribution is uniform, the product is single and pure, the requirements of electronic grade products are met, the process is environment-friendly, and the method is safe and reliable; overcomes the defects of the technical route at a time.

Disclosure of Invention

The utility model aims to solve the technical problem of providing a device for directly synthesizing ethylene carbonate or propylene carbonate aiming at the defects in the prior art, wherein the adopted catalyst is a resin catalyst, is insoluble in water, organic solvent or inorganic solvent, does not decompose metal ions, does not chemically react with raw materials in a reaction system such as carbon dioxide or EO/PO, and is used for catalyzing and synthesizing EO/PO and CO₂The chemical reaction is efficient, environment-friendly, safe and reliable.

In order to achieve the purpose, the utility model adopts the following technical scheme:

the utility model firstly provides a device for synthesizing ethylene carbonate or propylene carbonate, which comprises a material mixer, a tubular reactor, a flash tank, a light component removal tower, a heavy component removal tower and a refining tower which are connected in sequence, and is characterized in that:

the material mixer is provided with a feed inlet I-1, a feed inlet I-2 and a discharge outlet I, wherein: feed inlet I-1 and the supply of CO₂The devices are connected; the inlet I-2 is connected to a device capable of supplying Ethylene Oxide (EO) or Propylene Oxide (PO); the discharge port I is connected with the tubular reactor;

the shell and tube reactor is provided with a feed inlet II and a discharge outlet II, wherein: the feed port II is connected with a discharge port I of the material mixer, and the discharge port II is connected with the flash tank;

the flash tank is provided with CO at the top of the tower₂The discharge port, lower part is provided with feed inlet III in tower wall one side, and the opposite side middle part is provided with discharge gate III, wherein: CO 2₂The discharge port is connected with a compressor, and the outlet of the compressor is connected with a feed port I-1 of the material mixer; the feed inlet III is connected with a discharge outlet II of the tubular reactor; the discharge port III is connected with a lightness-removing tower;

the light component removing tower is characterized in that a feed inlet IV is formed in the middle of the light component removing tower, a light component outlet is formed in the top of the light component removing tower, and a discharge outlet IV is formed in the bottom of the light component removing tower, wherein: the feed inlet IV is connected with a discharge outlet III of the flash tank, a light component outlet is connected with a tail gas absorption system, and a discharge outlet IV is connected with a de-weighting tower;

heavy component removal tower, the middle part is provided with feed inlet V, the top is provided with discharge gate V, the bottom is provided with heavy component export, wherein: the feed inlet V is connected with a discharge outlet IV of the lightness-removing column, the heavy component outlet is connected with a heavy component recovery system, and the discharge outlet V is connected with the refining column;

the refining tower, the middle part is provided with feed inlet VI, the top is provided with exhaust emission port, the bottom is provided with discharge gate VI, wherein: the feed inlet VI is connected with a discharge port V of the de-weighting tower, a tail gas discharge port is connected with a tail gas absorption system, and the discharge port VI is connected with a device for harvesting Ethylene Carbonate (EC) or Propylene Carbonate (PC).

In the technical scheme, the tubular reactor is of a vertical tubular structure, the cross section of the tubular structure is hexagonal, vertically distributed tubular pipes are uniformly distributed in the tubular reactor, the number of the tubular pipes is 1-100000, the pipe diameter is 1-100mm, and the length is 1-100 m.

In the technical scheme, the catalyst is filled in the tubular reactor, and the catalyst is directly filled in a bulk form, namely in an original state; or packed catalyst, when the packed form is the form of packed catalyst, the structure of packed catalyst is preferably the same as that of packed catalyst in CN 201720485329.0; or in the form of a modular catalyst packing, when the packing is in the form of a modular catalyst, the structure of the modular catalyst is preferably the same as that of the modular catalyst in CN 201620189748.5.

In the technical scheme, the light component removal tower is filled with tower plates or structured packing, when the tower plates are filled, the number of layers is more than or equal to 1 and less than or equal to 200, and the distance between the plates is 0.1-1.0 m; when the structured packing is filled, the number of filling stages is more than or equal to 1 and less than or equal to 50, and the height of each stage is 1-3 m.

In the technical scheme, the light component removal tower is provided with the liquid distributor at the feed inlet IV.

In the technical scheme, the weight removal tower is filled with tower plates or structured packing, when the tower plates are filled, the number of layers is more than or equal to 1 and less than or equal to 100, and the distance between the plates is 0.1-0.5 m; when the structured packing is filled, the number of filling stages is more than or equal to 1 and less than or equal to 50, and the height of each stage is 1-3 m.

In the above technical scheme, the feed inlet V of the heavy component removing tower is provided with a liquid distributor.

In the technical scheme, the refining tower is filled with tower plates or structured packing, when the tower plates are filled, the number of layers is more than or equal to 1 and less than or equal to 200, and the distance between the plates is 0.1-0.8 m; when the structured packing is filled, the number of filling stages is more than or equal to 1 and less than or equal to 50, and the height of each stage is 1-3 m.

In the above technical scheme, the feed inlet VI of the refining tower is provided with a liquid distributor.

The utility model also provides a method for synthesizing ethylene carbonate or propylene carbonate, which comprises the following steps:

ethylene Oxide (EO) or Propylene Oxide (PO) with CO₂Mixing, reacting under the catalytic action of a catalyst to generate crude Ethylene Carbonate (EC) or Propylene Carbonate (PC), and sequentially reacting the crude Ethylene Carbonate (EC) or Propylene Carbonate (PC)Removing light components, removing heavy components and refining to obtain an electronic grade product Ethylene Carbonate (EC) or Propylene Carbonate (PC).

