KR101472322B1 - Method of preparation of glycerol carbonate by using the metal containing ionic liquid as catalyst - Google Patents
Method of preparation of glycerol carbonate by using the metal containing ionic liquid as catalyst Download PDFInfo
- Publication number
- KR101472322B1 KR101472322B1 KR20140085213A KR20140085213A KR101472322B1 KR 101472322 B1 KR101472322 B1 KR 101472322B1 KR 20140085213 A KR20140085213 A KR 20140085213A KR 20140085213 A KR20140085213 A KR 20140085213A KR 101472322 B1 KR101472322 B1 KR 101472322B1
- Authority
- KR
- South Korea
- Prior art keywords
- glycerol
- catalyst
- glycerol carbonate
- ionic liquid
- metal
- Prior art date
Links
Classifications
-
- 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
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a process for producing glycerol carbonate, which is capable of easily synthesizing glycerol carbonate under a relatively mild reaction condition by using a metal-containing ionic liquid (MIL) as a catalyst, Since the catalyst used in the present invention is a catalyst having both acid-base characteristics and the advantages of maintaining the advantages of the ionic liquid as a coordinated metal complex by precipitation reaction of a metal salt and various 1-alkylimidazoles in a solvent, And the catalyst is advantageous in that glycerol carbonate can be synthesized with a very high yield under relatively mild reaction conditions as compared with other catalysts.
Description
The present invention relates to a process for preparing glycerol carbonate by carbonylation of urea and glycerol using an ionic liquid comprising a metal having high activity and using the same as a catalyst.
With progressive depletion of fossil fuels such as petroleum, natural gas and coal, the world is seeing a significant increase in efforts to use petroleum-based bio-oils as energy and chemical raw materials. Biodiesel, which is an important part of it, is produced by the transesterification reaction between vegetable oil and alcohol, and it is known that 100 kg of glycerol per 1 ton of biodiesel is produced as a by-product. Glycerol is expected to be an important platform material due to the steady increase in demand for biodiesel and the sharp decline in glycerol prices, and the United States Department of Energy (DOE) has also recently introduced glycerol as a future biorefinery biorefinery) as a very important building block. Therefore, it is necessary to develop a technology that can produce high-value-added glycerol derivatives using glycerol which is inexpensive at a low price.
Glycerol is a very important substance that can be converted into various useful compounds such as 1,3-propanediol, epichlorohydrin, acrolein, and glycerol carbonate by various reactions. Among them, glycerol carbonate is widely used as polyurethane foam, coating material, a material for polycarbonate and polyurethane, a solvent for manufacturing cosmetics or pharmaceuticals, a raw material for producing glycidol with high added value, etc., and glycerol carbonate and its derivatives are used in automobiles But also as a solvent for a coating material, an electrolyte for a secondary battery, and the like, and its applicability is very high.
The process for preparing glycerol carbonate from glycerol is to react glycerol with a mixture of glycerol (1) carbon source (phosgene, dialkyl carbonate, alkylene carbonate), (2) urea, and (3) carbon monoxide and oxygen. However, the process using phosgene as a raw material has many problems in operation due to toxicity and corrosiveness of phosgene. In order to solve these problems, there is known a technique using sodium bicarbonate as a catalyst for producing glycerol carbonate by transesterification reaction of ethylene carbonate (hereinafter referred to as 'EC') with glycerol in Patent Document 1 , This process has a disadvantage in that it is necessary to neutralize the catalyst using phosphoric acid or sulfuric acid after completion of the reaction and to perform a distillation operation under reduced pressure in order to recover glycerol carbonate from the reaction mixture. In order to solve these drawbacks, Sugita et al. Developed a process for continuously removing ethylene glycol (EG), which is a product in the presence of aluminum oxide, which is a heterogeneous catalyst, to obtain glycerol carbonate from EC and glycerol in a high yield (Patent Document 3), and Mouloungui et al. Discloses a technique in which a process using Amberlyst A26 resin or zeolite as a catalyst is developed. In addition, in non-patent reference 1, Vieville et al. Have developed a method for producing glycerol carbonate by using supercritical carbon dioxide as a solvent and using strong basic water or zeolite as a catalyst.
