CN120398816A - A method for preparing vinylene carbonate - Google Patents
A method for preparing vinylene carbonateInfo
- Publication number
- CN120398816A CN120398816A CN202410103025.8A CN202410103025A CN120398816A CN 120398816 A CN120398816 A CN 120398816A CN 202410103025 A CN202410103025 A CN 202410103025A CN 120398816 A CN120398816 A CN 120398816A
- Authority
- CN
- China
- Prior art keywords
- group
- catalyst
- oxide
- carbonate
- oxides
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/40—Vinylene carbonate; Substituted vinylene carbonates
-
- 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
- B01J19/24—Stationary reactors without moving elements inside
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种碳酸亚乙烯酯的制备方法。具体地，本发明的制备方法包括如下步骤：将含有氯代碳酸乙烯酯的物料通入含有催化剂的反应床层中使其接触反应，从而得到碳酸亚乙烯酯；其中，所述的催化剂通过以下方法制备：用催化剂原料成型，然后任选地进行煅烧，然后降温从而得到催化剂颗粒。本发明的制备方法成本低、操作简单、转化率高、收率高，有利于工业化生产。The present invention discloses a method for preparing vinylene carbonate. Specifically, the method comprises the following steps: introducing a material containing chloroethylene carbonate into a reaction bed containing a catalyst to cause a contact reaction, thereby producing vinylene carbonate; wherein the catalyst is prepared by forming a catalyst raw material, optionally calcining it, and then cooling it to produce catalyst particles. The method is low in cost, simple to operate, and has high conversion and yield, making it suitable for industrial production.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a preparation method of vinylene carbonate.
Background
It is well known that vinylene carbonate (Vinylene Carbonate, VC) can be used for the production of chemicals, pharmaceutical products and crop protection agents, and in particular also for the production of polymers, coatings and battery dielectrics.
In the prior art, german patent DE 1135452 C2 discloses a catalyst which is cadmium chloride supported on an inert carrier and catalyzes chloroethylene carbonate to undergo HCl elimination reaction to generate vinylene carbonate.
Chinese patent CN 101175742A discloses a HCl elimination reaction of chloroethylene carbonate with zinc chloride supported on an inert carrier as a catalyst and in a completely mixed and stirred catalytic bed. In the method, a fluidized bed reaction device is adopted for reaction, so that the sufficient contact between materials and the catalyst is ensured, however, the reaction reactor is complex, and the product separation cost and the device cost are high. The fixed bed reactor (also called a packed bed reactor) has lower device cost, so the fixed bed reactor is more suitable for industrial production of vinylene carbonate, however, the catalysts adopted in the reactions in the prior art are all in powder form, if the catalysts are placed into a fixed bed reaction device for reaction, the problems of device blockage and the like are easily caused, the service life of the device is influenced, and the contact of materials and the catalysts is easily influenced by adopting a solid phase carrier to load the catalysts, so the reaction efficiency is further influenced.
Chinese patent CN108997301 a also discloses a process for the preparation of vinylene carbonate, which uses triethylamine to react with halogenated ethylene carbonate to remove hydrogen chloride to prepare the target product. However, according to the report of Chinese patent CN114797957A, the ethylene carbonate produced by the reaction is mixed with triethylamine hydrochloride to produce a black sticky substance which is difficult to separate, so that the target product ethylene carbonate is wrapped by the black sticky substance, which is unfavorable for subsequent separation. In addition, the triethylamine with equivalent weight is consumed, and the production cost is high. The technical scheme is only suitable for intermittent production, but not continuous production. In addition, the reaction is a liquid phase reaction, a large amount of solvent is needed, a large amount of three wastes are generated in the production process, and the method is not environment-friendly.
In view of the foregoing, there is a strong need in the art to develop a low cost, high efficiency process for the commercial production of vinylene carbonate.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for efficiently producing vinylene carbonate by a fixed bed or fluidized bed process.
It is an object of the present invention to provide a catalyst which is free of supported materials and which is suitable for use in a fixed bed production process of vinylene carbonate.
It is another object of the present invention to provide a process for preparing vinylene carbonate capable of stably operating for a longer period of time without performing catalyst regeneration.
In a first aspect of the invention, there is provided a process for the preparation of vinylene carbonate comprising the steps of introducing a material containing chloroethylene carbonate into a reaction bed containing a catalyst to effect a contact reaction, thereby obtaining vinylene carbonate;
Wherein the catalyst is prepared by molding the catalyst raw material, optionally calcining, and cooling to obtain catalyst particles, preferably at 100-400 ℃.
In another preferred embodiment, the contact time is 0.5 to 120s.
In another preferred embodiment, the reaction temperature is 300-400 ℃.
In another preferred embodiment, the shaping comprises pulverizing the catalyst materials, mixing thoroughly, and extruding.
In a preferred embodiment, the calcination includes calcination at 90-150 ℃ for 12-48 hours, followed by calcination at 450-550 ℃ for 5-15 hours.
In a preferred embodiment, the reaction is carried out in a reactor filled with a bed of catalyst particles.