In the above technical solution, the method specifically includes the following steps:

(1) catalytic synthesis:

CO₂feeding the mixture into a material mixer from a feeding hole I-1, feeding Ethylene Oxide (EO) or Propylene Oxide (PO) into the material mixer from a feeding hole I-2, mixing the mixture, feeding the mixture into a tubular reactor from a feeding hole II, reacting the mixture under the catalytic action of a catalyst in the tubular reactor, discharging a product from a discharging hole II, and feeding the product into a flash tank from a feeding hole III;

(2) flash separation:

the product enters a flash tank from a feed inlet III for flash evaporation, and CO is obtained at the top₂And obtaining Ethylene Carbonate (EC) or Propylene Carbonate (PC) reactant at the bottom; CO 2₂From CO₂After being discharged from a discharge port, the mixture is compressed by a compressor and then flows back to a material mixer for cyclic utilization; discharging Ethylene Carbonate (EC) or Propylene Carbonate (PC) reactants from a discharge port III and feeding the reactants into a light component removal tower from a feed port IV;

(3) removing light components:

ethylene Carbonate (EC) or Propylene Carbonate (PC) reactants enter a light component removal tower for light component removal reaction after being uniformly distributed from a feed inlet IV and a liquid distributor, light components are obtained at the top of the tower, Ethylene Carbonate (EC) or Propylene Carbonate (PC) crude products are obtained at the bottom of the tower, the light components are discharged into a tail gas absorption system from a light component outlet, the Ethylene Carbonate (EC) or Propylene Carbonate (PC) crude products are discharged from a discharge outlet IV at the bottom of the tower and enter a heavy component removal tower from a feed inlet V;

(4) removing heavy components:

ethylene Carbonate (EC) or Propylene Carbonate (PC) crude products are uniformly distributed from a feed inlet V through a liquid distributor and then enter a heavy component removing tower for heavy component removing reaction, Ethylene Carbonate (EC) or Propylene Carbonate (PC) primary products are obtained at the tower top, heavy components are obtained at the tower bottom, the heavy components are discharged into a heavy component recovery system through a heavy component outlet, the Ethylene Carbonate (EC) or Propylene Carbonate (PC) primary products are discharged from a discharge outlet V at the tower top and enter a refining tower through a feed inlet VI;

(5) refining:

ethylene Carbonate (EC) or Propylene Carbonate (PC) primary products enter a refining tower for refining after being uniformly distributed from a feeding hole VI through a liquid distributor, Ethylene Carbonate (EC) or Propylene Carbonate (PC) electronic-grade products are obtained at the bottom of the tower, tail gas obtained at the top of the tower is discharged into a tail gas recovery system through a tail gas discharge port, and Ethylene Carbonate (EC) or Propylene Carbonate (PC) electronic-grade products are discharged from a discharge hole VI for recovery.

In the above technical scheme, in the step (1), the Ethylene Oxide (EO) or Propylene Oxide (PO) and CO are used₂In a molar ratio of 1: 1.0-10.0.

In the above technical scheme, in the step (1), the Ethylene Oxide (EO) or Propylene Oxide (PO) and CO are used₂After mixing, the volume space velocity of the mixture entering the tubular reactor is 1000-10000h^-1Preferably 3000-^-1More preferably 8000h of 5000-^-1。

In the technical scheme, in the step (1), the reaction temperature of the tubular reactor is normal temperature to 200 ℃, and the pressure is normal pressure to 10 MPa.

In the above technical scheme, in the step (1), the catalyst comprises the following raw materials in parts by weight: 1-99 parts of polymerized monomer, 0.1-10 parts of cross-linking agent, 0.1-5 parts of benzoyl peroxide, 0.1-50 parts of siloxane, 0.1-100 parts of 1% polyvinyl alcohol solution, 1-50 parts of 80# microcrystalline wax, 1-400 parts of chloromethyl ether, 1-100 parts of zinc chloride, 1-50 parts of aminating agent, 1-100 parts of DMF (dimethyl formamide), 1-100 parts of N-ethylimidazole, 1-30 parts of polyepichlorohydrin and 1-100 parts of absolute ethyl alcohol.

In the above technical solution, the resin catalyst preferably comprises the following raw materials in parts by weight: 50-99 parts of polymerized monomer, 0.5-10 parts of cross-linking agent, 0.5-5 parts of benzoyl peroxide, 0.5-50 parts of siloxane, 0.5-100 parts of 1% polyvinyl alcohol solution, 1-50 parts of 80# microcrystalline wax, 5-400 parts of chloromethyl ether, 5-100 parts of zinc chloride, 5-50 parts of aminating agent, 5-100 parts of DMF (dimethyl formamide), 5-100 parts of N-ethylimidazole, 5-30 parts of polyepichlorohydrin and 5-100 parts of absolute ethyl alcohol.

In the above technical solution, the resin catalyst further preferably comprises the following raw materials in parts by weight: 80-99 parts of polymerized monomer, 0.8-10 parts of cross-linking agent, 0.8-5 parts of benzoyl peroxide, 0.8-50 parts of siloxane, 0.8-100 parts of 1% polyvinyl alcohol solution, 0.8-50 parts of 80# microcrystalline wax, 8-400 parts of chloromethyl ether, 8-100 parts of zinc chloride, 8-50 parts of aminating agent, 8-100 parts of DMF (dimethyl formamide), 8-100 parts of N-ethylimidazole, 8-30 parts of epichlorohydrin and 8-100 parts of absolute ethyl alcohol.

In the above technical scheme, the polymerized monomer is a mixture of any one, two or more of styrene, acrylic acid and methacrylic acid mixed in any proportion.

In the above technical solution, the polymerized monomer is preferably styrene.

In the technical scheme, the cross-linking agent is a mixture formed by mixing any one, two or more than two of divinylbenzene, dipropylene benzene and TAIC in any proportion.

In the above technical solution, the cross-linking agent is preferably divinylbenzene.

