CN104447342A - Method and device for directly preparing diethyl carbonate by adopting one-step method - Google Patents
Method and device for directly preparing diethyl carbonate by adopting one-step method Download PDFInfo
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- CN104447342A CN104447342A CN201410717334.0A CN201410717334A CN104447342A CN 104447342 A CN104447342 A CN 104447342A CN 201410717334 A CN201410717334 A CN 201410717334A CN 104447342 A CN104447342 A CN 104447342A
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- diethyl carbonate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for directly preparing diethyl carbonate by adopting a one-step method. The method comprises the following steps: mixing absolute ethanol, epoxy propane and a double-component metal oxide catalyst and sealing by a cover; charging CO2 until the pressure is 4MPa to 6MPa, heating to the temperature of 150 to 250 DEG C, and then pressurizing CO2 to the pressure of 7MPa to 12MPa; starting a stirring controller, stirring and reacting for at least 2 hours; decompressing a reaction kettle after cooling the reaction kettle to room temperature to obtain diethyl carbonate and receiving diethyl carbonate by using ethanol. The method disclosed by the invention has the advantages of being simple in process and easy to operate by adopting the one-step method to prepare diethyl carbonate; the used reaction raw materials are low in price and easy to obtain; the catalyst is good in stability and quite convenient to separate subsequently; due to the added epoxy propane, the reaction conversion rate is effectively increased.
Description
Technical field
The present invention relates to the preparation method of diethyl carbonate, particularly a kind of adopt single stage method directly to prepare diethyl carbonate method and device.
Background technology
Diethyl carbonate (DEC) is important organic synthesis intermediate, can be used as the oxygenated additive etc. of solvent, tensio-active agent and lithium cell solution additive and gasoline and diesel-fuel, has purposes widely.
DEC has multiple preparation method, mainly comprises: phosgenation, ethanol and CO
2direct synthesis technique, alcoholysis of urea and oxidation carbonylation method etc.Wherein, ethanol and CO
2directly synthesize DEC, raw material is the most cheap and easy to get, and for solution CO
2the Greenhouse effect caused have important meaning, are attractive novel environment-friendly process.This reaction equation is: 2C
2h
5oH+CO
2→ C
2h
5oCOOC
2h
5+ H
2o.
But because this reaction is not thermodynamically preponderated, and with the generation of water byproduct, so reaction conversion ratio is very low.Especially the water generated in reaction process can cause catalyst deactivation and DEC to decompose, and take ethanol as the per pass conversion all lower (<1%) of benchmark.In order to improve the transformation efficiency of reaction, there is investigator to attempt by adding acetonitrile or acetal, by coupling reaction one-step synthesis DEC, achieving higher DEC yield, but adding acetonitrile product complexity, generating many nitrogenous compounds; And acetal synthesis difficulty itself, be all unfavorable for that this reaction scale is amplified.
Present method, by adding propylene oxide (PO), directly synthesizes DEC with carbonic acid gas and ethanol single step reaction.Calculation of thermodynamics shows at CO
2with the Gibbs free energy introducing coupling reaction in the system of ethanol and can greatly reduce reaction, this reaction is made thermodynamically to be easy to realize, and this kind of method coproduction propylene carbonate (PC) and propylene glycol (PG).
Summary of the invention
The object of the invention is for above-mentioned existing problems, provide a kind of adopt single stage method directly to prepare diethyl carbonate method and device, the method carries out coupling reaction by adding propylene oxide (PO), improves ethanol and CO
2directly synthesize the transformation efficiency of DEC.
Technical scheme of the present invention:
Adopt single stage method directly to prepare a method for diethyl carbonate, step is as follows:
1) dehydrated alcohol of 5-50 mL is put in reactor, and add propylene oxide according to the ratio that the volume ratio of propylene oxide and dehydrated alcohol is 1:0.2-5, to add 0.1-0.5 g be mass ratio is simultaneously that the two-component metal oxide catalyst of 1:0.4 seals;
2) CO is passed into
2purging displaces air in reactor, then passes into CO
2gas, to 4-6MPa, is heated to temperature 150-250 oC, then by CO
2be pressurized to reaction pressure 7-12 Mpa;
3) open mixing control device, stirring velocity is 600-800rpm, at least reacts 2h;
4), after reaction terminates, question response still is cooled to room temperature, releases the pressure in reactor, obtains diethyl carbonate and receives product with ethanol.
