CN114957009B - Method for synthesizing glycerol carbonate - Google Patents
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- CN114957009B CN114957009B CN202210643221.5A CN202210643221A CN114957009B CN 114957009 B CN114957009 B CN 114957009B CN 202210643221 A CN202210643221 A CN 202210643221A CN 114957009 B CN114957009 B CN 114957009B
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- JFMGYULNQJPJCY-UHFFFAOYSA-N 4-(hydroxymethyl)-1,3-dioxolan-2-one Chemical compound OCC1COC(=O)O1 JFMGYULNQJPJCY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004202 carbamide Substances 0.000 claims abstract description 24
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229920001661 Chitosan Polymers 0.000 claims description 10
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 101100208039 Rattus norvegicus Trpv5 gene Proteins 0.000 description 6
- 238000010000 carbonizing Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002815 homogeneous catalyst Substances 0.000 description 3
- 238000010813 internal standard method Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910018580 Al—Zr Inorganic materials 0.000 description 1
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 101150019148 Slc7a3 gene Proteins 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 etc.) Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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)
Abstract
The invention discloses a method for synthesizing glycerol carbonate, belonging to the technical field of synthesizing glycerol carbonate by urea alcoholysis. Urea and glycerin with the mol ratio of 1.5:1 are used as raw materials; the preparation method comprises the steps of adding raw materials and a catalyst into a container, placing the container in a constant-temperature oil bath, and reacting for 6-8 h at 105-125 ℃ to obtain the glycerol carbonate. The catalyst used in the invention is a metal-free catalytic system, is a high-efficiency catalyst without adding metal for the first time in the system, and has the advantages of high reaction efficiency, low reaction temperature, good circulation stability, easy separation from the reaction system and the like.
Description
Technical Field
The invention belongs to the technical field of synthesizing glycerol carbonate by urea alcoholysis, and particularly relates to a method for synthesizing glycerol carbonate by taking urea and glycerol as raw materials through a urea alcoholysis process.
Background
The Glycerol Carbonate (GC) is used as a special biochemical substance and has the characteristics of high boiling point, low volatility, low freezing point, strong polarity, no toxicity, biodegradability and the like. Is widely applied to the fields of food, medicine, cosmetics, textile, paint, plastics, machinery, military, aviation, aerospace, integrated circuits, new energy and the like. Examples of the method for synthesizing glycerol carbonate include phosgene method, CO oxidative carbonylation method, transesterification method, glycerol and urea carbonylation method and CO 2 Conversion process. Among them, glycerolysis using glycerol and urea as raw materials is considered as a process with high molecular efficiency. Ammonia gas is a byproduct generated in the alcoholysis process of urea, and can also be used as a raw material for synthesizing urea, and is considered as a green process for synthesizing glycerol carbonate.
During the synthesis, it is important to select the catalyst.
The catalyst used for synthesizing the glycerol carbonate from the glycerol and the urea is mainly the following: zinc-based catalyst (Co) 3 O 4 ZnO and Co 50 Zn 50 -350 composite material, porous ZnO, zinc-aluminum composite material, etc.), magnesium-based catalyst (MgO, au-Pd-MgO, HT (Mg/Zn/Al) and Mg-Al-Zr), tungsten-based catalyst (SW 21 ，WO 3 /TiO 2 Ionic liquid catalyst (MPR [ pmim ]][Cl]+ZnO，PS-(Im) 2 ZnBr 2 Q-MMTs and [ PS- (Im) 2 MX 2 ]) And other catalysts (gamma-zirconium phosphate, la 2 O 3 ，La 2 Cu 0.5 Fe 0.5 O 4 Etc.).
These catalysts can be largely classified into two types, homogeneous catalysts and heterogeneous catalysts. Homogeneous catalysts have relatively high catalytic efficiency and high reaction rates. But has the problem of difficult separation of the product and the catalyst, and greatly increases the production cost. Heterogeneous catalysts can be separated from the product by simple filtration. However, since the catalyst and the reactants belong to heterogeneous systems, the catalytic efficiency is reduced, and the amount of the reactants converted per unit mass of the catalyst per unit time is small. In addition, existing catalysts all need to be at a higher temperature to achieve the conversion of glycerol to glycerol carbonate.