In the technical scheme, the structural formula of the siloxane is (R)₂SiO) x, wherein: x is 1-10 and R is CH₃-、CH₃CH₂-、 -CH₂Any one or more of alkyl groups such as-CH-and the like.

In the above technical solution, R of the siloxane is preferably CH3-, and x is preferably 4.

In the above technical scheme, the amination agent is a mixture of any one, two or more of dimethylamine, trimethylamine, diamine, hexamethylenetetramine and polyethylene polyamine (diethylenetriamine, triethylenetetramine and the like) mixed in any proportion.

In the above technical scheme, the aminating agent is preferably hexamethylenetetramine.

In the above technical scheme, in the step (1), the catalyst is prepared by the following method:

polymerization reaction: uniformly mixing 1-99 parts of polymerized monomer, 0.1-10 parts of cross-linking agent, 0.1-50 parts of siloxane, 0.1-5 parts of benzoyl peroxide and 1-50 parts of 80# microcrystalline wax, adding into 0.1-100 parts of polyvinyl alcohol solution, carrying out polymerization reaction at 40-100 ℃ and normal pressure for 10-15h to obtain macroporous white spheres, controlling the cross-linking degree of the macroporous white spheres to be 5-10%, extracting and removing the 80# microcrystalline wax, and drying for later use;

chloromethylation reaction: carrying out chloromethylation reaction on the macroporous white balls obtained in the step I, 1-100 parts of zinc chloride and 1-400 parts of chloromethyl ether at 30-55 ℃ under normal pressure for 15-20h to generate benzyl balls, wherein the chlorine content in the benzyl balls is controlled to be more than 17%;

amination reaction: adding 1-100 parts of DMF (dimethyl formamide) and 1-50 parts of aminating agent into the benzyl ball obtained in the step (II), adjusting the pH value of a system to 12-14, heating to 40-60 ℃, reacting for 12-15h under normal pressure for amination reaction, and washing a solid product with deionized water to be neutral to obtain the amine ball;

amidation reaction: uniformly mixing 1-100 parts of N-ethylimidazole, 1-100 parts of polyepichlorohydrin and 1-100 parts of absolute ethyl alcohol, heating to 30-90 ℃, reacting for 10-15 hours under normal pressure, adding the amine ball obtained in the step III into a system obtained after reaction, and adding N into the system obtained after reaction₂Supplementing pressure to 1MPa, heating to 110-160 ℃, reacting for 10-30h at the temperature, cooling to 70 ℃, and washing with absolute ethyl alcohol until no white color is formed to obtain the resin catalyst for synthesizing ethylene carbonate or propylene carbonate.

In the above-mentioned technical means, in the step (i), the polymerization reaction is preferably carried out under the following reaction conditions: heating to 60-80 deg.c and reacting at the temperature for 10-15 hr, and heating to 90-100 deg.c and reacting at the temperature for 10-30 hr; the polymerization reaction, the reaction conditions are more preferably: the temperature is increased to 80 ℃ and the reaction is carried out for 15h, and then the temperature is increased to 100 ℃ and the reaction is carried out for 30 h.

In the above technical scheme, in the second step, preferably, 100 parts of macroporous white balls, 100 parts of zinc chloride and 400 parts of chloromethyl ether are subjected to chloromethylation reaction; the chloromethylation reaction preferably adopts the following reaction conditions: the temperature was raised to 41 ℃ and the reaction was carried out at this temperature for 19 h.

In the technical scheme, in the third step, preferably 100 parts of benzyl balls are added into a system formed by 100 parts of DMF and 50 parts of aminating agent; the amination reaction preferably adopts the following reaction conditions: adding DMF and aminating agent, regulating system pH to 12-14 with 30% NaOH solution, heating to 45 deg.C, and reacting at the temperature for 13 h.

In the technical scheme, in the step (iv), preferably, 100 parts of amine balls are added into a reaction system obtained by 100 parts of N-ethylimidazole, 100 parts of polyepichlorohydrin and 100 parts of absolute ethyl alcohol; the amidation reaction preferably takes place under the following reaction conditions: mixing N-ethylimidazole, polyepichlorohydrin and ethanol uniformly, heating to 80 ℃, reacting for 30 hours at 80 ℃, adding an amine ball into a reaction system, and adding N₂The pressure is supplemented to 1MPa, the temperature is increased to 160 ℃, and the reaction is carried out for 30h at 160 ℃.

In the above technical solution, in the step (2), the flash tank has the following flash conditions: normal temperature-100 deg.c and normal pressure-0.5 MPa.

In the above technical scheme, in the step (2), the reflux ratio is 0.1-10.

In the above technical scheme, in the step (3), the light component removal reaction is performed under the following reaction conditions: the temperature is normal temperature-200 deg.C, preferably 40-150 deg.C, and the pressure is normal pressure-10 MPa, preferably normal pressure-1 MPa.

In the above technical scheme, in the step (4), the reaction conditions of the de-weighting reaction are as follows: the temperature is normal temperature-200 deg.C, preferably 40-150 deg.C, and the pressure is normal pressure-10 MPa, preferably normal pressure-1 MPa.

In the above technical solution, in the step (5), the refining is performed under the following conditions: the temperature is normal temperature-200 deg.C, preferably 40-150 deg.C, and the pressure is normal pressure-10 MPa, preferably normal pressure-1 MPa.

The apparatus and method of the present invention are also used for the preparation of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, diphenyl carbonate: dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and diphenyl carbonate can be produced by feeding Ethylene Carbonate (EC) or Propylene Carbonate (PC) from the feed port I-2 and methanol, ethanol or phenol from the feed port I-1, respectively.