Described two-component metal catalyzer adopts pickling process preparation: at 60-80 DEG C, first with the nitrate of transition metal for presoma, use NH
3h
2after there is precipitation in O titration, reflux digestion 4-10h, obtained transition metal oxide powder after drying roasting; And then flood 5-24h with alkali-metal nitrate solution, and then through super-dry, 400-800 ° of C roasting, the catalyzer of obtained bimetallic oxide; Described transition metal is Ce, Zr, La or Nu, and basic metal is K, Ba, Na or Mg; The mass ratio of alkali-metal nitrate solution and transition metal oxide powder is 1:0.2-1.
A kind of described employing single stage method directly prepares the device of diethyl carbonate, comprise magnetic agitation autoclave, dioxide bottle, carbon dioxide booster pump and sample reception bottle, magnetic agitation autoclave is sealed vessel, magnetic agitation autoclave is provided with filling tube and agitator, dioxide bottle air outlet is connected with carbon dioxide booster pump inlet mouth by pipeline, carbon dioxide booster pump air outlet enters magnetic agitation autoclave by pipeline and connects and be provided with valve on pipeline, magnetic agitation autoclave air outlet to be connected with sample reception bottle by pipeline and be provided with valve on pipeline.
Reaction mechanism of the present invention:
By selecting ethanol, carbonic acid gas to be raw material, add propylene oxide as couplant simultaneously.By choosing suitable catalyzer, and the processing condition such as suitable temperature of reaction, reaction pressure, in a reactor, achieve propylene oxide and carbon dioxide reaction and generate propylene carbonate, propylene carbonate carries out transesterify Formed diethyl phthalate and propylene glycol two further and reacts and be coupled with ethanol.That is:
Effectively can improve the transformation efficiency of reaction after adding propylene oxide, one way reaction diethyl carbonate yield (calculating with ethanol) brings up to more than 3.7% by 0.1%, improves nearly 40 times.The boiling point of diethyl carbonate is 126 oC simultaneously, and the boiling point of propylene glycol is 214 oC, and the boiling point of propylene carbonate is 242 oC, differs greatly, thus makes later separation more convenient.
Advantage of the present invention is: the method adopts single stage method directly to prepare diethyl carbonate, and technique is simple, processing ease, and reaction raw materials used is cheap and easy to get; Catalyst stability is good, and later separation is also very convenient; Adding of propylene oxide, effectively improve reaction conversion ratio.
Accompanying drawing explanation
Fig. 1 is experimental installation schematic diagram.
In figure: 1. magnetic agitation autoclave, 2. dioxide bottle, 3. carbon dioxide booster pump, 4. sample reception bottle, 5. filling tube, 6. agitator.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail.Preparation in following examples is all by implementing with lower device.
A kind of device adopting single stage method directly to prepare diethyl carbonate, comprise magnetic agitation autoclave 1, dioxide bottle 2, carbon dioxide booster pump 3 and sample reception bottle 4, magnetic agitation autoclave 1 is sealed vessel, magnetic agitation autoclave 1 is provided with filling tube 5 and agitator 6, dioxide bottle 2 air outlet is connected with carbon dioxide booster pump 3 inlet mouth by pipeline, carbon dioxide booster pump 3 air outlet enters magnetic agitation autoclave 1 by pipeline and be provided with valve on pipeline, magnetic agitation autoclave 1 air outlet to be connected with sample reception bottle 4 by pipeline and be provided with valve on pipeline.
Embodiment 1:
Adopt single stage method directly to prepare a method for diethyl carbonate, comprise following steps:
1) dehydrated alcohol of 20 mL is put in reactor, adds 20mL propylene oxide, add the two-component metal oxide catalyst K that 0.3g mass ratio is 1:0.4 simultaneously
2o/ZrO
2, seal;
Described two-component metal catalyzer K
2o/ZrO
2prepared by employing pickling process: at 70 DEG C, is first presoma with zirconium nitrate, uses NH
3h
2after there is precipitation in O titration, reflux digestion 6h, obtained ZrO after drying roasting
2powder; And then flood 6h with potassium nitrate solution, and then through super-dry, 600 ° of C roastings, the catalyzer K of obtained bimetallic oxide
2o/ ZrO
2; Saltpetre and ZrO
2the mass ratio of powder is 1:0.4.