In view of the above, the above-mentioned catalysts have certain drawbacks in catalyzing the reaction of urea and glycerol to synthesize glycerol carbonate. Mainly in the aspects of catalytic efficiency and catalyst separation, and especially at lower temperature, the catalytic performance is poor.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects existing in the background technology and providing a method for synthesizing the glycerol carbonate by a urea alcoholysis method, which takes glycerol and urea as raw materials and synthesizes the glycerol carbonate by the urea alcoholysis through a kettle reaction in the presence of a catalyst. The effects of high yield of the glycerol carbonate, short reaction time, low energy consumption (reducing reaction temperature) and no pollution are realized.
The catalyst used in the invention is a solid nitrogen-containing nano carbon catalyst (carbon quantum dots). The catalyst is nano-scale micro carbon particles, can form colloid in a reaction system, is highly dispersed in a reaction liquid, achieves the purpose of ultra-efficient catalytic conversion, and the dosage of the catalyst is only a few thousandths of that of the prior reports. In addition, separation of the product and the catalyst can be achieved by simple centrifugation techniques after the reaction.
The specific technical scheme of the invention is as follows:
a method for synthesizing glycerol carbonate uses urea and glycerol with a mol ratio of 1.5:1 as raw materials; in the presence of a catalyst, carrying out urea alcoholysis reaction to obtain glycerol carbonate, wherein the specific steps are that raw materials and the catalyst are added into a container, and the container is placed into a constant-temperature oil bath to react for 6 to 8 hours at the temperature of 105 to 125 ℃ to obtain the glycerol carbonate; the catalyst is a solid nitrogen-containing nano carbon material (carbon quantum dot), and the dosage of the catalyst is 0.002% -0.006% of the weight of the glycerol.
The catalyst is prepared by the following steps: chitosan, aluminum nitrate nonahydrate, citric acid and water with the molar ratio of 2.0-5.0:1.5:1.0:1000 are placed in a round-bottom flask, after continuous stirring until the mixture is completely dissolved, phosphoric acid is added, the dosage of the phosphoric acid is the same as the dosage of the aluminum nitrate nonahydrate, ammonia water with the ratio of 1:1 is used for regulating the pH value of the reaction solution to be 4.5, stirring is continued for 3 hours, water is removed by evaporation on a water bath with the temperature of 80 ℃ for 24 hours, the evaporated product is placed in a muffle furnace with the temperature of 300 ℃ for carbonization, the carbonized product is cooled to room temperature, and the obtained carbon material is ground into powder with the particle size of 40-60 meshes; stirring the ground powder and nitric acid with the concentration of 4mol/L for 5 hours at the temperature of 60 ℃ according to the proportion of 1g to 10mL, washing with water, filtering, and drying for 24 hours at the temperature of 80 ℃ to obtain the catalyst.
Preferably, the molar ratio of chitosan, aluminum nitrate nonahydrate, citric acid and water is: 3.0:1.5:1.0:1000.
The beneficial effects are that:
1. the catalyst used in the invention is a metal-free catalytic system, and is a high-efficiency catalyst without metal added in the first example of the system.
2. The reaction efficiency is high, and under the same conditions, TOF is thousands of times that of a homogeneous catalyst reported in literature.
3. The reaction temperature is low, and the reaction can efficiently synthesize the glycerol carbonate at the temperature of 110-125 ℃.
4. The catalyst has good circulation stability and is easy to separate from the reaction system.
Drawings
FIG. 1 is an XPS map of Cat2 prepared in example 2.
FIG. 2 is a cyclic reaction diagram of Cat2 prepared in example 2.
FIG. 3 is a schematic of the interruption response of Cat2 prepared in example 2.
Detailed Description
Example 1
(1) Method for preparing nitrogen-containing nano carbon catalyst by sol-gel method
2.68g of chitosan, 4.8g of aluminum nitrate nonahydrate, 1.60g of citric acid and 140ml of water (molar ratio, chitosan/aluminum nitrate nonahydrate/citric acid/water=2.0/1.5/1.0/1000) were taken in a round bottom flask, after continuous stirring until completely dissolved, 0.9ml of phosphoric acid was added, the reaction solution was adjusted to ph=4.5 with 1:1 aqueous ammonia, stirring was continued for 3 hours, the reaction solution was poured into a crucible, and water was removed by evaporation on an 80 ℃ water bath for 24 hours. And (3) carbonizing the evaporated product in a muffle furnace at 300 ℃, cooling to room temperature after carbonizing, and grinding the obtained carbon material into powder with the particle size of 40-60 meshes. 1g of ground powder and 10ml of nitric acid with the concentration of 4mol/L are added into a single-mouth bottle with magnetic stirring, stirred for 5 hours under the heating condition of 60 ℃, then washed with water, filtered by suction, dried for 24 hours under the condition of 80 ℃ to obtain the solid nano carbon material Cat1 (the nitrogen content is 6%).