Compared with the prior art, the method has the following characteristics:

1. according to the utility model, siloxane is grafted on the catalyst, so that the stability and temperature resistance of the basic group of the catalyst are enhanced; the amine ball adopts hexamethylenetetramine as an aminating agent, the mass exchange capacity is high, polyether imidazole is grafted on the amidation reaction resin, the catalyst activity is high, the service life is long, and the conversion rate of ethylene oxide or propylene oxide reaches more than 95%; according to the utility model, the 80# microcrystalline wax is used as a pore-foaming agent, so that the aperture of the prepared resin catalyst is controlled to be 50-100nm, the affinity of the catalyst to alkyl carbonate materials is obviously improved, the raw materials for synthesis reaction are easier to approach the active center, the reaction is easier to carry out, the reaction efficiency is improved, and the reaction energy consumption is reduced.

2. The resin catalyst in the utility model is used for catalyzing and synthesizing EC/PC, no hazardous waste such as carbonate can be generated, and because methanol potassium sodium or ethanol potassium sodium or ionic liquid is used as the catalyst, hazardous waste-carbonate can be generated, so that the pipeline is directly blocked, safety accidents or device production halt are caused, and the defects are visual and serious;

3. the resin catalyst in the utility model is used for catalytically synthesizing EC/PC, does not generate any hazardous waste, is green and environment-friendly, safe and reliable, is mild in operation, and is easy to control operation and production;

4. the resin catalyst in the utility model is used for catalyzing and synthesizing EC/PC, a tube array fixed bed technology is adopted, the EO/PO conversion rate is almost 100%, the catalysis effect is high, the selectivity is as high as 100%, and the product purity reaches the electronic grade. The method meets the requirement of extremely high purity of electronic chemicals.

Drawings

FIG. 1 is a schematic view of the overall structure of an apparatus for synthesizing ethylene carbonate or propylene carbonate according to the present invention;

wherein: 1 is a material mixer, 2 is a tubular reactor, 3 is a flash tank, 4 is a compressor, 5 is a light component removal tower, 6 is a heavy component removal tower, and 7 is a refining tower.

Detailed Description

The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:

the utility model provides a device for synthesizing ethylene carbonate or propylene carbonate, which comprises a material mixer 1, a tubular reactor 2, a flash tank 3, a light component removal tower 5, a heavy component removal tower 6 and a refining tower 7 which are connected in sequence, as shown in figure 1:

the material mixer 1 is provided with a feed inlet I-1, a feed inlet I-2 and a discharge outlet I, wherein: feed inlet I-1 and can supply CO₂The devices are connected; the inlet I-2 is connected to a device capable of supplying Ethylene Oxide (EO) or Propylene Oxide (PO); the discharge port I is connected with the tubular reactor 2;

the shell and tube reactor 2 is provided with a feed inlet II and a discharge outlet II, wherein: the feed port II is connected with a discharge port I of the material mixer, and the discharge port II is connected with the flash tank (3);

the flash tank 3 is provided with CO at the top of the tower₂The discharge port, lower part is provided with feed inlet III in tower wall one side, and the opposite side middle part is provided with discharge gate III, wherein: CO 2₂The discharge port is connected with a compressor 4, and the outlet of the compressor is connected with a feed port I-1 of the material mixer; the feed inlet III is connected with a discharge outlet II of the tubular reactor; the discharge port III is connected with a lightness-removing tower;

the light component removing tower 5 is provided with a feeding hole IV in the middle, a light component outlet at the top and a discharging hole IV at the bottom, wherein: the feed inlet IV is connected with a discharge outlet III of the flash tank, a light component outlet is connected with a tail gas absorption system, and a discharge outlet IV is connected with a de-heavy tower 6;

heavy component removal tower 6, the middle part is provided with feed inlet V, the top is provided with discharge gate V, the bottom is provided with heavy component export, wherein: the feed inlet V is connected with a discharge outlet IV of the lightness-removing column, the heavy component outlet is connected with a heavy component recovery system, and the discharge outlet V is connected with a refining column 7;

refining tower 7, the middle part is provided with feed inlet VI, the top is provided with exhaust outlet, the bottom is provided with discharge gate VI, wherein: the feed inlet VI is connected with a discharge port V of the de-weighting tower, a tail gas discharge port is connected with a tail gas absorption system, and the discharge port VI is connected with a device for harvesting Ethylene Carbonate (EC) or Propylene Carbonate (PC).

In the utility model, the whole tubular reactor 2 is of a vertical tubular structure, the cross section of the tubular structure is hexagonal, vertically distributed tubular reactors are uniformly distributed in the tubular reactor, the number of the tubular reactors is 1-100000, the tubular diameter is 1-100mm, and the length is 1-100 m.

In the utility model, the tubular reactor 2 is filled with catalyst, or the catalyst is directly filled in a bulk form, namely in an original state; or packed catalyst, when the packed form is the form of packed catalyst, the structure of packed catalyst is preferably the same as that of packed catalyst in CN 201720485329.0; or in the form of a modular catalyst packing, when the packing is in the form of a modular catalyst, the structure of the modular catalyst is preferably the same as that of the modular catalyst in CN 201620189748.5.

In the utility model, the light component removal tower is filled with tower plates or structured packing, when the tower plates are filled, the number of layers is more than or equal to 1 and less than or equal to 200, and the distance between the plates is 0.1-1.0 m; when the structured packing is filled, the number of filling stages is more than or equal to 1 and less than or equal to 50, and the height of each stage is 1-3 m.

In the light component removal tower, a liquid distributor is arranged at a feed inlet IV.

In the utility model, the weight removal tower is filled with tower plates or structured packing, when the tower plates are filled, the number of layers is more than or equal to 1 and less than or equal to 100, and the distance between the plates is 0.1-0.5 m; when the structured packing is filled, the number of filling stages is less than or equal to 1 and less than or equal to 50, and the height of each stage is 1-3 m.

In the heavy component removing tower, a liquid distributor is arranged at a feed inlet V.