In a preferred embodiment, the catalyst has a particle size of 1mm to 5mm, preferably 2mm to 4mm.
In a preferred embodiment, the internal diameter of the cavity in the reactor for filling the catalyst particle bed is 20mm-30mm, and the filling amount of the catalyst is 250-350mL.
In another preferred embodiment, the specific surface area of the catalyst is not less than 200m 2/g, preferably the specific surface area of the catalyst is 200m 2/g-1000m2/g.
In a preferred embodiment, the catalyst is prepared by molding the catalyst raw material, then calcining at 100-150 ℃ for 20-36 hours, calcining at 450-550 ℃ for 8-12 hours, and then cooling to obtain catalyst particles.
In a preferred embodiment, the catalyst feedstock comprises a catalyst selected from group A, or the catalyst feedstock comprises a catalyst selected from group A and a catalyst selected from group B;
group A, oxides of group IIA, sulfates of group IIA, elemental metals of group IB, chlorides of group IB, oxides of group IIB, chlorides of group IIIA, oxides of group IIIB, oxides of group IIIA, oxides of group VB, chlorides of group VIB, oxides of group VIIB, elemental metals of group VIII, oxides of group VIII, chlorides of group VIII, or combinations thereof;
Group B, group IIIA element oxides, group IVA element simple substances, group IVA element oxides, group IVB metal oxides, group VIIB metal oxides or combinations thereof.
In a preferred embodiment, the catalyst feedstock comprises a catalyst selected from group A, or the catalyst feedstock comprises a catalyst selected from group A and a catalyst selected from group B;
Group A, ferroferric oxide, magnesium oxide, copper chloride, silver, gallium chloride, gallium oxide, manganous oxide, zinc oxide, indium oxide, cobalt oxide, ferric oxide, ruthenium, cerium oxide, chromium trichloride, calcium sulfate, palladium oxide, palladium dichloride, nickel oxide, manganese dioxide, vanadium pentoxide, or a combination thereof;
Group B titanium dioxide, manganese dioxide, alumina (preferably gamma-alumina), silica, activated carbon, zirconia, or combinations thereof.
In a preferred embodiment, the catalyst feedstock comprises a catalyst selected from group A, or the catalyst feedstock comprises a catalyst selected from group A and a catalyst selected from group B;
Group A, ferroferric oxide, magnesium oxide, copper chloride, silver, gallium chloride, gallium oxide, manganous oxide, zinc oxide, indium oxide, cobalt oxide, ferric oxide, ruthenium, cerium oxide, or combinations thereof;
Group B titanium dioxide, manganese dioxide, alumina (preferably gamma-alumina), silica, activated carbon, zirconia, or combinations thereof.
In a preferred embodiment, the gaseous or liquid chloroethylene carbonate is not stirred during the contact with the catalyst.
In a preferred embodiment, the chloroethylene carbonate-containing material is formed by introducing a carrier gas preheated to 300-450 ℃ and chloroethylene carbonate into a gasification tank preheated to 300-450 ℃ and gasifying and mixing the chloroethylene carbonate with the carrier gas to form the chloroethylene carbonate-containing material.
In a preferred embodiment, the carrier gas is selected from the group consisting of argon, helium, neon, nitrogen, carbon monoxide, carbon dioxide, hydrogen chloride gas, water vapor, or combinations thereof.
In a preferred embodiment, the chloroethylene carbonate-containing material is formed by introducing chloroethylene carbonate into a gasification tank having an internal pressure of 100Pa-10000Pa and preheated to 300 ℃ to 450 ℃ to gasify the chloroethylene carbonate, thereby forming a chloroethylene carbonate-containing material.
In another preferred embodiment, the chloroethylene carbonate-containing material is formed by introducing chloroethylene carbonate into a gasification tank having an internal pressure of 700Pa-1000Pa and preheated to 300 ℃ to 450 ℃ to gasify the chloroethylene carbonate, thereby forming a chloroethylene carbonate-containing material.
In a preferred embodiment, the method further comprises the step of condensing the product gas stream in a condenser to obtain a crude vinylene carbonate, and preferably, the method further comprises the step of rectifying the crude vinylene carbonate to obtain vinylene carbonate.
In another preferred embodiment, the temperature in the condenser is 50-60 ℃.
In another preferred embodiment, the preparation method comprises the following steps:
S1, forming a catalyst raw material, calcining for 12-48 hours at 90-150 ℃, calcining for 5-15 hours at 450-550 ℃, and cooling to obtain catalyst particles, wherein the particle size of the catalyst particles is 1-5 mm;
s2, filling 250-350mL of catalyst into a reaction bed layer of the reactor;
S3, simultaneously introducing carrier gas preheated to 300-450 ℃ and chloroethylene carbonate into a gasification tank preheated to 300-450 ℃ to gasify the chloroethylene carbonate and mix the chloroethylene carbonate with the carrier gas, so as to form a material gas stream containing the chloroethylene carbonate;
s4, introducing the material gas flow containing chloroethylene carbonate into the reaction bed layer containing the catalyst to perform contact reaction to obtain a product gas flow, wherein the reaction temperature is 300-400 ℃;
s5, introducing the product gas flow into a condenser for condensation, so as to obtain a crude product of vinylene carbonate;
s6, rectifying the crude vinylene carbonate product to obtain vinylene carbonate.
