CN113816937B - Method for preparing vinylene carbonate - Google Patents
Method for preparing vinylene carbonate Download PDFInfo
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- CN113816937B CN113816937B CN202111389822.XA CN202111389822A CN113816937B CN 113816937 B CN113816937 B CN 113816937B CN 202111389822 A CN202111389822 A CN 202111389822A CN 113816937 B CN113816937 B CN 113816937B
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- carbonate
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000010949 copper Substances 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- 230000003197 catalytic effect Effects 0.000 claims abstract description 14
- 238000005859 coupling reaction Methods 0.000 claims abstract description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 4
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 42
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 30
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 18
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 7
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical group O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 22
- 239000000047 product Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 239000012018 catalyst precursor Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000011049 filling Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000002378 acidificating effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OYOKPDLAMOMTEE-UHFFFAOYSA-N 4-chloro-1,3-dioxolan-2-one Chemical compound ClC1COC(=O)O1 OYOKPDLAMOMTEE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000000852 hydrogen donor Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- HFJHNGKIVAKCIW-UHFFFAOYSA-N Stearyl monoglyceridyl citrate Chemical compound OCC(O)CO.OC(=O)CC(O)(CC(O)=O)CC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O HFJHNGKIVAKCIW-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- 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
- B01J23/72—Copper
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of vinylene carbonate, belongs to the technical field of organic synthesis, and can solve the technical problems of complex operation steps, long reaction time, easy equipment corrosion, high reaction temperature, low yield and the like of the existing preparation method of vinylene carbonate. The technical scheme comprises the following steps: adding a certain mass of supported copper-based catalyst, ethylene carbonate and a hydrogen acceptor into a reaction device, and carrying out catalytic dehydrogenation-hydrogenation coupling reaction in a nitrogen atmosphere at the temperature of 200-. The invention has the characteristics of simple preparation process, low cost, low reaction temperature, high yield and the like. The method can be applied to the aspect of vinylene carbonate preparation.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of vinylene carbonate.
Background
Vinylene carbonate, also known as 1, 3-dioxol-2-one, has the property of being colorless transparent liquid, and is a novel organic film-forming additive and overcharge protection additive for lithium ion batteries.
At present, ethylene carbonate is mainly prepared by two methods, one is that ethylene carbonate generates monochloroethylene carbonate (CEC) through a photochlorination reaction, then hydrogen chloride is removed under an alkaline environment condition to generate a crude product of the vinylene carbonate, and the crude product is purified to obtain commercial vinylene carbonate (for example, chinese patent applications CN110483471A, CN108864031A, CN106632225A and the like). The method not only relates to toxic and harmful substances such as chlorine, carbon tetrachloride or xanthic chloride, but also has two-step reaction, long reaction time, and serious corrosion to equipment because chlorine atoms are introduced and then removed to form hydrogen chloride; secondly, the ethylene carbonate is dehydrogenated by one step by adopting a catalytic dehydrogenation method to prepare the vinylene carbonate (Chinese patent application CN 1789259A), the reaction needs to be carried out at the temperature of more than 300 ℃ in an inert atmosphere, the highest chromatographic yield is only 60 percent, and the yield is lower, mainly because the activation energy needed by the dehydrogenation of carbon-carbon bonds is higher, and simultaneously, the hydrogen removed from the carbon-carbon double bonds can react again to form the ethylene carbonate structure.
Therefore, how to develop a method for preparing vinylene carbonate with simple preparation process, low cost, low reaction temperature and high yield is the key point for solving the problems.
Disclosure of Invention
The invention provides a preparation method of vinylene carbonate, which is simple in preparation process, low in cost, low in reaction temperature and high in yield, aiming at the technical problems of complex operation steps, long reaction time, high equipment corrosion possibility, high reaction temperature, low yield and the like in the existing preparation method of vinylene carbonate.
In order to achieve the purpose, the invention adopts the technical scheme that:
the preparation method of the vinylene carbonate comprises the following steps:
adding a certain mass of supported copper-based catalyst, ethylene carbonate and a hydrogen acceptor into a reaction device, and carrying out catalytic dehydrogenation-hydrogenation coupling reaction in a nitrogen atmosphere at the temperature of 200-;
the hydrogen acceptor is selected from any one of furfural or furan.