In the utility model, the refining tower is filled with tower plates or structured packing, when the tower plates are filled, the number of layers is less than or equal to 1 and less than or equal to 200, and the distance between the plates is 0.1-0.8 m; when the structured packing is filled, the number of filling stages is more than or equal to 1 and less than or equal to 50, and the height of each stage is 1-3 m.

In the refining tower, a liquid distributor is arranged at a feed inlet VI.

The utility model also provides a method for synthesizing ethylene carbonate or propylene carbonate, which comprises the following steps:

(1) catalytic synthesis:

CO₂the mixture enters a material mixer 1 from a feed inlet I-1, Ethylene Oxide (EO) or Propylene Oxide (PO) enters the material mixer from a feed inlet I-2, the mixture enters a tubular reactor 2 from a feed inlet II after being mixed, the reaction is carried out under the catalytic action of a catalyst in the tubular reactor, and a product is discharged from a discharge outlet II and enters a flash tank 3 from a feed inlet III;

(2) flash separation:

the product enters a flash tank from a feed inlet III for flash evaporation, and CO is obtained at the top₂And obtaining Ethylene Carbonate (EC) or Propylene Carbonate (PC) reactant at the bottom; CO 2₂From CO₂After being discharged from a discharge port, the mixture is compressed by a compressor 4 and then flows back to a material mixer for cyclic utilization; discharging Ethylene Carbonate (EC) or Propylene Carbonate (PC) reactants from a discharge port III and feeding the reactants into a light component removal tower from a feed port IV;

(3) removing light components:

ethylene Carbonate (EC) or Propylene Carbonate (PC) reactants enter a light component removal tower for light component removal reaction after being uniformly distributed from a feed inlet IV and a liquid distributor, light components are obtained at the top of the tower, Ethylene Carbonate (EC) or Propylene Carbonate (PC) crude products are obtained at the bottom of the tower, the light components are discharged into a tail gas absorption system from a light component outlet, the Ethylene Carbonate (EC) or Propylene Carbonate (PC) crude products are discharged from a discharge outlet IV at the bottom of the tower and enter a heavy component removal tower from a feed inlet V;

(4) removing heavy components:

ethylene Carbonate (EC) or Propylene Carbonate (PC) crude products are uniformly distributed from a feed inlet V through a liquid distributor and then enter a heavy component removing tower for heavy component removing reaction, Ethylene Carbonate (EC) or Propylene Carbonate (PC) primary products are obtained at the tower top, heavy components are obtained at the tower bottom, the heavy components are discharged into a heavy component recovery system through a heavy component outlet, the Ethylene Carbonate (EC) or Propylene Carbonate (PC) primary products are discharged from a discharge outlet V at the tower top and enter a refining tower through a feed inlet VI;

(5) refining:

ethylene Carbonate (EC) or Propylene Carbonate (PC) primary products enter a refining tower for refining after being uniformly distributed from a feeding hole VI through a liquid distributor, Ethylene Carbonate (EC) or Propylene Carbonate (PC) electronic-grade products are obtained at the bottom of the tower, tail gas obtained at the top of the tower is discharged into a tail gas recovery system through a tail gas discharge port, and Ethylene Carbonate (EC) or Propylene Carbonate (PC) electronic-grade products are discharged from a discharge hole VI for recovery.

The utility model is illustrated below with reference to specific examples:

example 1:

an apparatus for synthesizing ethylene carbonate or propylene carbonate, in this embodiment:

(1) the catalyst packed in the tubular reactor is in the form of packed catalyst, preferably of the same structure as the packed catalyst in CN 201720485329.0: the catalyst is uniformly distributed on the plane silk screen, and the stainless steel corrugated silk screen and the plane silk screen are tiled, overlapped and cover the catalyst, the edge is sealed, and one end is used as an axis to be rolled into a packed catalyst. The diameter or the minimum peripheral size of the catalyst is larger than the mesh diameters of the stainless steel corrugated wire mesh and the flat wire mesh; the packaged catalyst is rolled into a solid cylinder shape, the diameter of the packaged catalyst is more than or equal to 50 mm, the height of the packaged catalyst is more than or equal to 100mm, and the catalyst on the cross section of the packaged catalyst is uniformly distributed. When packing the catalyst, N packing catalysts are axially packed from top to bottom in a tube array, the distribution amount of the catalysts in the tube array increases progressively from top to bottom in the unit of packing catalysts, and the increase amplitude follows the following rule: n is a natural positive integer of 1, 2, 3, 4, 5, 6.. N, where K: when k is 1, the catalyst is uniformly distributed in the whole tube array, and when k is 0 < k < 1, the catalyst is gradually increased along the tube array in a unit of each bale, namely, the catalyst content in each bale is more increased and is uniformly increased as the catalyst is moved to the lower part of the catalytic section.

(2) The light component removing tower is filled with filler, the filling layer number is 10 sections, and each section is 2m in height

(3) The heavy component removing tower is filled with filler, the filling layer number is 5 sections, and each section is 2 meters in height.

(4) The refining tower is filled with filler, the filling layer number is 8 sections, and each section is 2 meters in height.

Example 2:

an apparatus for synthesizing ethylene carbonate or propylene carbonate, in this embodiment:

(1) the catalyst packing packed in the catalytic section of the catalytic distillation column is in the form of a modular catalyst, preferably having the same structure as the modular catalyst in CN 201620189748.5: the catalyst module comprises a catalyst, a metal wire mesh and metal wire mesh corrugated plates, wherein the module catalyst is arranged in parallel at intervals by the metal wire mesh and the metal wire mesh corrugated plates, a catalyst layer is formed by containing catalyst particles between the two metal wire meshes, and the catalyst particles in the catalyst layer are arranged at intervals by the metal wire mesh corrugated plates; catalyst layers in the module catalyst are arranged at intervals. Preferably, the module catalyst is peripherally fixed by metal wires; the outline of the module catalyst is wrapped, fixed and closed by a metal wire mesh to form a geometric shape; one or two layers of corrugated wire mesh plates (1 layer in example 2) are arranged between the wire meshes at intervals; the catalyst layers are arranged with one or two layers of wire mesh corrugated plates (1 layer in example 2) between them; the catalyst layer is formed by arranging one or two (1 layer in the embodiment 2) corrugated plates of the wire mesh between two layers of wire mesh at intervals, and the catalyst particles are filled in the catalyst layer; the geometric shape is a cube and a cylinder (the cylinder in the embodiment 2); the wire mesh and the wire mesh corrugated plate are made of stainless steel materials, and the wire mesh or the wire mesh corrugated plate can be replaced by a stainless steel plate with holes (stainless steel in the embodiment 2); the wire mesh and the wire mesh corrugated plate are vertically arranged; the catalyst layer is provided with a reinforced outer wall, and the wire mesh and the stainless steel perforated corrugated plate are used as the outer wall of the catalyst layer.

(2) The light component removing tower is filled with filler, the filling layer number is 10 sections, and each section is 2 meters in height.

(3) The heavy component removing tower is filled with filler, the number of filling layers is 5, and each section is 2 meters in height.

(4) The refining tower is filled with filler, the filling layer number is 8 sections, and each section is 2 meters in height.

Example 3:

the apparatus and materials involved in this example are as follows:

1. device for measuring the position of a moving object

A constant temperature water bath kettle (0-100 ℃), an adjustable electric stirrer (0-2000r), a three-mouth bottle (2000mL), a plastic stirring paddle, a thermometer (0-150 ℃), a rubber stopper (No. 5), a constant temperature oil bath kettle (0-300 ℃), a 100mL measuring cylinder and a 250mL high-pressure reaction kettle.

2. Main raw materials

Divinylbenzene, outsourcing technical grade; styrene, outsourcing technical grade; siloxane, outsourcing technical grade; chloromethyl ether, outsourcing technical grade; 80# microcrystalline wax, commercially available technical grade; ethanol, purchased technical grade; water, deionized water; dimethyl carbonate, outsourcing commercial grade; ethanol, purchased technical grade; n-ethylimidazole, outsourcing technical grade; polyepichlorohydrin, purchased in the outside industry; hexamethylenetetramine, commercially available.

A resin catalyst for synthesizing ethylene carbonate or propylene carbonate is prepared through the following steps

(1) Polymerisation reaction

In a reaction kettle, uniformly mixing 99 parts by weight of styrene, 14 parts by weight of 63.5% divinylbenzene, 40 parts by weight of 80# microcrystalline wax, 5 parts by weight of octamethyltetrasilane, and 1 part by weight of benzoyl peroxide, adding the mixture into 25 parts by weight of 1% polyvinyl alcohol solution, adding the mixture, heating to 80 ℃ to react for 15 hours, heating to 100 ℃ to react for 30 hours to obtain a product, namely a macroporous white ball, extracting the 80# microcrystalline wax cleanly, and drying for later use; wherein, the crosslinking degree of the polymerization reaction is controlled to be 7.9%;

(2) chloromethylation reaction

Putting 100 parts by weight of the macroporous white balls obtained in the step (1), 100 parts by weight of zinc chloride and 400 parts by weight of 40% chloromethyl ether into a reaction kettle, feeding materials, heating to 41 ℃ for reacting for 19 hours, controlling the chlorine content to be 18.5%, and generating benzyl balls after the reaction is finished;

(3) amination reaction

Adding 100 parts by weight of the benzyl balls prepared in the step (2) into a reaction kettle, adding 100 parts by weight of DMF (dimethyl formamide), adding 50 parts by weight of hexamethylenetetramine, adjusting the pH value of the system to 12 by using 30% NaOH, heating to 45 ℃, keeping the temperature for reaction for 13 hours, cooling, and washing to be neutral for later use.

(4) Amidation reaction

Uniformly mixing 100 parts by weight of N-ethylimidazole, 100 parts by weight of polyepichlorohydrin and 100 parts by weight of absolute ethyl alcohol, heating to 80 ℃ for reaction for 15 hours, adding 100 parts by weight of amine ball obtained in the step (3) into a system after reaction, and adding N into the system₂And (3) supplementing pressure to 1MPa, heating to 160 ℃ for reaction for 30h, cooling to 70 ℃, and washing with absolute ethyl alcohol until no white color exists to obtain the resin catalyst for synthesizing ethylene carbonate or propylene carbonate.

Example 4

A resin catalyst for synthesizing ethylene carbonate or propylene carbonate is prepared through the following steps

(1) Polymerisation reaction

In a reaction kettle, uniformly mixing 99 parts by weight of styrene, 16 parts by weight of 63.5% divinylbenzene, 40 parts by weight of 80# microcrystalline wax, 5 parts by weight of octamethyltetrasilane, and 1 part by weight of benzoyl peroxide, adding the mixture into 250 parts by weight of 1% polyvinyl alcohol solution, feeding, heating to 80 ℃ for reaction for 15 hours, heating to 105 ℃ for reaction for 30 hours to obtain a product, namely a macroporous white ball, extracting the 80# microcrystalline wax cleanly, and drying for later use; wherein, the crosslinking degree of the polymerization reaction is controlled to be 8.8 percent;

(2) chloromethylation reaction

Putting 100 parts by weight of the macroporous white balls obtained in the step (1), 50 parts by weight of zinc chloride and 400 parts by weight of 40% chloromethyl ether into a reaction kettle, feeding materials, heating to 41 ℃ for reacting for 19 hours, controlling the chlorine content to be 18.5%, and generating benzyl balls after the reaction is finished;

(3) amination reaction

Adding 100 parts by weight of the benzyl balls prepared in the step (2) into a reaction kettle, adding 100 parts by weight of DMF (dimethyl formamide), adding 100 parts by weight of hexamethylenetetramine, adjusting the pH value of the system to 12 by 30% of NaOH, heating to 45 ℃, carrying out heat preservation reaction for 30 hours, cooling, and washing to be neutral for later use.