In another preferred embodiment, the preparation method comprises the following steps:
S1, forming a catalyst raw material, calcining for 12-48 hours at 90-150 ℃, calcining for 5-15 hours at 450-550 ℃, and cooling to obtain catalyst particles, wherein the particle size of the catalyst particles is 1-5 mm;
s2, filling 250-350mL of catalyst into a reaction bed layer of the reactor;
S3, introducing chloroethylene carbonate into a gasification tank with the internal pressure of 100Pa-10000Pa and preheating to 300-450 ℃ to gasify the chloroethylene carbonate, thereby forming a material gas flow containing the chloroethylene carbonate;
s4, introducing the material gas flow containing chloroethylene carbonate into the reaction bed layer containing the catalyst to perform contact reaction to obtain a product gas flow, wherein the reaction temperature is 300-400 ℃;
s5, introducing the product gas flow into a condenser for condensation, so as to obtain a crude product of vinylene carbonate;
s6, rectifying the crude vinylene carbonate product to obtain vinylene carbonate.
It is understood that within the scope of the present invention, the above-described technical features of the present invention and technical features specifically described below (e.g., in the examples) may be combined with each other to constitute new or preferred technical solutions. And are limited to a space, and are not described in detail herein.
Drawings
FIG. 1 is a schematic diagram of the structure of a continuous flow reaction apparatus used in examples 1-2 of the present invention.
Detailed Description
After long and intensive research, the applicant has unexpectedly found that a catalyst for producing vinylene carbonate with long service life and good mechanical strength can be prepared by adopting a method of calcining after molding, and the catalyst can be used for producing vinylene carbonate by a fixed bed or fluidized bed process, has low equipment complexity and low production cost and is suitable for industrial production. Based on the above findings, the inventors have completed the present invention.
Terminology
As used herein, the term "group VIII element" refers to Fe, co, ni, ruthenium (Ru), rhodium (Rh), palladium (Pb), osmium (Os), iridium (Ir), platinum (Pt).
As used herein, the term "group IB element" refers to Cu, ag, au.
As used herein, the term "group IIB element" refers to Zn, cadmium (Cd), hg.
As used herein, the term "group IIIB element" refers to scandium (Sc), yttrium (Y), lanthanoids, actinoids, wherein lanthanoids include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu).
As used herein, the term "group IVB element" refers to titanium (Ti), zirconium (Zr), hafnium (Hf).
As used herein, the term "group VB element" refers to vanadium (V), niobium (Nb), tantalum (Ta).
As used herein, the term "group VIB element" refers to chromium (Cr), molybdenum (Mo), tungsten (W).
As used herein, the term "group VIIB element" refers to manganese (Mn), technetium (Tc), rhenium (Re).
As used herein, the term "group IA metal element" refers to lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), francium (Fr).
As used herein, the term "group IIA element" refers to beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), radium (Ra).
As used herein, the term "group IIIA element" refers to boron (B), aluminum (Al), gallium (Ga), indium (In), thallium (Tl).
As used herein, the term "group IVA element" refers to carbon (C), silicon (Si), germanium (Ge), tin (Sn), lead (Pb).
In this context, when the element has a plurality of valence states, the corresponding cation may be in any valence state, for example, the salt formed by Cu may be a copper salt (Cu 2+) or a copper salt (Cu +).
As used herein, the terms "phosphate" and "phosphate compound" are used interchangeably and refer to salts of the cations of the corresponding elements that are formed together with phosphate (PO 4 3-).
As used herein, the terms "sulfate" or "sulfate compound" are used interchangeably and refer to salts of the cations of the corresponding elements that are formed together with sulfate (SO 4 2-).
The terms "carbonate" or "carbonate compound" are used interchangeably and refer to salts formed by the cations of the corresponding elements together with carbonate (CO 3 2-).
The term "oxide" refers to a complex of a corresponding element with oxygen, wherein the element may be in any valence state when the element has multiple stable valence states.
The term "fluoride" refers to a complex of a corresponding element with fluorine, wherein the element may be in any valence state when the element has multiple stable valence states.
The term "chloride" refers to a complex of a corresponding element with chlorine, wherein the element may be in any valence state when the element has multiple stable valence states.
As used herein, the term "elemental carbon" includes any elemental carbon, such as activated carbon, or graphene, among others.
Catalyst preparation suitable for fixed bed preparation process
In the present invention, the preparation of vinylene carbonate is carried out using a fixed bed process, and since a catalyst conventionally used for this type of reaction is in a powder form and cannot be produced in the case of being used for the fixed bed process, the inventors processed the catalyst in this reaction to form a molded structure for use in the fixed bed process.