Preferably, the supported copper-based catalyst is an acidic carrier, a basic carrier or a mixture of an acidic carrier and a basic carrier.
Preferably, the acidic carrier is selected from any one or more of aluminum oxide, zinc oxide or iron oxide.
Preferably, the basic support is selected from either or both of lanthanum oxide and magnesium oxide.
Preferably, the reaction device is a continuous fixed bed reactor or a batch process reaction kettle.
Preferably, the feeding ratio of the ethylene carbonate to the hydrogen acceptor is (2: 1) - (1: 1).
Preferably, furfuryl alcohol and tetrahydrofuran are also produced by the method for producing vinylene carbonate.
Preferably, the yield of furfuryl alcohol is 40-70% and the yield of tetrahydrofuran is 20-40%.
The invention also provides vinylene carbonate prepared by the vinylene carbonate preparation method in any one of the preferable technical schemes, and the yield of the vinylene carbonate is 75-90%.
Compared with the prior art, the invention has the advantages and positive effects that:
1. the method for preparing the vinylene carbonate provided by the invention adopts a supported copper-based catalyst, the vinylene carbonate is used as a hydrogen donor, furfural or furan is used as a hydrogen acceptor, and the vinylene carbonate as a target product is prepared by a one-step method of catalytic dehydrogenation-hydrogenation coupling reaction;
2. according to the preparation method of the vinylene carbonate, the vinylene carbonate can be prepared, and two products with high added values, namely furfuryl alcohol and tetrahydrofuran, can also be prepared;
3. the preparation method of vinylene carbonate provided by the invention has the characteristics of simple preparation process, short reaction time, no need of adding toxic and harmful substances, low cost and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a preparation method of vinylene carbonate, which comprises the following steps:
adding a certain mass of supported copper-based catalyst, ethylene carbonate and a hydrogen acceptor into a reaction device, and carrying out catalytic dehydrogenation-hydrogenation coupling reaction in a nitrogen atmosphere at the temperature of 200-;
the hydrogen acceptor is selected from any one of furfural or furan.
In the above embodiment, a novel method for preparing vinylene carbonate is provided, the method uses a supported copper-based catalyst, the vinylene carbonate is used as a hydrogen donor, and a hydrogen acceptor is added to perform a catalytic dehydrogenation-hydrogenation coupling reaction one-step method to prepare the vinylene carbonate as a target product.
In the preferred embodiment described above, furfural or furan were chosen as the hydrogen acceptor for the reasons: the two raw materials can be subjected to reactions such as halogenation, sulfonation, hydrogenation and the like, are commonly used in organic synthesis reactions, and have higher added value when being used as a hydrogen acceptor for synthesizing furfural or furan.
In addition, the catalyst adopted in the embodiment of the invention is a cheap and easily-obtained supported copper-based catalyst, and the dehydrogenation-hydrogenation coupling reaction is catalyzed by adopting a continuous method or a batch method, so that the desorbed hydrogen can directly perform hydrogenation reaction with another raw material under the condition of ensuring higher yield of a target product, and a product with high added value is obtained.
In a preferred embodiment, the supported copper-based catalyst is an acidic carrier, a basic carrier or a mixture of an acidic carrier and a basic carrier.
In a preferred embodiment, the acidic carrier is selected from any one or more of aluminum oxide, zinc oxide or iron oxide.
In a preferred embodiment, the basic support is selected from either or both lanthanum oxide and magnesium oxide.
In a preferred embodiment, the reaction device is a continuous fixed bed reactor or a batch process reaction kettle.
In a preferred embodiment, the feeding ratio of the ethylene carbonate to the hydrogen acceptor is (2: 1) - (1: 1).
In the above preferred embodiment, the ethylene carbonate to hydrogen acceptor feed ratio is defined as (2: 1) - (1: 1) for the reason that: in order to balance the yield of vinylene carbonate with the yields of two high value-added products on the basis of ensuring that the yield of vinylene carbonate is higher and enable the comprehensive yield of the products to reach an ideal state, a large number of screening experiments prove that the yield of vinylene carbonate and the yields of the two high value-added products can be well balanced when the feeding ratio of the vinylene carbonate to a hydrogen acceptor is (2: 1) - (1: 1).
In a preferred embodiment, furfuryl alcohol and tetrahydrofuran are also produced using the vinylene carbonate production process.
In a preferred embodiment, the yield of furfuryl alcohol is 40-70% and the yield of tetrahydrofuran is 20-40%.
The invention also provides vinylene carbonate, which is prepared by the vinylene carbonate preparation method in any one of the preferred embodiments, and the yield of the vinylene carbonate is 75-90%.
In order to more clearly describe the method for preparing vinylene carbonate provided by the embodiment of the present invention in detail, the following description will be given with reference to the specific embodiment.
Example 1
The embodiment provides a preparation method of vinylene carbonate, which specifically comprises the following steps:
(1) preparation of supported copper-based catalyst:
preparing 1mol/L copper nitrate aqueous solution, and then adding 500-mesh Al into the aqueous solution2O3Uniformly stirring the powder to prepare solution A; preparing 1mol/L sodium carbonate aqueous solution to prepare solution B, adding the solution B into the solution A by using a constant-pressure dropping funnel, filtering to obtain a precipitate after all the solution is dropped, and obtaining a catalyst precursor with the diameter of 5mm by using a bar extruder; drying the catalyst precursor at 120 ℃, roasting at 500 ℃ for 5h, introducing nitrogen-hydrogen (hydrogen volume accounts for 5%) mixed gas into a tubular furnace, and reducing at 400 ℃ for 3h to obtain Cu/Al2O3A catalyst wherein the Cu loading is 10 wt%.
(2) Preparation of vinylene carbonate:
catalytic reaction is carried out by adopting a continuous fixed bed reactor, and 3g of Cu/Al is added203Filling a catalyst into a reactor, introducing nitrogen, preparing a mixed raw material with the molar ratio of ethylene carbonate to furfural being 1.2:1 at the flow rate of 10L/h, adding the mixed raw material into the reactor, performing catalytic dehydrogenation-hydrogenation coupling reaction at the flow rate of 20g/h at the temperature of 260 ℃, taking the material every 2h, performing gas chromatography test, and detecting the yield of vinylene carbonate and furfuryl alcohol.
Example 2
The embodiment provides a preparation method of vinylene carbonate, which specifically comprises the following steps:
(1) preparation of supported copper-based catalyst:
preparing 1mol/L copper nitrate aqueous solution, and then adding 500-mesh La into the aqueous solution2O3Uniformly stirring the powder to prepare solution A; preparing 1mol/L sodium carbonate aqueous solution to prepare solution B, adding the solution B into the solution A by using a constant-pressure dropping funnel, filtering to obtain a precipitate after all the solution is dropped, and obtaining a catalyst precursor with the diameter of 5mm by using a bar extruder; drying the catalyst precursor at 120 ℃, roasting at 500 ℃ for 5h, introducing nitrogen-hydrogen (hydrogen volume accounts for 5%) mixed gas into a tubular furnace, and reducing at 400 ℃ for 3h to obtain Cu/La2O3A catalyst wherein the Cu loading is 15 wt%.
(2) Preparation of vinylene carbonate:
the reaction kettle is used as a reactor for reaction, and 5g of Cu/La is filled at the bottom of the kettle2O3The method comprises the steps of preparing 100g of a mixed material of ethylene carbonate and furfural with a molar ratio of 1.2:1, placing the mixed material into a reaction kettle, sealing the kettle, filling nitrogen, replacing for 3 times, carrying out catalytic dehydrogenation-hydrogenation coupling reaction at a reaction temperature of 220 ℃ for 3 hours, after the reaction is finished, cooling the kettle to room temperature, and detecting the yield of vinylene carbonate and furfuryl alcohol by adopting a gas chromatography test.
Example 3
The embodiment provides a preparation method of vinylene carbonate, which specifically comprises the following steps:
(1) preparation of supported copper-based catalyst: the preparation method is the same as example 2.
(2) Preparation of vinylene carbonate:
carrying out catalytic reaction by adopting a fixed bed reactor, and adding 3g of Cu/La2O3Filling the materials into a reactor, introducing nitrogen at the flow rate of 10L/h, preparing a mixed raw material with the molar ratio of ethylene carbonate to furfural of 1.2:1, adding the mixed raw material into the reactor at the flow rate of 20g/h, carrying out catalytic dehydrogenation-hydrogenation coupling reaction at the temperature of 300 ℃, taking the materials every 2h, carrying out gas chromatography test, and detecting the yield of vinylene carbonate and furfuryl alcohol.
Example 4
The embodiment provides a preparation method of vinylene carbonate, which specifically comprises the following steps:
(1) preparation of supported copper-based catalyst:
preparing 1mol/L copper nitrate aqueous solution, and then adding 500-mesh La into the aqueous solution2O3And Al2O3Uniformly stirring the powder to prepare solution A; preparing 1mol/L sodium carbonate aqueous solution to prepare solution B, adding the solution B into the solution A by using a constant-pressure dropping funnel, filtering to obtain a precipitate after all the solution is dropped, and obtaining a catalyst precursor with the diameter of 5mm by using a bar extruder; drying the catalyst precursor at 120 ℃, roasting at 500 ℃ for 5h, introducing nitrogen-hydrogen (hydrogen volume accounts for 5%) mixed gas into a tubular furnace, and reducing at 400 ℃ for 3h to obtain Cu/Al2O3-La2O3A catalyst wherein the Cu loading is 5 wt%.
(2) Preparation of vinylene carbonate:
the reaction kettle is used as a reactor for reaction, and 5g of Cu/Al is filled at the bottom of the kettle2O3-La2O3Catalyst, preparing 100g of mixed material of ethylene carbonate and furan with the molar ratio of 1.6:1, placing the mixed material into a reaction kettle, sealing the kettle, filling nitrogen, replacing for 3 times, wherein the nitrogen pressure in the kettle is 0.1MPa, carrying out catalytic dehydrogenation-hydrogenation coupling reaction at the reaction temperature of 240 ℃, the reaction time is 3 hours, finishing the reaction, cooling the kettle to room temperature, and adopting gas chromatographyAnd testing and detecting the yield of vinylene carbonate and tetrahydrofuran.
Example 5
The embodiment provides a preparation method of vinylene carbonate, which specifically comprises the following steps:
(1) preparation of supported copper-based catalyst: the preparation method is the same as example 4.
(2) Preparation of vinylene carbonate:
catalytic reaction is carried out by adopting a fixed bed reactor, and 5g of Cu/Al is added203-La2O3Filling the mixture into a reactor, introducing nitrogen at the flow rate of 3L/h, preparing a mixed raw material with the molar ratio of ethylene carbonate to furan of 1.8:1, adding the mixed raw material into the reactor at the flow rate of 15g/h, carrying out catalytic dehydrogenation-hydrogenation coupling reaction at the reaction temperature of 300 ℃, taking the material every 2h, carrying out gas chromatography test, and detecting the yield of vinylene carbonate and tetrahydrofuran.
Example 6
The embodiment provides a preparation method of vinylene carbonate, which specifically comprises the following steps:
(1) preparation of supported copper-based catalyst: the preparation method is the same as example 4.
(2) Preparation of vinylene carbonate:
the reaction kettle is used as a reactor for reaction, and 5g of Cu/Al is filled at the bottom of the kettle2O3-La2O3Preparing 120g of mixed material with the molar ratio of ethylene carbonate to furan being 2:1, placing the mixed material into a reaction kettle, sealing the kettle, filling nitrogen, replacing for 3 times, carrying out catalytic dehydrogenation-hydrogenation coupling reaction under the condition that the nitrogen pressure in the kettle is 0.1MPa and the reaction temperature is 200 ℃, wherein the reaction time is 2 hours, after the reaction is finished, detecting the yield of the vinylene carbonate and the tetrahydrofuran by adopting a gas chromatography test when the temperature of the kettle is reduced to room temperature.
Comparative example 1
The comparative example provides a preparation method of vinylene carbonate, which specifically comprises the following steps:
(1) preparation of supported copper-based catalyst:
preparing 1mol/L nitric acidAn aqueous copper solution, to which 500 mesh La was then added2O3And Al2O3Uniformly stirring the powder to prepare solution A; preparing 1mol/L sodium carbonate aqueous solution to prepare solution B, adding the solution B into the solution A by using a constant-pressure dropping funnel, filtering to obtain a precipitate after all the solution is dropped, and obtaining a catalyst precursor with the diameter of 5mm by using a bar extruder; drying the catalyst precursor at 120 ℃, roasting at 500 ℃ for 5h, introducing nitrogen-hydrogen (hydrogen volume accounts for 5%) mixed gas into a tubular furnace, and reducing at 400 ℃ for 3h to obtain Cu/Al2O3-La2O3A catalyst wherein the Cu loading is 5 wt%.
(2) Preparation of vinylene carbonate:
the reaction kettle is used as a reactor for reaction, and 5g of Cu/Al is filled at the bottom of the kettle2O3-La2O3The method comprises the steps of preparing 100g of a mixed material with a molar ratio of ethylene carbonate to furan of 3:1, placing the mixed material into a reaction kettle, sealing the kettle, filling nitrogen, replacing for 3 times, wherein the nitrogen pressure in the kettle is 0.1MPa, carrying out catalytic dehydrogenation-hydrogenation coupling reaction at the reaction temperature of 240 ℃, the reaction time is 3 hours, after the reaction is finished, cooling the kettle to room temperature, and detecting the yield of vinylene carbonate and tetrahydrofuran by adopting a gas chromatography test.
Comparative example 2
The comparative example provides a preparation method of the traditional vinylene carbonate, which comprises the following specific steps:
the method comprises the steps of accurately weighing 300g of chlorinated ethylene carbonate, 900g of dimethyl carbonate (water content is less than 500 ppm), 0.9g of polymerization inhibitor BHT and 242g of triethylamine (water content is less than 500 ppm) in a ventilation cabinet, firstly adding the chlorinated ethylene carbonate, the dimethyl carbonate and the polymerization inhibitor into a 2L three-neck flask with mechanical stirring and backflow, placing the flask in a water bath, when the flask is heated to the reaction temperature, dripping the triethylamine into the three-neck flask through a constant-pressure dropping funnel (keeping 2-3 drops/s and ensuring that the dripping can be finished within 2 hours), after the dripping of the triethylamine is finished, controlling the reaction temperature to be constant at the designated temperature, preserving the temperature for 2-3 hours, and sampling and performing control detection in a gas chromatography.
Comparative example 3
The comparative example provides a preparation method of vinylene carbonate, which specifically comprises the following steps:
(1) preparation of the catalyst:
Al2O3crushing and sieving the carrier, selecting 20-40 meshes, firstly activating at 500 ℃ for 2h, and loading the iron catalyst on Al2O3On a support to obtain Fe2O3With Al2O3The mass ratio of (A) to (B) is 1: 4.
(2) Preparation of vinylene carbonate:
adding a catalyst into a fixed bed reactor, continuously introducing ethylene carbonate into a miniature fixed bed reactor at the airspeed of 2 g/h.mlcat. by using a trace sample injection pump, wherein the reaction temperature is 360 ℃, the reaction pressure is 0.2MPa, simultaneously introducing nitrogen as a carrier gas and a protective gas for reaction, collecting a reaction product by using a condensing device, analyzing by using gas chromatography, and detecting the yield of the vinylene carbonate.
Yield determination of related products
The yield of vinylene carbonate, furfuryl alcohol and tetrahydrofuran prepared in the above examples and comparative examples was determined by gas chromatography, and the specific results were as follows:
TABLE 1 results of yield measurement of related products obtained in examples 1 to 6 and comparative examples 1 to 3
As can be seen from the above table, the yield of vinylene carbonate prepared by increasing the molar ratio of ethylene carbonate to furan by using the method provided in comparative example 1 is reduced to 60%, the yield of vinylene carbonate prepared by using the methods of comparative examples 2-3 is not high, and high value-added products such as furfuryl alcohol and tetrahydrofuran are not generated in the preparation process, while the yield of vinylene carbonate prepared by using the method provided in the embodiment of the present invention is high, up to 90%, and two high value-added products of furfuryl alcohol and tetrahydrofuran can be prepared.
Further, the preparation method provided in comparative example 1 has an unsatisfactory yield of the vinylene carbonate due to an excessively high molar ratio of the vinylene carbonate to furan, the preparation method provided in comparative example 2 is a conventional two-step reaction, toxic and harmful substances such as chloroethylene carbonate are used in the preparation process, and thus, the preparation method has the disadvantages of long reaction time, high possibility of causing corrosion of equipment, more solid wastes, poor treatment and the like, and the adoption of the toxic substances also fails to meet the current requirements of green chemistry, the preparation method adopted in comparative example 3 is a reaction for preparing vinylene carbonate by further dehydrogenating the vinylene carbonate, although the reaction is a one-step reaction, the required reaction temperature is high (generally above 300 ℃), and the yield of the vinylene carbonate is not high, and the preparation method provided in the embodiment of the present invention adopts a supported copper-based catalyst, the method can improve the yield of the vinylene carbonate, reduce the reaction temperature, reduce the production cost of the vinylene carbonate, and simultaneously can prepare two products with high added values, namely furfuryl alcohol and tetrahydrofuran. Therefore, the preparation process provided by the invention has more advantages in the aspects of production cost and product performance.
Claims (5)
1. The preparation method of the vinylene carbonate is characterized by comprising the following steps:
adding a certain mass of supported copper-based catalyst, ethylene carbonate and a hydrogen acceptor into a reaction device, and carrying out catalytic dehydrogenation-hydrogenation coupling reaction in a nitrogen atmosphere at the temperature of 200-;
the hydrogen acceptor is selected from any one of furfural or furan, and the carrier of the supported copper-based catalyst is La2O3、Al2O3。
2. The method according to claim 1, wherein the reaction apparatus is a continuous fixed bed reactor or a batch reactor.
3. The method for producing vinylene carbonate according to claim 1, wherein the feeding ratio of the vinylene carbonate to the hydrogen acceptor is (2: 1) - (1: 1).
4. The method for producing vinylene carbonate according to claim 1, wherein furfuryl alcohol and tetrahydrofuran are also produced.
5. The method for producing vinylene carbonate according to claim 4, wherein the yield of furfuryl alcohol is 40-70% and the yield of tetrahydrofuran is 20-40%.
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| KR1020237032750A KR20230145491A (en) | 2021-11-23 | 2022-06-15 | Method for producing vinylene carbonate |
| PCT/CN2022/098802 WO2022258072A1 (en) | 2021-11-23 | 2022-06-15 | Method for preparing vinylene carbonate |
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| CN116375678B (en) * | 2023-02-21 | 2024-03-22 | 山东孚日新能源材料有限公司 | Synthesis method of vinylene carbonate |
| CN116693494B (en) * | 2023-05-22 | 2023-12-08 | 大连华一锂电科技有限公司 | Synthesis method of vinylene carbonate |
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| CN109569604A (en) * | 2019-01-18 | 2019-04-05 | 中国科学院青岛生物能源与过程研究所 | A kind of copper-based catalysts and preparation method thereof and the purposes in furfural hydrogenation catalysis |
| CN109731596A (en) * | 2019-01-18 | 2019-05-10 | 厦门大学 | A kind of copper-based method for preparing catalyst of the modification of Furfural hydrogenation to furfural alcohol |
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| US3457279A (en) * | 1964-10-21 | 1969-07-22 | Jefferson Chem Co Inc | Vinylene carbonate production |
| 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 |
| CN101161647A (en) * | 2007-11-26 | 2008-04-16 | 中国海洋石油总公司 | Preparation method of vinylene carbonate for lithium ion-cell |
| CN104327037A (en) * | 2014-10-16 | 2015-02-04 | 荣成青木高新材料有限公司 | Vinylene carbonate preparation method |
| CN107501231B (en) * | 2017-07-25 | 2018-08-14 | 苏州华一新能源科技有限公司 | A kind of preparation method of vinylene carbonate |
| CN110483471A (en) * | 2019-09-08 | 2019-11-22 | 淮安瀚康新材料有限公司 | A kind of synthetic method of vinylene carbonate |
| CN111072624B (en) * | 2019-12-16 | 2020-12-15 | 苏州华一新能源科技有限公司 | Preparation method and application of vinylene carbonate |
| CN110981848A (en) * | 2019-12-20 | 2020-04-10 | 泰兴华盛精细化工有限公司 | Production process 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 |
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