(2) Reaction test experiment for synthesizing glycerol carbonate by alcoholysis of urea
45g of urea, 46g of glycerin and 0.001g of catalyst (less than 1/2000 of the dosage of the prior reported catalyst) are added into a three-necked flask, the mixture is placed into a constant-temperature water bath, heated to 115 ℃ and the pressure is 7kPa for reduced pressure reaction, sampling is carried out after the reaction is carried out for 6 hours, chromatographic analysis is carried out, and the yield of the glycerin carbonate is obtained through calculation by using an internal standard method. The selectivity of the glycerol carbonate was 95%, and the yield of the glycerol carbonate was 62.9%.
Example 2
(1) Method for preparing nitrogen-containing nano carbon catalyst by sol-gel method
4.05g of chitosan, 4.80g of aluminum nitrate nonahydrate, 1.60g of citric acid and 140ml of water (chitosan/aluminum nitrate nonahydrate/citric acid/water=3.0/1.5/1.0/1000) were taken in a round bottom flask, after continuous stirring until completely dissolved, 0.9ml of phosphoric acid was added, the reaction solution was adjusted to ph=4.5 with 1:1 aqueous ammonia, stirring was continued for 3 hours, the reaction solution was poured into a crucible, and water was removed by evaporation on a 80 ℃ water bath for 24 hours. And (3) carbonizing the evaporated product in a muffle furnace at 300 ℃, cooling to room temperature after carbonizing, and grinding the obtained carbon material into powder with the particle size of 40-60 meshes. 1g of ground powder and 10ml of nitric acid with the concentration of 4mol/L are added into a single-mouth bottle with magnetic stirring, stirred for 5 hours under the heating condition of 60 ℃, then washed with water, filtered by suction, dried for 24 hours under the condition of 80 ℃ to obtain the solid nano carbon material Cat2 (the nitrogen content is 12%). The XPS diagram of the prepared solid nano carbon material Cat2 is shown in figure 1.
(2) Reaction test experiment for synthesizing glycerol carbonate by alcoholysis of urea
45g of urea, 46g of glycerin and 0.002g of Cat2 are added into a three-necked flask, the three-necked flask is placed into a constant-temperature water bath, the mixture is heated to 125 ℃ and the pressure is 7kPa for reduced pressure reaction, sampling is carried out in the reaction for 8 hours respectively, chromatographic analysis is carried out, and the yield of the glycerin carbonate is obtained through calculation by using an internal standard method. The selectivity of the glycerol carbonate is 99%, and the yield of the glycerol carbonate is 93.2%. In addition, the catalyst is recovered by a filtration method, dried for 24 hours at 80 ℃ in a vacuum oven and recycled for 5 times. The specific results are shown in table 1 and fig. 2. In addition, the catalyst was subjected to heterogeneous test, the catalyst was filtered while it was still hot after 4 hours of reaction, and the obtained filtrate was continuously reacted under the same conditions, and the reaction result was shown in fig. 3. It is proved that no loss of active components occurs during the reaction.
TABLE 1 Experimental results of cyclic reactions for catalytic Synthesis of glycerol carbonate with solid catalyst
| Number of reactions | Glycerol carbonate selectivity | Yield of glycerol carbonate |
| 1 | 99％ | 93.2％ |
| 2 | 99％ | 91.8％ |
| 3 | 98％ | 91.6％ |
| 4 | 98％ | 90.9％ |
| 5 | 99％ | 90.1％ |
Example 3:
(1) Method for preparing nitrogen-containing nano carbon catalyst by sol-gel method
6.69g of chitosan, 4.80g of aluminum nitrate nonahydrate, 1.60g of citric acid and 140ml of water (chitosan/aluminum nitrate nonahydrate/citric acid/water=5.0/1.5/1.0/1000) were taken in a round bottom flask, after continuous stirring until completely dissolved, 0.9ml of phosphoric acid was added, the reaction solution was adjusted to ph=4.5 with 1:1 aqueous ammonia, stirring was continued for 3 hours, the reaction solution was poured into a crucible, and water was evaporated on a 80 ℃ water bath for 24 hours to remove water. And (3) carbonizing the evaporated product in a muffle furnace at 300 ℃, cooling to room temperature after carbonizing, and grinding the obtained carbon material into powder with the particle size of 40-60 meshes. 1g of ground powder and 10ml of nitric acid with the concentration of 4mol/L are added into a single-mouth bottle with magnetic stirring, stirred for 5 hours under the heating condition of 60 ℃, then washed with water, filtered by suction, dried for 24 hours under the condition of 80 ℃ to obtain the solid nano carbon material Cat3 (the nitrogen content is 15%).