In the present invention, an exemplary catalyst is prepared by molding a catalyst raw material, then calcining, and then cooling to obtain catalyst particles. Preferably, the calcination includes calcination at 90-130 ℃ for 12-48 hours, followed by calcination at 450-550 ℃ for 5-15 hours.
The catalyst of the invention can be a single-component catalyst or a composite catalyst. In a preferred class of embodiments, the catalyst used in the present invention comprises (or consists of) a catalyst selected from group A, or the catalyst comprises (or consists of) a catalyst selected from group A and a catalyst selected from group B;
group A, oxides of group IIA, sulfates of group IIA, elemental metals of group IB, chlorides of group IB, oxides of group IIB, chlorides of group IIIA, oxides of group IIIB, oxides of group IIIA, oxides of group VB, chlorides of group VIB, oxides of group VIIB, elemental metals of group VIII, oxides of group VIII, chlorides of group VIII, or combinations thereof;
Group B, group IIIA element oxides, group IVA element simple substances, group IVA element oxides, group IVB metal oxides, group VIIB metal oxides or combinations thereof.
In another preferred embodiment, the catalyst comprises a catalyst selected from group A, or the catalyst comprises a catalyst selected from group A and group B;
Group A, ferroferric oxide, magnesium oxide, copper chloride, silver, gallium chloride, gallium oxide, manganous oxide, zinc oxide, indium oxide, cobalt oxide, ferric oxide, ruthenium, cerium oxide, chromium trichloride, calcium sulfate, palladium oxide, palladium dichloride, nickel oxide, manganese dioxide, vanadium pentoxide, or a combination thereof;
Group B titanium dioxide, manganese dioxide, alumina (preferably gamma-alumina), silica, activated carbon, zirconia, or combinations thereof.
In another preferred embodiment, the catalyst comprises a catalyst selected from group A, or the catalyst comprises a catalyst selected from group A and group B;
Group A, ferroferric oxide, magnesium oxide, copper chloride, silver, gallium chloride, gallium oxide, manganous oxide, zinc oxide, indium oxide, cobalt oxide, ferric oxide, ruthenium, cerium oxide, or combinations thereof;
Group B titanium dioxide, manganese dioxide, alumina (preferably gamma-alumina), silica, activated carbon, zirconia, or combinations thereof.
In a preferred embodiment of the present invention, the catalyst starting material comprises a catalyst combination selected from the group consisting of silica, ferric trichloride, barium fluoride, titania, nickel oxide, manganese dioxide, vanadium pentoxide, nickel oxide, zinc chloride, palladium dichloride/gamma-alumina, palladium oxide/silica, calcium sulfate, zinc chloride/silica, chromium trichloride, ferric oxide, gamma-alumina/magnesia, ferric oxide/silica, cupric chloride/activated carbon, silver/silica, magnesium oxide/titania/silica, gallium chloride/silica, gallium oxide/magnesia, manganous oxide/zirconia, zinc oxide/silica, indium oxide/gamma-alumina, cobalt oxide, ferric oxide/silica, silver/silica, ferric oxide, magnesium oxide/titania/silica, ruthenium/activated carbon, manganese dioxide/gamma-alumina/ceria, calcium phosphate, zirconia, or combinations thereof.
In the present invention, a catalyst suitable for a fixed bed process is formed by molding and calcining, thereby obtaining a method capable of producing vinylene carbonate with high efficiency. In a preferred embodiment, when the catalyst is a single component catalyst, the method comprises the steps of:
And (3) molding the raw materials, calcining for 24 hours at 110 ℃, heating to 500 ℃, continuously calcining for 10 hours, and naturally cooling to obtain the modified calcium carbonate. The mechanical strength of the catalyst is greater than 50N.
When the catalyst is a multicomponent catalyst, the method comprises the following steps:
Mixing the raw materials of all the components uniformly, molding, calcining for 24 hours at 110 ℃, heating to 500 ℃, continuously calcining for 10 hours, and naturally cooling to obtain the composite material. The mechanical strength of the catalyst is greater than 50N.
In another preferred embodiment, when the catalyst component contains a feedstock (e.g., ferric chloride, zinc chloride, etc.) having a melting point below 500 ℃, the feedstock is shaped and used directly in a packed fixed bed without calcination.
Reactor for preparing vinylene carbonate by continuous flow reaction
In the following examples, the reaction apparatus used was a continuous flow reaction apparatus, the schematic structure of which is shown in FIG. 1, and it comprises a gasification tank, a reactor, a condenser and a receiving tank.
The gasification tank has at least one inlet for introducing chloroethylene carbonate and carrier gas at the same time, and in some embodiments the inlet for introducing carrier gas is closed off by introducing chloroethylene carbonate directly without introducing carrier gas. The outlet of the gasification tank is communicated with the reactor.
The reactor is provided with at least one inlet and one outlet, the inlet of the reactor is communicated with the outlet of the gasification tank, and the outlet of the reactor is communicated with the condenser. The reactor also has at least one cavity for containing a catalyst. The cavity is cylindrical, the inner diameter is 26mm, and the height is 300mm. Specifically, the reaction used in examples 1-2 was a fixed bed reactor, and in other examples a fluidized bed reactor may be used. Preferably, no stirring means are contained in the reactor.