2) CO is passed into
2purging displaces air in reactor, then passes into CO
2gas, to 5MPa, is heated to temperature 150oC, then by CO
2be pressurized to reaction pressure 10Mpa;
3) open mixing control device, stirring velocity is 800rpm, reaction 4h;
4), after reaction terminates, question response still is cooled to room temperature, releases the pressure in reactor, obtains diethyl carbonate and receives product with ethanol.
Product checking:
Adopt Agilent 6890N gas-chromatography to analyze product, capillary chromatographic column is HP-5MS type (30m × 0.32mm × 0.250 μm, Agilent company of the U.S.).Analytical conditions for gas chromatography is: vaporization temperature 200 DEG C, and High Purity Nitrogen is carrier gas, and pressure 40KPa before post, split stream sampling, splitting ratio is 50:1.Column temperature adopts temperature programming: starting temperature 60 DEG C, retains 2min, rises to 150 DEG C with 20 DEG C/min.Be that internal standard substance is analyzed with n-propyl alcohol.Detected result is: the yield of diethyl carbonate (calculating with ethanol) reaches 4.5%, and selectivity is 36%.
Embodiment 2:
Adopt single stage method directly to prepare a method for diethyl carbonate, comprise following steps:
1) dehydrated alcohol of 10 mL is put in reactor, adds 30mL propylene oxide, add the two-component metal oxide catalyst K that 0.1g mass ratio is 1:0.4 simultaneously
2o/CeO
2, seal;
Two-component metal oxide catalyst K
2o/CeO
2preparation method substantially the same manner as Example 1, difference is that transition metal is Ce;
2) CO is passed into
2purging displaces air in reactor, then passes into CO
2gas, to 4MPa, is heated to temperature 150oC, then by CO
2be pressurized to reaction pressure 7Mpa;
3) open mixing control device, stirring velocity is 600rpm, reaction 8h;
4), after reaction terminates, question response still is cooled to room temperature, releases the pressure in reactor, obtains diethyl carbonate and receives product with ethanol.
Product inspection method is identical with embodiment 1.Detected result is: the yield of diethyl carbonate (calculating with ethanol) reaches 8.5%, and selectivity is 41%.
Embodiment 3:
Adopt single stage method directly to prepare a method for diethyl carbonate, comprise following steps:
1) dehydrated alcohol of 30 mL is put in reactor, adds 10mL propylene oxide, add the two-component metal oxide catalyst MgO/Nu that 0.5g mass ratio is 1:0.4 simultaneously
2o
3, seal;
Two-component metal oxide catalyst MgO/Nu
2o
3preparation method substantially the same manner as Example 1, difference is that transition metal is Nu, and basic metal is Mg;
2) CO is passed into
2purging displaces air in reactor, then passes into CO
2gas, to 5MPa, is heated to temperature 150oC, then by CO
2be pressurized to reaction pressure 7Mpa;
3) open mixing control device, stirring velocity is 700rpm, reaction 8h;
4), after reaction terminates, question response still is cooled to room temperature, releases the pressure in reactor, obtains diethyl carbonate and receives product with ethanol.
Product inspection method is identical with embodiment 1.Detected result is: the yield of diethyl carbonate (calculating with ethanol) reaches 3.5%, and selectivity is 52%.
Embodiment 4:
Adopt single stage method directly to prepare a method for diethyl carbonate, comprise following steps:
1) dehydrated alcohol of 30 mL is put in reactor, adds 15mL propylene oxide, add the two-component metal oxide catalyst Na that 0.3g mass ratio is 1:0.4 simultaneously
2o/La
2o
3, seal;
Two-component metal oxide catalyst Na
2o/La
2o
3preparation method substantially the same manner as Example 1, difference is that transition metal is La, and basic metal is Na;
2) CO is passed into
2purging displaces air in reactor, then passes into CO
2gas, to 5MPa, is heated to temperature 200oC, then by CO
2be pressurized to reaction pressure 9Mpa;
3) open mixing control device, stirring velocity is 700rpm, reaction 8h;
4), after reaction terminates, question response still is cooled to room temperature, releases the pressure in reactor, obtains diethyl carbonate and receives product with ethanol.
Product inspection method is identical with embodiment 1.Detected result is: the yield of diethyl carbonate (calculating with ethanol) reaches 6.5%, and selectivity is 39%.
Claims (3)
1. adopt single stage method directly to prepare a method for diethyl carbonate, it is characterized in that step is as follows:
1) dehydrated alcohol of 5-50 mL is put in reactor, and add propylene oxide according to the ratio that the volume ratio of propylene oxide and dehydrated alcohol is 1:0.2-5, to add 0.1-0.5 g be mass ratio is simultaneously that the two-component metal oxide catalyst of 1:0.4 seals;
2) CO is passed into
2purging displaces air in reactor, then passes into CO
2gas, to 4-6MPa, is heated to temperature 150-250 oC, then by CO
2be pressurized to reaction pressure 7-12 Mpa;
3) open mixing control device, stirring velocity is 600-800rpm, at least reacts 2h;
4), after reaction terminates, question response still is cooled to room temperature, releases the pressure in reactor, obtains diethyl carbonate and receives product with ethanol.
2. adopt single stage method directly to prepare the method for diethyl carbonate according to claim 1, it is characterized in that: described two-component metal catalyzer adopts pickling process preparation: at 60-80 DEG C, first with the nitrate of transition metal for presoma, use NH
3h
2after there is precipitation in O titration, reflux digestion 4-10h, obtained transition metal oxide powder after drying roasting; And then with alkali-metal nitrate solution dipping 5-24h, then through super-dry, 400-800 ° of C roasting, the catalyzer of obtained bimetallic oxide; Described transition metal is Ce, Zr, La or Nu, and basic metal is K, Ba, Na or Mg; The mass ratio of alkali-metal nitrate solution and transition metal oxide powder is 1:0.2-1.
3. a described employing single stage method directly prepares the device of diethyl carbonate, it is characterized in that: comprise magnetic agitation autoclave, dioxide bottle, carbon dioxide booster pump and sample reception bottle, magnetic agitation autoclave is sealed vessel, magnetic agitation autoclave is provided with filling tube and agitator, dioxide bottle air outlet is connected with carbon dioxide booster pump inlet mouth by pipeline, carbon dioxide booster pump air outlet enters magnetic agitation autoclave by pipeline and connects and be provided with valve on pipeline, magnetic agitation autoclave air outlet to be connected with sample reception bottle by pipeline and be provided with valve on pipeline.
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|---|---|---|---|
| CN201410717334.0A CN104447342A (en) | 2014-12-03 | 2014-12-03 | Method and device for directly preparing diethyl carbonate by adopting one-step method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410717334.0A CN104447342A (en) | 2014-12-03 | 2014-12-03 | Method and device for directly preparing diethyl carbonate by adopting one-step method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689850A (en) * | 2018-07-01 | 2018-10-23 | 北京化工大学 | A kind of method of cerium zirconium oxide/molecular sieve catalytic synthesizing diethyl carbonate |
| CN110075823A (en) * | 2019-05-30 | 2019-08-02 | 新奥科技发展有限公司 | Preparation method, preparation facilities and the application method of DEC catalyst for synthesizing |
| CN110563585A (en) * | 2019-10-11 | 2019-12-13 | 山东德普化工科技有限公司 | Preparation method of dimethyl carbonate |
-
2014
- 2014-12-03 CN CN201410717334.0A patent/CN104447342A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| BHALCHANDRA M.BHANAGE,ET AL.: "Synthesis of dimethyl carbonate and glycols from carbon dioxide epoxides,and methanol using heterogeneous basic metal oxide catalysts with high activity and selectivity", 《APPLIED CATALYSIS A:GENERAL》 * |
| 张军等: "二氧化碳和乙醇直接合成碳酸二乙酯的研究", 《化学工程》 * |
| 王新等: "环氧丙烷、二氧化碳和甲醇催化合成碳酸二甲酯", 《化学反应工程与工艺》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108689850A (en) * | 2018-07-01 | 2018-10-23 | 北京化工大学 | A kind of method of cerium zirconium oxide/molecular sieve catalytic synthesizing diethyl carbonate |
| CN110075823A (en) * | 2019-05-30 | 2019-08-02 | 新奥科技发展有限公司 | Preparation method, preparation facilities and the application method of DEC catalyst for synthesizing |
| CN110075823B (en) * | 2019-05-30 | 2022-04-12 | 新奥科技发展有限公司 | Preparation method, preparation device and application method of catalyst for DEC synthesis |
| CN110563585A (en) * | 2019-10-11 | 2019-12-13 | 山东德普化工科技有限公司 | Preparation method of dimethyl carbonate |
| CN110563585B (en) * | 2019-10-11 | 2021-02-09 | 山东德普化工科技有限公司 | Preparation method of dimethyl carbonate |
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Application publication date: 20150325 |