(2) Reaction test experiment for synthesizing glycerol carbonate by alcoholysis of urea
45g of urea, 46g of glycerin and 0.003g of catalyst are added into a three-necked flask, the three-necked flask is placed into a constant-temperature water bath, the three-necked flask is heated to 105 ℃ and the pressure is 7kPa for reduced pressure reaction, samples are taken after 7h of reaction respectively, chromatographic analysis is carried out, and the yield of the glycerin carbonate is obtained through calculation by using an internal standard method. The selectivity of the glycerol carbonate is 98%, and the yield of the glycerol carbonate is 78.4%.
Claims (2)
1. A method for synthesizing glycerol carbonate uses urea and glycerol with a mol ratio of 1.5:1 as raw materials; in the presence of a catalyst, carrying out urea alcoholysis reaction to obtain glycerol carbonate, wherein the specific steps are that raw materials and the catalyst are added into a container, and the container is placed into a constant-temperature oil bath to react for 6 to 8 hours at the temperature of 105 to 125 ℃ to obtain the glycerol carbonate; the catalyst is solid nitrogen-containing nano carbon quantum dots, and the dosage of the catalyst is 0.002% -0.006% of the weight of the glycerol;
the catalyst is prepared by the following steps: chitosan, aluminum nitrate nonahydrate, citric acid and water with the molar ratio of 2.0-5.0:1.5:1.0:1000 are placed in a round-bottom flask, after continuous stirring until the mixture is completely dissolved, phosphoric acid is added, the dosage of the phosphoric acid is the same as the dosage of the aluminum nitrate nonahydrate, ammonia water with the ratio of 1:1 is used for regulating the pH value of the reaction solution to be 4.5, stirring is continued for 3 hours, water is removed by evaporation on a water bath with the temperature of 80 ℃ for 24 hours, the evaporated product is placed in a muffle furnace with the temperature of 300 ℃ for carbonization, the carbonized product is cooled to room temperature, and the obtained carbon material is ground into powder with the particle size of 40-60 meshes; stirring the ground powder and nitric acid with the concentration of 4mol/L for 5 hours at the temperature of 60 ℃ according to the proportion of 1g to 10mL, washing with water, filtering, and drying for 24 hours at the temperature of 80 ℃ to obtain the catalyst.
2. A method of synthesizing glycerol carbonate according to claim 1, wherein the molar ratio of chitosan, aluminum nitrate nonahydrate, citric acid and water is 3.0:1.5:1.0:1000.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6025504A (en) * | 1998-04-30 | 2000-02-15 | Organisation Nationale Interprofessionnelle Des Oleagineux (O.N.I.D.Ol.) | Method for preparing glycerol carbonate |
| CN102643263A (en) * | 2012-04-26 | 2012-08-22 | 陕西师范大学 | Method for preparing glycerol carbonate by liquid-phase oxidation and carbonylation of glycerol |
| KR20130115028A (en) * | 2012-04-10 | 2013-10-21 | 한국생산기술연구원 | A catalyst for preparing glycerol carbonate from glycerol, a preparation method thereof, and a preparation method of glycerol carbonate from glycerol by using the catalyst |
| KR20140014563A (en) * | 2012-07-24 | 2014-02-06 | 제우스유화공업(주) | Method of preparing glycerol carbonate having improved yield |
| CN105664907A (en) * | 2016-03-14 | 2016-06-15 | 江南大学 | Preparation method of catalyst for synthesizing glycerol carbonate through urea method |
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| US7851645B2 (en) * | 2008-02-11 | 2010-12-14 | Catalytic Distillation Technologies | Process for continuous production of organic carbonates or organic carbamates and solid catalysts therefore |
| WO2014197329A1 (en) * | 2013-06-03 | 2014-12-11 | Trustees Of Boston University | Fiber coated nanopores |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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