(4) Amidation reaction

Uniformly mixing 100 parts by weight of N-ethylimidazole, 100 parts by weight of polyepichlorohydrin and 100 parts by weight of absolute ethyl alcohol, heating to 80 ℃ for reaction for 15 hours, and carrying out the steps(3) Adding 100 parts of amine balls into the reacted system, and using N₂And (3) supplementing pressure to 1MPa, heating to 160 ℃ for reaction for 30h, cooling to 70 ℃, and washing with absolute ethyl alcohol until no white color exists to obtain the resin catalyst for synthesizing ethylene carbonate or propylene carbonate.

Example 5:

a method for synthesizing ethylene carbonate or propylene carbonate, using the apparatus of example 1, comprising the steps of:

(1) catalytic synthesis:

CO₂enters a material mixer (1) from a feed inlet I-1, and Ethylene Oxide (EO) enters the material mixer from a feed inlet I-2 with the mixing molar ratio of 1.5:1, and the volume space velocity is 5000h after mixing^-1The feeding amount of the reaction product enters the tubular reactor (2) from the feeding port II (volume), the reaction is carried out under the catalytic action of the catalyst in the tubular reactor, the reaction temperature is 72-77 ℃, the reaction pressure is 0.42-0.72MPa, the product is discharged from the discharging port II and enters the flash tank (3) from the feeding port III; the catalyst used in this example was the resin catalyst obtained in example 3;

(2) flash separation:

and the product enters a flash tank from a feed inlet III for flash evaporation, and the flash evaporation conditions are as follows: at 50 ℃ and normal pressure; overhead CO production₂Obtaining Ethylene Carbonate (EC) reactant at the bottom; CO 2₂From CO₂After being discharged from the discharge port, the mixture is compressed by a compressor (4) and then totally flows back to the material mixer for recycling; discharging Ethylene Carbonate (EC) reactant from a discharge hole III and feeding the reactant into a light component removal tower from a feed hole IV;

(3) removing light components:

ethylene Carbonate (EC) reactants enter a lightness-removing tower for lightness-removing reaction after being uniformly distributed from a feed inlet IV and a liquid distributor, wherein the temperature is 77-82 ℃, and the reaction pressure is 0.35-0.65 MPa; light components are obtained at the top of the tower, Ethylene Carbonate (EC) crude products are obtained at the bottom of the tower, the light components are discharged from a light component outlet at the top of the tower to a tail gas absorption system, and the Ethylene Carbonate (EC) crude products are discharged from a discharge port IV at the bottom of the tower and enter a de-weighting tower from a feed port V;

(4) removing heavy components:

the Ethylene Carbonate (EC) crude product is uniformly distributed from a feed inlet V by a liquid distributor and then enters a de-weighting tower for de-weighting reaction, the temperature is 87-92 ℃, and the reaction pressure is 0.45-0.75 MPa; the Ethylene Carbonate (EC) primary product is obtained at the top of the tower, the heavy component is obtained at the bottom of the tower, the heavy component is discharged to a heavy component recovery system from a heavy component outlet at the bottom of the tower, the Ethylene Carbonate (EC) primary product is discharged from a discharge hole V at the top of the tower and enters a refining tower from a feed hole VI;

(5) refining:

the Ethylene Carbonate (EC) primary product is fed into a refining tower for refining after being uniformly distributed from a feed inlet VI and a liquid distributor, the temperature is 88-93 ℃, and the reaction pressure is 0.46-0.76 MPa; and Ethylene Carbonate (EC) electronic-grade products are obtained at the bottom of the tower, tail gas at the top of the tower is discharged from a tail gas discharge port at the top of the tower to a tail gas absorption system for recovery, the Ethylene Carbonate (EC) electronic-grade products are discharged from a discharge port VI for recovery, the yield is 99.6%, and the purity is 99.99%.

Example 6:

a method for synthesizing ethylene carbonate or propylene carbonate, using the apparatus of example 2, comprising the steps of:

(1) catalytic synthesis:

CO₂enters a material mixer (1) from a feed inlet I-1, and Ethylene Oxide (EO) enters the material mixer from a feed inlet I-2 with the mixing molar ratio of 1.5:1, and the volume space velocity is 5000h after mixing^-1The feeding amount of the reaction product enters the tubular reactor (2) from the feeding port II (volume), the reaction is carried out under the catalytic action of the catalyst in the tubular reactor, the reaction temperature is 74-79 ℃, the reaction pressure is 0.45-0.75MPa, the product is discharged from the discharging port II and enters the flash tank (3) from the feeding port III; the catalyst used in this example was the resin catalyst obtained in example 4;

(2) flash separation:

and the product enters a flash tank from a feed inlet III for flash evaporation, and the flash evaporation conditions are as follows: at 60 ℃ and under normal pressure; top generation of CO₂And obtaining Propylene Carbonate (PC) reactant at the bottom; CO 2₂From CO₂After being discharged from the discharge port, is pressedAfter being compressed, the compressed material is totally refluxed to a material mixer for recycling; discharging a Propylene Carbonate (PC) reactant from a discharge hole III and feeding the Propylene Carbonate (PC) reactant into a light component removal tower from a feed hole IV;

(3) removing light components:

uniformly distributing a Propylene Carbonate (PC) reactant from a feed inlet IV through a liquid distributor, and then feeding the reactant into a light component removal tower for light component removal reaction at 79-84 ℃ and the reaction pressure of 0.38-0.68 MPa; obtaining light components at the top of the tower, obtaining crude Propylene Carbonate (PC) at the bottom of the tower, discharging the light components from a light component outlet at the top of the tower to a tail gas absorption system for recycling, discharging the crude Propylene Carbonate (PC) from a discharge hole IV at the bottom of the tower and feeding the crude Propylene Carbonate (PC) into a de-heavy tower from a feed inlet V;