In Patent Document 5, Teles et al. Have developed a process for producing glycerol carbonate by directly reacting a mixed gas of carbon monoxide and oxygen with glycerol. However, the above patent discloses that nitrobenzene is used as a solvent and high pressure is required And the reaction time was as long as about 20 hours.
On the other hand, the production of glycerol carbonate by reaction between urea and glycerol is known in Patent Document 4, which has developed a process using zinc sulfate, which is calcined by Claude et al., As a catalyst, It is disadvantageous that high yield can be obtained only by continuously removing ammonia. In addition, it is known that Okutsu Munehisa et al. In Patent Document 6 has developed a method of producing glycerol carbonate which reacts glycerol with urea. However, such a patent discloses a method of producing an alkaline earth metal oxide such as zinc oxide and magnesium oxide The use of a metal oxide as the catalyst increases the yield. Non-Patent Document 2 reports that a catalyst having a balanced Lewis acid-base exhibits excellent properties in the synthesis of glycerol carbonate from urea and glycerol.
As described above, the conventional process for producing glycerol carbonate has difficulty in complicated operations such as using a toxic reactant such as phosgene or carbon monoxide, using vacuum, reduced pressure distillation, supercritical carbon dioxide, etc., And the like.
Therefore, the inventors of the present invention have found that, by using an ionic liquid having various Lewis acid-base properties and various combinations through coordination depending on various kinds of metal salts and organic ligands, The synthesis of glycerol carbonate from urea and glycerol has led to the completion of the present invention.
For reference, the ionic liquid containing the metal according to the present invention not only has the advantage of the ionic liquid but also contains the metal, thereby having the property of Lewis acid-base and controlling the ratio of acid and base.
On the other hand, an ionic liquid is a salt made by combining an organic (nonmetal) anion and an organic (metal) cation, but other salts are present in a liquid state at room temperature rather than melting at a temperature higher than 800 ° C. Ionic liquids have the ability to dissolve many water-like substances as well as they are not volatile, so they do not suffer from the common nasty smell of organic solvents, they do not cause explosion and do not pollute the environment. Conventional chiral catalysts are not only costly but also highly toxic, so they can not be widely used. However, ionic liquids can be used in various combinations of cations and anions depending on the purpose of use. Thus, ionic liquids have unique chemical, physical and electrical properties such as non-volatility, non-flammability, stability to liquids up to 400 ° C, high solubility in organic and inorganic materials, non-coordination to metals and high electrical conductivity It is a new concept of clean medium. Also, many examples of the reaction using this catalyst have been reported.
In order to overcome the above-mentioned problems, the present invention provides a metal complex which is coordinated through a precipitation reaction of a metal salt and a 1-alkylimidazole, and has advantages of an ionic liquid and a Lewis acid- Characterized in that glycerol carbonate is easily produced at a high yield under comparatively mild reaction conditions by using various ionic liquids having the same properties as the catalyst and using the ionic liquid as a catalyst to produce glycerol carbonate And to provide a method to solve the problem.
According to an aspect of the present invention, there is provided a process for carbonylation of glycerol using an ionic liquid catalyst comprising urea and a metal, wherein the carbonylation reaction is carried out at a temperature of 140 to 150 캜, an absolute pressure of 1.1 to 28.0 kPa Or 50 to 150 mL / min nitrogen purge for 4 to 7 hours, and (RIm) 2 MX 2, which is an ionic liquid catalyst containing the metal, The metal salt and the alkylimidazole are dissolved and mixed in ethanol or distilled water solvent, and the mixture is stirred at 45 to 55 ° C for 2 to 3 hours. The resulting precipitate is filtered, sufficiently washed with the used solvent, And then drying the mixture to prepare a glycerol carbonate.
In (RIm) 2 MX 2 ,
R is H, a methyl group, an ethyl group or a hydroxyethyl group,
Im is an imidazole group,
M is Zn, Mg, or Cu,
X is Cl, Br or I;
delete
The present invention by the above-mentioned problem solving means not only maintains the advantage of the ionic liquid having excellent properties as a catalyst but also produces an ionic liquid having both Lewis acid-base properties and synthesizes glycerol carbonate using a catalyst, And the glycerol carbonate can be synthesized with a high yield under relatively mild conditions.
The present invention relates to a method for producing glycerol carbonate using a metal-containing ionic liquid (hereinafter referred to as MIL) as a catalyst, and a method for producing glycerol carbonate from urea and glycerol Here's how to do it.
The present invention is characterized by the use of only glycerol and urea to carry out the carbonylation reaction and no additional solvent is used.
In the present invention, glycerol carbonate is mixed with glycerol and urea at a molar ratio of 1: 1, and the amount of the ionic liquid catalyst to be added is 1 to 2.5 mole / mole of catalyst / glycerol based on the amount of glycerol. If the amount of the added catalyst is less than 1 mole percent, the glycerol and urea may not sufficiently react to leave unreacted glycerol and urea in the reactant. If the amount of the catalyst exceeds 2.5 mole percent The mixture of the reactant and the catalyst is poor and the catalytic activity may decrease.
The reaction conditions for the synthesis of glycerol carbonate are preferably 4 to 7 hours under nitrogen purge conditions at 140 to 150 ° C., 1.1 to 28.0 kPa (absolute pressure) or 50 to 150 mL / min, If the condition is less than the range defined above, there is a fear that the yield of the product is decreased. If the condition is beyond the range defined above, the product may be decomposed or the yield may decrease.
Therefore, it is characterized in that a high yield can be obtained when glycerol carbonate is synthesized using the ionic liquid catalyst prepared according to the present invention.
The metal-containing ionic liquid (MIL) catalyst according to the present invention is (RIm) 2 MX 2 , which is prepared by dissolving a metal salt and an alkylimidazole in a solvent as shown in the following Chemical Formula 1 to coordinate bond.
(Formula 1)
In Formula 1,
R is H, a methyl group, an ethyl group or a hydroxyethyl group,
Im is an imidazole group,
M is Zn, Mg, or Cu,
X is Cl, Br or I;
A specific method for producing (RIm) 2 MX 2 as an ionic liquid (MIL) catalyst according to the present invention will be described below.
First, two solutions are prepared by dissolving zinc chloride (ZnCl 2 ) and two equivalents of N -imidazole ( N- imidazole) as a solvent in ethanol or distilled water, respectively, as one equivalent of a metal salt. Then, the two solutions were mixed and stirred at 45 to 55 ° C for 2 to 3 hours. The precipitated product was filtered, washed sufficiently with ethanol, and vacuum dried to finally produce (HIm) 2 ZnCl 2 .
If the reaction conditions for producing the (Rm) 2 MX 2 catalyst deviate from the reaction conditions defined above, the reaction yield may be lowered.
(CH 3 Im) 2 ZnCl 2 ,, (C 2 H 5 Im) 2 ZnCl 2, (C 2 H 5 -OHIm) 2 ZnCl 2 1- methylimidazole (1-methylimidazole) for the production of a ligand, (HIm) 2 ZnCl 2 was prepared by using 1-ethylimidazole and 1- (2-hydroxyethyl) imidazole, respectively, Respectively.
On the other hand, when the halogen anions other (C 2 H 5 Im) 2 ZnBr 2 and (C 2 H 5 Im) 2 using a metal salt for the production of ZnI 2, each of zinc bromide (ZnBr 2) and the iodide of zinc (ZnI 2) Was prepared in the same manner as (C 2 H 5 Im) 2 ZnCl 2 . (MgCl 2 ) and copper chloride (CuCl 2 ) were used as metal salts as distilled water for the preparation of (C 2 H 5 Im) 2 MgCl 2 and (C 2 H 5 Im) 2 CuCl 2 . Was prepared in the same manner as (C 2 H 5 Im) 2 ZnCl 2 .
The catalyst prepared by the above method not only has the advantages of the ionic liquid but also has acidity and basicity and is excellent in reactivity.