In a preferred embodiment, the condenser has at least one inlet and one liquid phase outlet, the inlet of the condenser being in communication with the outlet of the reactor and the liquid phase outlet of the condensed gas being in communication with the receiving tank.
In a preferred embodiment, the receiving tank has at least one inlet and one outlet, the inlet of the receiving tank being in communication with the outlet of the condenser, the outlet of the receiving tank being for discharging the collected product.
In a preferred embodiment, both the gasification tank and the reactor have heating and temperature control functions.
In a preferred embodiment, the condenser also has a gas phase outlet for discharging the non-condensed components (mainly HCl). In another preferred embodiment, the non-condensed components are passed into water for further absorption after exiting the gas phase outlet.
THE ADVANTAGES OF THE PRESENT INVENTION
(1) The preparation method of the vinylene carbonate adopts a fixed bed process, and does not need to carry out additional stirring on the catalyst in the reaction process, thereby greatly reducing the cost of a production device, simplifying the production process and avoiding the pulverization phenomenon of the catalyst even if the catalyst runs for a long time.
(2) The invention provides a catalyst suitable for a fixed bed, which is molded and calcined in the process of preparing the catalyst, the obtained catalyst has higher mechanical strength, no pulverization phenomenon occurs in the reaction process, the single service life of the catalyst can reach more than 100 hours, and the cumulative service life after activation can reach more than 1000 hours.
(3) In the prior art, the use of a variety of different elemental metals or complexes as catalysts has been suggested, however, the inventors have found that when a fixed bed process is employed, using a catalyst comprising an oxide as the catalyst can achieve yields far superior to those obtained when other catalyst types are employed.
(4) The novel composite catalyst is adopted, and the side reaction of deep cracking is reduced under the condition that the conversion rate is more than 98%, so that the product yield is Gao Kedi to 84%, and the method is superior to the prior art.
In order to make the technical means, the creation features, the achievement of the purpose and the effect of the present invention easy to understand, the present invention is specifically described below with reference to the embodiments and the drawings. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The experimental procedures, which are not specified in the following examples, are generally carried out under conventional conditions or under conditions recommended by the manufacturer. Percentages and parts are weight percent and parts unless otherwise indicated, each raw material being a commercially available product.
General procedure for the preparation of the catalyst
In various embodiments of the present invention, when the catalyst is a single component catalyst, the catalyst is prepared by the steps of:
i. The raw materials are molded, the raw materials are ground into powder and fully mixed, extruded by a single screw rod and pelletized into spheres;
calcining at 110 ℃ for 24 hours, heating to 500 ℃ and continuing calcining for 10 hours;
And iii, naturally cooling to obtain the product.
When the catalyst is a multicomponent catalyst, the catalyst is prepared by the following steps:
I. mixing the raw materials uniformly, shaping, namely pulverizing the raw materials into powder, fully mixing, extruding by a single screw, and granulating into spheres;
calcining at 110 ℃ for 24 hours, and heating to 500 ℃ for continuous calcining for 10 hours;
III, naturally cooling to obtain the product.
Performance test of catalyst
The mechanical strength of the catalyst was measured according to GB 3635-1983 and the measurement showed that the mechanical strength of the resulting catalyst was greater than 50N.
In addition, the specific surface area of each catalyst prepared by the method is larger than 200m 2/g by using a BET test method.
EXAMPLE 1 preparation of vinylene carbonate
The embodiment provides a preparation method of vinylene carbonate, which comprises the following reaction steps:
The pressure in the gasification tank is controlled between 800Pa and 900Pa, the internal atmosphere is heated to 300 ℃, the chloroethylene carbonate is introduced into the gasification tank at a feed rate of 25mL/min, the chloroethylene carbonate entering the gasification tank is rapidly gasified, and the gasified chloroethylene carbonate is introduced into the reactor at a rate of 25 mL/min. The reactor interior was preheated to 360 ℃ and filled with 300mL of a ferroferric oxide catalyst having an average particle size of 3 mm. Under the action of a catalyst, chloroethylene carbonate is subjected to a cracking reaction to generate vinylene carbonate, and the average residence time of materials in the reactor is 1s. The product gas stream is passed from the reactor and enters a condenser where the product is condensed to 50 ℃ where the product liquefies to a liquid and the liquefied product is passed to a receiving tank for collection to obtain a crude product.
Sampling from the outlet of the condenser when the reaction is carried out for 48h, carrying out GC detection on the sample, wherein the GC spectrogram is shown in the following table, and the reaction conversion rate is still as high as 99.2% when the reaction is carried out for 48h, wherein the content of target product vinylene carbonate in the sample is 91.2%:
< Peak Table >
FID1
And collecting the crude product generated by the reaction within 48 hours, rectifying and purifying, and finally obtaining the vinylene carbonate with the purity of 99.5% in a yield of 76%.