(4) removing heavy components:

the crude product of Propylene Carbonate (PC) enters a de-weighting tower for de-weighting reaction after being uniformly distributed from a feed inlet V through a liquid distributor, the temperature is 88-93 ℃, and the reaction pressure is 0.47-0.77 MPa; obtaining a Propylene Carbonate (PC) primary product at the tower top, obtaining a heavy component at the tower bottom, discharging the heavy component from a heavy component outlet at the tower bottom to a heavy component recovery system for recovery, discharging the Propylene Carbonate (PC) primary product from a discharge port V at the tower top and feeding the Propylene Carbonate (PC) primary product into a refining tower from a feed port VI;

(5) refining:

the Propylene Carbonate (PC) primary product is uniformly distributed from a feed inlet VI by a liquid distributor and then enters a refining tower for refining, wherein the temperature is 90-95 ℃, and the reaction pressure is 0.49-0.79 MPa; and obtaining a Propylene Carbonate (PC) electronic grade product at the bottom, discharging tail gas at the top of the tower from the top of the tower to a tail gas absorption system for recycling, discharging the Propylene Carbonate (PC) electronic grade product from a discharge hole VI, and harvesting, wherein the yield is 99.8% and the purity is 99.99%.

The apparatus and method of the present invention are also used for the preparation of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, diphenyl carbonate: dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate and diphenyl carbonate can be produced by feeding Ethylene Carbonate (EC) or Propylene Carbonate (PC) from the feed port I-2 and methanol, ethanol or phenol from the feed port I-1, respectively.

The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (6)

1. The utility model provides a device of synthetic ethylene carbonate or propylene carbonate, includes material blender (1), shell and tube reactor (2), flash tank (3), lightness-removing tower (5), heavy-removing tower (6), refining tower (7) that connect gradually, its characterized in that:

the material mixer (1) is provided with a feed inlet I-1, a feed inlet I-2 and a discharge outlet I, wherein: feed inlet I-1 and can supply CO₂The devices are connected; the inlet I-2 is connected to a device capable of supplying Ethylene Oxide (EO) or Propylene Oxide (PO); the discharge port I is connected with the tubular reactor (2);

the shell and tube reactor (2) is provided with a feed inlet II and a discharge outlet II, wherein: the feed inlet II is connected with a discharge outlet I of the material mixer, and the discharge outlet II is connected with the flash tank (3);

the flash tank (3) is provided with CO at the top of the tower₂The discharge port, lower part is provided with feed inlet III in tower wall one side, and the opposite side middle part is provided with discharge gate III, wherein: CO 2₂The discharge port is connected with a compressor (4), and the outlet of the compressor is connected with a feed port I-1 of the material mixer; the feed inlet III is connected with a discharge outlet II of the tubular reactor; the discharge port III is connected with a lightness-removing column;

take off light tower (5), the middle part is provided with feed inlet IV, the top is provided with the light component export, the bottom is provided with discharge gate IV, wherein: the feed inlet IV is connected with a discharge outlet III of the flash tank, a light component outlet is connected with a tail gas absorption system, and a discharge outlet IV is connected with a de-heavy tower (6);

heavy component removal tower (6), the middle part is provided with feed inlet V, the top is provided with discharge gate V, the bottom is provided with the heavy ends export, wherein: the feed inlet V is connected with a discharge outlet IV of the lightness-removing tower, a heavy component outlet is connected with a heavy component recovery system, and the discharge outlet V is connected with a refining tower (7);

the refining tower (7), the middle part is provided with feed inlet VI, the top is provided with exhaust emission port, the bottom is provided with discharge gate VI, wherein: the feed inlet VI is connected with a discharge port V of the de-weighting tower, a tail gas discharge port is connected with a tail gas absorption system, and the discharge port VI is connected with a device for harvesting Ethylene Carbonate (EC) or Propylene Carbonate (PC).

2. The apparatus of claim 1, wherein: the tubular reactor (2) is integrally of a vertical tubular structure, the cross section of the tubular structure is hexagonal, vertically distributed tubular pipes are uniformly distributed in the tubular reactor, the number of the tubular pipes is 1-100000, the pipe diameter is 1-100mm, and the length is 1-100 m.

3. The apparatus of claim 2, wherein: the tubular reactor (2) is filled with catalyst, or the catalyst is directly filled in a bulk form, namely in an original state; or packing catalyst; or for modular catalyst loading.

4. The apparatus of claim 1, wherein: the light component removing tower is filled with tower plates or structured packing, when the tower plates are filled, the number of layers is less than or equal to 1 and less than or equal to 200, and the distance between the plates is 0.1-1.0 m; when the structured packing is filled, the number of filling sections is more than or equal to 1 and less than or equal to 50, and the height of each section is 1-3 m; and a liquid distributor is arranged at a feed inlet IV of the lightness-removing tower.

5. The apparatus of claim 1, wherein: the weight removal tower is filled with tower plates or structured packing, when the tower plates are filled, the number of layers is less than or equal to 1 and less than or equal to 100, and the distance between the plates is 0.1-0.5 m; when the structured packing is filled, the number of filling sections is more than or equal to 1 and less than or equal to 50, and the height of each section is 1-3 m; and a feed inlet V of the heavy component removing tower is provided with a liquid distributor.

6. The apparatus of claim 1, wherein: the refining tower is filled with column plates or structured packing, when the column plates are filled, the number of layers is less than or equal to 1 and less than or equal to 200, and the distance between the plates is 0.1-0.8 m; when the structured packing is filled, the number of filling sections is more than or equal to 1 and less than or equal to 50, and the height of each section is 1-3 m; and a liquid distributor is arranged at a feed inlet VI of the refining tower.

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