Hereinafter, the present invention will be described in detail with reference to examples. However, the scope of the present invention is not limited to these examples.
(Examples 1 to 4)
The reaction of synthesizing glycerol carbonate by the carbonylation reaction of urea and glycerol was carried out using (RIm) 2 ZnCl 2 catalyst, which is an ionic liquid containing metal, without using a solvent.
(HIm) 2 ZnCl 2 , (CH 3 Im) 2 ZnCl 2 , (C 2 H 5 Im) 2 ZnCl 2 , and (C 2 H 5 -OHIm) 2 ZnCl 2 as the above- The reaction results of the synthesis of glycerol carbonate for 6 hours under the reduced pressure of 140 캜 and 14.7 kPa from 50 mmol urea and 50 mmol glycerol using 0.5 mmol (1 mol% of glycerol), respectively, ].
The metal ion-containing liquid (HIm) 2 ZnCl 2 catalyst prepared in this Example 1 was prepared by first adding 20 mmol of zinc chloride as a metal salt and 40 mmol of N -imidazole as a ligand to 50 mL of ethanol at room temperature Followed by dissolving with stirring, followed by mixing and stirring at 50 ° C for 2 hours. The resulting precipitate was filtered, sufficiently washed with ethanol, dried at 100 ° C under vacuum for one day, and finally (HIm) 2 ZnCl 2 was prepared.
(CH 3 Im) 2 ZnCl 2 , (C 2 H 5 Im) 2 ZnCl 2, (C 2 H 5 -OHIm) 2 preparation of the ZnCl 2 (HIm) 2 the same as the recipe for each (RIm) of ZnCl 2 2 ZnCl < 2 & gt ;, respectively. (CH 3 Im) 2 ZnCl 2 is 1-methyl imidazole of 40 mmol for the production of the sol, (C 2 H 5 Im) ZnCl 2 l of 40 mmol for the production of ethyl 2 imidazole, (C 2 H 5- OHIm) 2 ZnCl 2 , 40 mmol 1- (2-hydroxyethyl) imidazole was used. [Table 1] shows the yield of glycerol carbonate (GC) according to the functional group of (RIm) 2 ZnCl 2 .
As can be seen from the above Table 1, when (C 2 H 5 -OHIm) 2 ZnCl 2 prepared using 1- (2-hydroxyethyl) imidazole as a ligand was used, the yield of the highest glycerol carbonate Respectively.
(Examples 5 to 6)
The catalyst used in this example was synthesized as follows. 20 mmol of zinc bromide and zinc iodide as a metal salt were reacted with 40 mmol of 1-ethylimidazole as a ligand to prepare (C 2 H 5 Im) 2 ZnBr 2 , (C 2 H 5 Im) 2 ZnI 2 .
(C 2 H 5 Im) 2 ZnBr 2 and (C 2 H 5 Im) 2 ZnI 2 were used in place of 0.5 mmol (1 mol% of glycerol), respectively. Are shown in Table 2 below. [Table 2] shows the yield of glycerol carbonate (GC) according to the change of the halogen anion of (C 2 H 5 Im) 2 ZnBr 2 .
As can be seen from the above Table 2, when (C 2 H 5 Im) 2 ZnI 2 prepared by using zinc iodide as a metal salt was used, the yield of the highest glycerol carbonate was shown. However, when the anion of halide was Br, the yield of glycerol carbonate of Cl (Example 3) was not greatly different from that of Cl.
(Examples 7 to 8)
The (C 2 H 5 Im) 2 MgCl 2 and (C 2 H 5 Im) 2 CuCl 2 catalysts, which are the ionic liquids containing the metal prepared in Example 7, were first prepared by dissolving 20 mmol of magnesium chloride, (C 2 H 5 Im) 2 MgCl 2 and (C 2 H 5 Im) 2 (in the same manner as the C 2 H 5 Im) 2 MgCl 2 catalyst used in Example 3 using 50 mL of distilled water as a solvent CuCl 2 , respectively.
Reactivity experiments were carried out under the same conditions as in Example 3 using 0.5 mmol (1 mol% of glycerol) of (C 2 H 5 Im) 2 MgCl 2 and (C 2 H 5 Im) 2 CuCl 2 as catalysts Are shown in Table 3 below. [Table 3] shows the yield of glycerol carbonate (GC) according to the change of metal of (C 2 H 5 Im) 2 MgCl 2 .
As can be seen from the above Table 3, among the ionic liquid catalysts containing metals, the catalyst containing Zn used in Example 3 exhibited the highest catalytic activity.
(Examples 9 to 11)
The reaction was carried out under the same conditions as in Example 3, but the yield of glycerol carbonate was measured by varying the reaction temperature. The results are shown in Table 4 below. [Table 4] shows the yield of glycerol carbonate (GC) according to the change of the reaction temperature.
As can be seen in Table 4, the yield of glycerol carbonate was found to be 72% at a reaction temperature of 140 to 150 ° C, and the selectivity of glycerol carbonate decreased at 160 ° C due to the formation of by- Is significantly low. On the other hand, the reaction did not proceed sufficiently at 130 ° C, and the yield of glycerol carbonate was low.
(Examples 12 to 14)
The reaction was carried out under the same conditions as in Example 3, but the yield of glycerol carbonate was measured by varying the reaction time. The results are shown in Table 5 below. Table 5 below shows the yield of glycerol carbonate (GC) according to the change of reaction time.
As can be seen in Table 5, the reaction time steadily increases from 4 hours to 6 hours. However, when the reaction time was more than 7 hours, the equilibrium reaction was reached.
(Examples 15 to 18)
The reaction was carried out under the same conditions as in Example 3 to determine the degree of decompression and the yield of glycerol carbonate in nitrogen purge to remove ammonia as a by-product during the reaction. The results are shown in Table 6 below . Table 6 below shows the yield of glycerol carbonate (GC) according to the degree of decompression.
As can be seen from Table 6, since the absolute pressure is smaller than the atmospheric pressure of 101.3 kPa, the higher the decompression degree, the more effectively the ammonia can be removed, so the yield of glycerol carbonate increased with the degree of decompression. Also, it can be seen that the yield of glycerol carbonate is as high as that in the decompression state even in the nitrogen purge state. Therefore, it can be seen that the produced ammonia can be effectively removed even in the purge state of nitrogen.
(Comparative Examples 1 and 2)
In this Comparative Example, examples of the results of synthesizing glycerol carbonate in Patent Document 5 and Patent Document 6, which are methods for synthesizing glycerol carbonate from urea and glycerol under similar conditions as in Example 4, are shown in Table 7 below. Table 7 below shows the yield of glycerol carbonate (GC) according to the type of catalyst.
As can be seen from the above Table 7, comparing Comparative Examples 1 and 2 with Example 4 showing the highest yield in the present invention, Example 4 shows a higher yield, And glycerol carbonate from glycerol.
Thus, as shown in the above examples, the ionic liquid catalyst comprising the metal prepared according to the present invention is excellent in reactivity and stability, and it is confirmed that glycerol carbonate can be synthesized at a relatively high yield under relatively mild reaction conditions .
The present invention described above is not necessarily limited to the above-described configuration, and various substitutions, modifications, and changes may be made without departing from the technical spirit of the present invention.
Claims (3)
The carbonylation reaction is carried out at a temperature of 140 to 150 ° C., an absolute pressure of 1.1 to 28.0 kPa or a nitrogen purge of 50 to 150 mL / min for 4 to 7 hours,
(RIm) 2 MX 2, which is an ionic liquid catalyst containing the metal, The metal salt and the alkylimidazole are dissolved and mixed in ethanol or distilled water solvent, and the mixture is stirred at 45 to 55 ° C for 2 to 3 hours. The resulting precipitate is filtered, sufficiently washed with the used solvent, And drying the resulting mixture to prepare a glycerol carbonate.
In (RIm) 2 MX 2 ,
R is H, a methyl group, an ethyl group or a hydroxyethyl group,
Im is an imidazole group,
M is Zn, Mg, or Cu,
X is Cl, Br or I;
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20140085213A KR101472322B1 (en) | 2014-07-08 | 2014-07-08 | Method of preparation of glycerol carbonate by using the metal containing ionic liquid as catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20140085213A KR101472322B1 (en) | 2014-07-08 | 2014-07-08 | Method of preparation of glycerol carbonate by using the metal containing ionic liquid as catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR101472322B1 true KR101472322B1 (en) | 2014-12-24 |
Family
ID=52678748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR20140085213A KR101472322B1 (en) | 2014-07-08 | 2014-07-08 | Method of preparation of glycerol carbonate by using the metal containing ionic liquid as catalyst |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101472322B1 (en) |
-
2014
- 2014-07-08 KR KR20140085213A patent/KR101472322B1/en active IP Right Grant
Non-Patent Citations (4)
| Title |
|---|
| Journal of Catalysis, 2010, 269, 140-149 * |
| Journal of CO2 Utilization, 2014, 6, 69-74 * |
| Korean Chem. Eng. Res., 2013, 51(3), 347-351 * |
| Korean J. Chem. Eng., 2014, 31(6), 972-980 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100478338C (en) | Process for preparing annular carbonate | |
| Zhao et al. | Eco-friendly acetylcholine-carboxylate bio-ionic liquids for controllable N-methylation and N-formylation using ambient CO 2 at low temperatures | |
| Yang et al. | CO2 chemistry: task-specific ionic liquids for CO2 capture/activation and subsequent conversion | |
| KR102073830B1 (en) | Process for preparing carbonate and diol products | |
| Shi et al. | Development of ionic liquids as green reaction media and catalysts | |
| Park et al. | Isolation and characterization of intermediate catalytic species in the Zn-catalyzed glycerolysis of urea | |
| CN110105321A (en) | A kind of method of eutectic ionic liquid catalysis carbon dioxide synthesizing annular carbonate | |
| CN110330459B (en) | Carboxylate ionic liquid and preparation method and application thereof | |
| JP2009503031A (en) | Method for preparing alkylene glycol | |
| US20200171474A1 (en) | Catalysts for the transformation of carbon dioxide and glycerol to formic acid and lactic acid and methods of making the same | |
| Li et al. | Cascade strategy for atmospheric pressure CO2 fixation to cyclic carbonates via silver sulfadiazine and Et4NBr synergistic catalysis | |
| WO2012065879A1 (en) | Process for the preparation of 2-oxo-[1,3] dioxolane-4-carboxylic acid esters | |
| CN108404978B (en) | Application of alkyl quaternary phosphonium salt as catalyst in synthesis of carbonic acid dibasic esters | |
| KR101545257B1 (en) | Method of preparation of glycerol carbonate by using the zirconium containing metal organic frameworks as catalysts | |
| KR101368349B1 (en) | Method of preparation of glycerol carbonate by using the metal organic frameworks as catalysts | |
| KR101472322B1 (en) | Method of preparation of glycerol carbonate by using the metal containing ionic liquid as catalyst | |
| KR20140011937A (en) | Process for preparing n,n'-substituted urea derivatives using cerium dioxide catalyst | |
| Wang et al. | Synthesis of a novel diol-functionalized poly (ethylene glycol)-bridged dicationic ionic liquid and its application in copper-catalyzed amination of aryl halides | |
| KR101416706B1 (en) | Method for preparing glycidol | |
| CN114989015B (en) | Method for preparing dimethyl carbonate by catalyzing transesterification with inorganic salt | |
| KR101199999B1 (en) | Supported Copper Catalysts for Synthesis of Dimethyl Carbonate by Oxidative Carbonylation of Methanol | |
| ES2392468T3 (en) | Procedure for the preparation of dialkyl carbonate | |
| KR20160084738A (en) | Method for preparation of glycerol carbonate by using ZIF-95 as catalyst | |
| KR101684640B1 (en) | A manufacturing method of glycidol using glycerol and glycidol manufactured by the method | |
| CN113563189A (en) | One-step method for efficiently catalyzing CO2Method for converting dimethyl carbonate catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20171204 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20181129 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20191204 Year of fee payment: 6 |