EXAMPLE 2 preparation of vinylene carbonate
The embodiment provides a preparation method of vinylene carbonate, which comprises the following reaction steps:
Nitrogen as a carrier gas is heated to 300 ℃ and then introduced into a gasification tank preheated to 300 ℃ at a rate of 8L/min, and meanwhile, liquid chloroethylene carbonate is introduced into the gasification tank at a rate of 25mL/min, so that the chloroethylene carbonate is rapidly gasified, and the gasified chloroethylene carbonate enters a reactor along with the carrier gas. The reactor interior was preheated to 360 ℃ and the reactor was filled with 300mL of ferroferric oxide having an average particle size of 3 mm. Under the action of a catalyst, chloroethylene carbonate is subjected to a cracking reaction to generate vinylene carbonate, and the average residence time of materials in the reactor is 1.5s. The product gas stream is passed from the reactor and enters a condenser where the product is condensed to 50 ℃ where the product liquefies to a liquid and the liquefied product is passed to a receiving tank for collection to obtain a crude product.
Sampling from the outlet of the condenser when the reaction is carried out for 48h, and carrying out GC detection on the sample, wherein the GC detection results are shown in the following table, the reaction conversion rate is still as high as 99.2% when the reaction is carried out for 48h, and the content of the target product vinylene carbonate in the sample is 85.1%:
< Peak Table
FID1
And collecting the crude product generated by the reaction within 48 hours, rectifying and purifying, and finally obtaining the vinylene carbonate with the purity of 99.5% in 69% yield.
Example 3 screening of catalysts
This example screens catalysts based on examples 1-2. The screening method comprises the following two steps:
Method A:
The pressure in the gasification tank is controlled between 800Pa and 900Pa, the internal atmosphere is heated to 300 ℃, the chloroethylene carbonate is introduced into the gasification tank at a feed rate of 25mL/min, the chloroethylene carbonate entering the gasification tank is rapidly gasified, and the gasified chloroethylene carbonate is introduced into the reactor at a rate of 25 mL/min. The reactor interior was preheated to 360 ℃ and filled with 300mL of catalyst having an average particle size of 3 mm. Under the action of a catalyst, chloroethylene carbonate is subjected to a cracking reaction to generate vinylene carbonate, and the average residence time of materials in the reactor is 1.5s. The product gas flow is led out of the reactor and enters a condenser, the product is condensed to 50 ℃ in the condenser, the product is liquefied into liquid, samples are taken as samples from the outlet of the condenser every 30min, and the reaction conversion rate and the content of vinylene carbonate in the samples are detected. The liquefied product is passed to a receiving tank for collection to give a crude product. And (3) collecting and rectifying crude products collected in 48h of reaction, and purifying to obtain vinylene carbonate.
Method B:
Nitrogen as a carrier gas is heated to 300 ℃ and then introduced into a gasification tank preheated to 300 ℃ at a rate of 8L/min, and meanwhile, liquid chloroethylene carbonate is introduced into the gasification tank at a rate of 25mL/min, so that the chloroethylene carbonate is rapidly gasified, and the gasified chloroethylene carbonate enters a reactor along with the carrier gas. The reactor interior was preheated to 360 ℃ and filled with 300mL of catalyst having an average particle size of 3 mm. Under the action of a catalyst, chloroethylene carbonate is subjected to a cracking reaction to generate vinylene carbonate, and the average residence time of materials in the reactor is 1.5s. The product gas flow is led out of the reactor and enters a condenser, the product is condensed to 50 ℃ in the condenser, the product is liquefied into liquid, samples are taken as samples from the outlet of the condenser every 30min, and the reaction conversion rate and the content of vinylene carbonate in the samples are detected. The liquefied product is passed to a receiving tank for collection to give a crude product. And (3) collecting and rectifying crude products collected in 48h of reaction, and purifying to obtain vinylene carbonate.
The results of the screening are shown in Table 1.
TABLE 1 screening of catalysts
A. in the multicomponent catalyst, each percentage is mass percent;
b. conversion = (1-chloroethylene carbonate content) ×100%, chloroethylene carbonate content = chloroethylene carbonate content determined by GC detection in a sample taken from the condenser outlet when the reaction proceeded to 48 h;
Vc content = vinylene carbonate content determined by GC detection in a sample taken from the condenser outlet at 48h of the reaction;
Vc yield = molar amount of vinylene carbonate obtained after rectifying crude product collected from 0-48 h/molar amount of chloroethylene carbonate consumed by 0-48h, purity of vinylene carbonate obtained after rectifying is not less than 99.5%;
e. catalyst life = time from reaction start to conversion for the first time below 50%;
f. Reactor temperature 300 ℃;
g. Prepared with reference to example 1 of cn200680016151. X;
h. The preparation method is that the raw materials are mixed and then molded, and the molding method is the same as other catalysts, but does not comprise a calcining step.
From the above table, the catalyst effect provided by the application is obviously better than some catalyst effects reported in the prior literature. The catalyst provided by the application has the advantages that the integral mechanical strength is far higher than that of the traditional catalyst using a carrier through steps of molding, calcining and the like, so that the pulverization phenomenon can not occur in the reaction process, and the service life of the catalyst can reach more than 100 hours. As can be seen from entries 25 and 36 of Table 1, the catalyst life and product conversion were significantly improved with the same other conditions, with only the catalyst calcined. This result shows that calcination of the catalyst is effective in improving catalyst life, product conversion, and the amount of VC in the product in the process of the present application.
In terms of catalyst type selection, the applicant found that the effect of chloride is widely deviated because the chloride transition metal chloride catalyst typified by zinc chloride causes an increase in side reactions of deep cracking, and the catalyst is severely carbonized, resulting in failure of the catalytic reaction to proceed smoothly. However, the use of an oxide as a catalyst can achieve yields far superior to those obtained when other catalyst species are employed.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
All documents mentioned in this disclosure are incorporated by reference in this disclosure as if each were individually incorporated by reference. Further, it will be appreciated that various changes and modifications may be made by those skilled in the art after reading the above teachings, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Claims (14)
1. A method for preparing vinylene carbonate is characterized by comprising the following steps of introducing a material containing chloroethylene carbonate into a reaction bed layer containing a catalyst to make the material contact and react, so as to obtain vinylene carbonate;
Wherein the catalyst is prepared by molding the catalyst raw material, optionally calcining, and cooling to obtain catalyst particles, preferably at 100-400 ℃.
2. The method according to claim 1, wherein the calcination comprises calcination at 90 to 150℃for 12 to 48 hours, followed by calcination at 450 to 550℃for 5 to 15 hours.
3. The method of claim 1, wherein the reaction is carried out in a reactor filled with a bed of catalyst particles.
4. The preparation method according to claim 1, wherein the particle size of the catalyst is 1mm-5mm, preferably 2mm-4mm.
5. A method of preparing according to claim 3, wherein the internal diameter of the cavity in the reactor for filling the bed of catalyst particles is 20mm to 30mm and the filling amount of the catalyst is 250 mL to 350mL.
6. The preparation method according to claim 1, wherein the catalyst is prepared by molding a catalyst raw material, then calcining at 100-150 ℃ for 20-36 hours, calcining at 450-550 ℃ for 8-12 hours, and then cooling to obtain catalyst particles.
7. The process according to claim 1, wherein the catalyst raw material comprises a catalyst selected from group A or the catalyst raw material comprises a catalyst selected from group A and a catalyst selected from group B;
group A, oxides of group IIA, sulfates of group IIA, elemental metals of group IB, chlorides of group IB, oxides of group IIB, chlorides of group IIIA, oxides of group IIIB, oxides of group IIIA, oxides of group VB, chlorides of group VIB, oxides of group VIIB, elemental metals of group VIII, oxides of group VIII, chlorides of group VIII, or combinations thereof;
Group B, group IIIA element oxides, group IVA element simple substances, group IVA element oxides, group IVB metal oxides, group VIIB metal oxides or combinations thereof.
8. The process of claim 7 wherein the catalyst feedstock comprises a catalyst selected from group A or the catalyst feedstock comprises a catalyst selected from group A and a catalyst selected from group B;
Group A, ferroferric oxide, magnesium oxide, copper chloride, silver, gallium chloride, gallium oxide, manganous oxide, zinc oxide, indium oxide, cobalt oxide, ferric oxide, ruthenium, cerium oxide, chromium trichloride, calcium sulfate, palladium oxide, palladium dichloride, nickel oxide, manganese dioxide, vanadium pentoxide, or a combination thereof;
Group B titanium dioxide, manganese dioxide, alumina (preferably gamma-alumina), silica, activated carbon, zirconia, or combinations thereof.
9. The process of claim 7 wherein the catalyst feedstock comprises a catalyst selected from group A or the catalyst feedstock comprises a catalyst selected from group A and a catalyst selected from group B;
Group A, ferroferric oxide, magnesium oxide, copper chloride, silver, gallium chloride, gallium oxide, manganous oxide, zinc oxide, indium oxide, cobalt oxide, ferric oxide, ruthenium, cerium oxide, or combinations thereof;
Group B titanium dioxide, manganese dioxide, alumina (preferably gamma-alumina), silica, activated carbon, zirconia, or combinations thereof.
10. The process of claim 1, wherein the gaseous or liquid chloroethylene carbonate is contacted with the catalyst without agitation.
11. The process of claim 1 wherein the chloroethylene carbonate-containing material is formed by introducing a carrier gas preheated to 300 ℃ to 450 ℃ and chloroethylene carbonate into a gasification tank preheated to 300 ℃ to 450 ℃ and gasifying the chloroethylene carbonate and mixing with the carrier gas to form the chloroethylene carbonate-containing material.
12. The method of claim 11, wherein the carrier gas is selected from the group consisting of argon, helium, neon, nitrogen, carbon monoxide, carbon dioxide, hydrogen chloride gas, water vapor, and combinations thereof.
13. The method according to claim 1, wherein the material containing vinyl chloride carbonate is formed by introducing vinyl chloride carbonate into a gasification tank having an internal pressure of 100Pa to 10000Pa and preheated to 300 ℃ to 450 ℃ to gasify the vinyl chloride carbonate, thereby forming the material containing vinyl chloride carbonate.
14. The process according to claim 1, further comprising condensing the product gas stream in a condenser to obtain a crude vinylene carbonate, and preferably rectifying the crude vinylene carbonate to obtain vinylene carbonate.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410103025.8A CN120398816A (en) | 2024-01-24 | 2024-01-24 | A method for preparing vinylene carbonate |
| PCT/CN2024/107107 WO2025156579A1 (en) | 2024-01-24 | 2024-07-23 | Preparation method for vinylene carbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410103025.8A CN120398816A (en) | 2024-01-24 | 2024-01-24 | A method for preparing vinylene carbonate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN120398816A true CN120398816A (en) | 2025-08-01 |
Family
ID=96523540
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410103025.8A Pending CN120398816A (en) | 2024-01-24 | 2024-01-24 | A method for preparing vinylene carbonate |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN120398816A (en) |
| WO (1) | WO2025156579A1 (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3156702A (en) * | 1961-03-28 | 1964-11-10 | Huels Chemische Werke Ag | Method of producing vinylene carbonate |
| DE102005021964A1 (en) * | 2005-05-12 | 2006-11-16 | Lanxess Deutschland Gmbh | Process for the preparation of vinylene carbonate |
| CN1789259A (en) * | 2005-12-14 | 2006-06-21 | 中国科学院山西煤炭化学研究所 | Process for synthesizing vinylene carbonate |
| US9505693B2 (en) * | 2011-10-20 | 2016-11-29 | Akzo Nobel Chemicals International B.V. | Process for the hydrodechlorination of a liquid feed comprising dichloroacetic acid |
| CN113527251B (en) * | 2021-09-01 | 2022-10-21 | 上海如鲲新材料股份有限公司 | A kind of preparation method of vinylene carbonate |
| CN113816937B (en) * | 2021-11-23 | 2022-02-22 | 山东海科创新研究院有限公司 | Method for preparing vinylene carbonate |
| CN117263901B (en) * | 2023-11-21 | 2024-04-05 | 山东海化集团有限公司 | Method for continuously producing vinylene carbonate |
-
2024
- 2024-01-24 CN CN202410103025.8A patent/CN120398816A/en active Pending
- 2024-07-23 WO PCT/CN2024/107107 patent/WO2025156579A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2025156579A1 (en) | 2025-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3520900B2 (en) | Method for producing pentafluoroethane, catalyst for fluorination and method for producing the same | |
| US20240116770A1 (en) | Metal-Supported Material and Ammonia Synthesis Catalyst | |
| US20180273454A1 (en) | Multicomponent heterogeneous catalysts for direct co2 hydrogenation to methanol | |
| US7700068B2 (en) | Method of making NiO and Ni nanostructures | |
| JP2733588B2 (en) | Method for producing catalyst capable of promoting oxidative conversion of methane to higher hydrocarbons | |
| CN116390893A (en) | Ammonia decomposition catalyst | |
| WO2011016759A1 (en) | Support for catalyst of exothermic processes and catalyst prepared thereon | |
| JP2021130100A (en) | Ammonia decomposition catalyst | |
| WO2017184710A1 (en) | Heterogeneous catalyst process and nickel catalyst | |
| CN108654618B (en) | Metal oxide catalyst, method for preparing same, and method for preparing alcohol using same | |
| JP7246101B2 (en) | ELECTRONIC OR HYDRIDE ION SORTING OR DESTROYING COMPOSITIONS, TRANSITION METAL SUPPORTS AND CATALYSTS, AND THEIR RELATED USE | |
| Sancheti et al. | CuO-ZnO-MgO as sustainable and selective catalyst towards synthesis of cyclohexanone by dehydrogenation of cyclohexanol over monovalent copper | |
| WO2022028236A1 (en) | Method for synthesizing difluoromethane by means of gas phase catalysis | |
| CN120398816A (en) | A method for preparing vinylene carbonate | |
| Luidold et al. | Production of niobium powder by magnesiothermic reduction of niobium oxides in a cyclone reactor | |
| Shiozaki et al. | Sustainable Ni/BaTiO3 catalysts for partial oxidation of methane to synthesis gas | |
| EP2894144A1 (en) | Method for producing 7-octenal | |
| WO2018015363A2 (en) | A catalyst composition for direct synthesis of vinyl chloride from ethylene | |
| US20050101806A1 (en) | Process for the catalytic preparation of alkali metal alkoxides | |
| JPH0371174B2 (en) | ||
| JP4048332B2 (en) | Method for producing hydrogen | |
| JP3968532B2 (en) | Method for producing mixed gas of carbon monoxide and hydrogen | |
| JP2544207B2 (en) | Cyclododecanone manufacturing method | |
| JP4671006B2 (en) | Carbon monoxide production method | |
| CN101412654A (en) | Preparation of 1,1-difluoroethane and fluorating catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |