CN117361504A - Carbon quantum dot with double functions of catalysis and high heat absorption, preparation method thereof and application thereof in esterification reaction - Google Patents
Carbon quantum dot with double functions of catalysis and high heat absorption, preparation method thereof and application thereof in esterification reaction Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000005886 esterification reaction Methods 0.000 title claims abstract description 53
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 24
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 90
- 230000005496 eutectics Effects 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- 150000001413 amino acids Chemical class 0.000 claims abstract description 13
- -1 silicate compound Chemical class 0.000 claims abstract description 10
- 238000009841 combustion method Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 24
- 235000001014 amino acid Nutrition 0.000 claims description 12
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 12
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 6
- 235000013922 glutamic acid Nutrition 0.000 claims description 6
- 239000004220 glutamic acid Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 230000009977 dual effect Effects 0.000 claims description 5
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 4
- 235000003704 aspartic acid Nutrition 0.000 claims description 4
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000004760 silicates Chemical class 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 claims description 3
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 18
- 230000032050 esterification Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 42
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 30
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 21
- YYZUSRORWSJGET-UHFFFAOYSA-N ethyl octanoate Chemical compound CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 description 14
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 12
- 230000001133 acceleration Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000007795 chemical reaction product Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000004445 quantitative analysis Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 239000004475 Arginine Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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
- B01J21/18—Carbon
-
- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
Abstract
The invention relates to the technical field of carbon quantum dots, and particularly discloses a carbon quantum dot with double functions of catalysis and high heat absorption, a preparation method thereof and application thereof in esterification reaction. The eutectic solvent prepared by acidic amino acid and silicate compound is used as a precursor, and the functional carbon quantum dot is prepared by a combustion method. The functional carbon quantum dot provided by the invention not only contains rich carboxyl and other acidic groups to realize efficient catalysis of esterification reaction, but also improves the reaction efficiency and replaces the traditional industrial heavy-pollution concentrated sulfuric acid catalyst; the catalyst also has siloxane groups and alkyl functional groups with excellent heat absorption performance, is favorable for absorbing the reaction heat released in the esterification process, and reduces the thermal risk in the esterification reaction process. In addition, the solid carbon quantum dots obtained by the combustion method are beneficial to recycling for multiple times. The carbon quantum dot can improve the esterification reaction efficiency and the safety of the esterification reaction process, and provides a novel method for the safe and efficient production of the esterification reaction.
Description
Technical Field
The invention relates to the technical field of carbon quantum dots, in particular to a carbon quantum dot with double functions of catalysis and high heat absorption, a preparation method thereof and application thereof in esterification reaction.
Background
The product of the esterification reaction, namely carboxylate, is an important compound, is a raw material for a plurality of organic synthesis reactions, is widely applied to the fields of foods, medicines, daily chemicals, plastics and the like, and has higher and higher demands for carboxylate along with the increasing living standard of people. The esterification reaction is exothermic, and the heat generated in the esterification reaction process can lead to the continuous increase of the temperature of the reaction system, so that the reaction rate is continuously accelerated, and the whole reaction system is caused to be out of control. At present, the esterification reaction also needs a catalyst to improve the esterification conversion rate, and the industrial synthetic carboxylic ester mainly comprises concentrated sulfuric acid, phosphoric acid, p-toluenesulfonic acid and the like. These traditional catalysts, while having relatively high catalytic activity and low cost, are readily available, suffer from a number of drawbacks such as: the catalytic efficiency needs to be further improved, the side reaction is more, the product purity is low, the equipment corrosion is serious, the waste acid yield is high, the environmental pollution is serious, and the like.
In order to solve the above-mentioned drawbacks of the conventional esterification catalysts, researchers have developed a series of novel esterification catalysts to replace the conventional catalysts. At present, the novel esterification catalyst mainly comprises a phase transfer catalyst, an ionic liquid catalyst, an inorganic salt catalyst, a resin catalyst, a molecular sieve catalyst, a heteropolyacid catalyst, a solid super acid catalyst and the like. These new catalysts all have a high catalytic activity, but at present there are still some problems. For example, the reaction heat of the system cannot be effectively controlled, so that more side reactions are caused, and the process safety is poor; the catalyst recycling cost is high; the active components of the catalyst are easy to lose, the catalytic activity is unstable, etc. Therefore, the development of a novel catalyst which has low production cost, is environment-friendly, can effectively reduce the reaction heat and improve the conversion rate of the esterification reaction has important industrial application value.
Disclosure of Invention
Aiming at the problems that the esterification conversion rate of an esterification reaction catalyst in the prior art is low, side reactions are more caused by the fact that the reaction heat of a system cannot be effectively controlled, and the like, the invention provides a carbon quantum dot with double functions of catalysis and high heat absorption, a preparation method thereof and application thereof in esterification reaction.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the carbon quantum dot with double functions of catalysis and high heat absorption is prepared by taking a eutectic solvent prepared from acidic amino acid and silicate compounds as a precursor and adopting a combustion method.
Compared with the prior art, the functional carbon quantum dot provided by the invention has the advantages that the acid amino acid is used as a hydrogen bond donor, the silicate compound is used as a hydrogen bond acceptor, the eutectic solvent precursor with good chemical stability is prepared through the hydrogen bond action among substances, and then the precursor is subjected to a combustion method to prepare the carbon quantum dot. According to the invention, the carbon quantum dots are subjected to functional modification by using specific acidic amino acid and silicate compounds, so that the carbon quantum dots have acidic groups such as carboxyl groups with high reactivity, and the efficiency of catalytic esterification reaction of the carbon quantum dots is greatly improved. Meanwhile, the high chemical bond energy of the silicon oxygen bond (bond energy 443 kJ/mol) and the alkyl strong carbon hydrogen bond (bond energy 413 kJ/mol) of the carbon quantum dot can obviously improve the heat absorption capacity of the carbon quantum dot, and the potential safety hazard possibly caused by high heat release in the esterification reaction process is solved. In addition, the raw materials selected by the invention are green and environment-friendly, the cost is low, the prepared carbon quantum dots have uniform particle size, good dispersibility in a reaction system and high thermal stability, the conversion rate and the process safety of the esterification reaction are effectively ensured, and the method has wide application prospect in the field of the esterification reaction.
Preferably, the acidic amino acid is at least one of glutamic acid or aspartic acid.
Preferably, the silicate compound is at least one of tetraethyl silicate, isopropyl silicate or tetrabutyl silicate.
Preferably, the molar ratio of the acidic amino acid to the silicate compound is 1:3-1:7.
Preferably, a eutectic solvent with stable performance can be formed between the acidic amino acid and the silicate compound through hydrogen bonds, and the acidic amino acid and the silicate compound can also carry out functional group modification on the surface of the carbon quantum dot, so that the distribution of the modification groups on the surface of the carbon quantum dot is optimized, and the catalytic activity and the heat absorption function of the carbon quantum dot are further improved.
Preferably, the acidic amino acid and the silicate compound are uniformly mixed, heated to 80-120 ℃, and kept at a constant temperature until the system is uniform and transparent, thus obtaining the eutectic solvent.
The invention also provides a preparation method of the carbon quantum dot with double functions of catalysis and high heat absorption, which comprises the following steps: preheating the eutectic solvent to 100-200 ℃, preserving heat for a preset time, and then heating to 300-500 ℃ to perform high-temperature combustion reaction to obtain the carbon quantum dot with double functions of catalysis and high heat absorption.
Preferably, the preset time is 5 min-25 min.
Preferably, the high-temperature combustion reaction time is 2-5 hours.
The preparation method of the carbon quantum dot provided by the invention is simple and easy to implement, the raw material sources are wide, the prepared carbon quantum dot has uniform particle size, good dispersibility and high thermal stability, the esterification reaction efficiency can be effectively improved, the reaction heat of the esterification reaction is reduced, the preparation method is suitable for large-scale production, and the application of the carbon quantum dot in the aspects of energy development, chemical safety and the like is effectively expanded.
The invention also provides application of the carbon quantum dot with the double functions of catalysis and high heat absorption in esterification reaction.
The functional carbon quantum dot provided by the invention has good dispersibility, is beneficial to promoting the full contact of the carbon quantum dot and an esterification reactant, not only contains specific carboxyl acid groups for catalysis to improve the esterification reaction efficiency, but also loads rich high-bond-energy silica groups and alkyl functional groups, is beneficial to absorbing the reaction heat in the esterification process, reduces the thermal risk of the esterification reaction, simultaneously keeps the self stability of the carbon quantum dot, and is beneficial to the repeated recycling of the carbon quantum dot.
Specifically, the carbon quantum dot with double functions of catalysis and high heat absorption is applied to the preparation of esterification reaction of C4-C10 carboxylic ester.
Illustratively, the esterification reaction includes, but is not limited to, an esterification reaction of acetic acid with ethanol to produce ethyl acetate, acetic acid with n-butanol to produce n-butyl acetate, n-octanoic acid with ethanol to produce a C4-C10 carboxylic acid ester such as ethyl octanoate.
The invention also provides a method for preparing the C4-C10 carboxylic ester, which comprises the following steps:
and uniformly mixing the carbon quantum dots with the double functions of catalysis and high heat absorption with acid and alcohol corresponding to the preparation of the C4-C10 carboxylic ester, heating to 60-120 ℃, and carrying out heat preservation reaction to obtain the C4-C10 carboxylic ester.
Preferably, the addition amount of the functional carbon quantum dots is 1% -5% of the mass of the alcohol.
Preferably, the time of the heat preservation reaction is 0.5 to 3 hours.
More preferably, the temperature of the esterification reaction is 75-115 ℃, and the time of the esterification reaction is 1-2 h.
The carbon quantum dot provided by the invention has higher catalytic activity on the esterification reaction for preparing C4-C10 carboxylic ester, the highest yield of the esterification reaction can reach 99.5%, the reaction time is shorter, and the high-efficiency catalytic conversion of the target esterification reaction can be realized at a lower reaction temperature. Compared with the conventional esterification reaction, the esterification reaction heat which can be reduced by adding the functional carbon quantum dots can be up to 25 percent. After the reaction is finished, the carbon quantum dots can be separated from the esterification product through simple filtration, the separated carbon quantum dots can be repeatedly utilized, and the functions of high catalytic activity and reaction heat reduction are still maintained.
The method for preparing the C4-C10 carboxylic ester is a novel efficient and economic method for realizing catalytic esterification reaction and reducing esterification reaction heat, provides a novel direction for the safe production of the esterification reaction in the future, and has wide application prospect in the field of chemical production.
Drawings
Fig. 1 is a TEM image of a carbon quantum dot a prepared in example 1 of the present invention;
FIG. 2 is a graph showing the particle size distribution of the carbon quantum dot A prepared in example 1 of the present invention;
FIG. 3 is an XPS chart of the carbon quantum dot A prepared in example 1 of the present invention;
FIG. 4 is a graph showing the exothermic change in the course of the esterification reaction measured by an adiabatic acceleration calorimeter in example 6 of the present invention;
fig. 5 is a TEM image of the carbon quantum dot A1 prepared in comparative example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to better illustrate the present invention, the following examples are provided for further illustration.
Example 1
The embodiment of the invention provides a functional carbon quantum dot, which is prepared by the following steps:
s1, adding 0.1mol of glutamic acid and 0.2mol of tetraethyl silicate into a 100mL three-necked flask, heating to 105 ℃, and reacting for 50min to obtain a uniform and transparent eutectic solvent;
s2, placing 10g of the prepared eutectic solvent into a crucible, heating to 150 ℃ by using an electric furnace, pretreating for 20min, then placing the pretreated substance into a muffle furnace, reacting for 3h at 350 ℃, and grinding after the reaction is finished to obtain the functional carbon quantum dot A.
The TEM image of the functional carbon quantum dot a prepared in this embodiment is shown in fig. 1, and it can be seen from the image that the carbon quantum dot is spherical, and the carbon quantum dot is uniformly dispersed and has a relatively uniform particle size distribution. As can be seen from the particle size distribution diagram of the carbon quantum dot a in fig. 2, the particle size is mainly concentrated in 3 to 10nm.
The XPS spectrum of the carbon quantum dot A is shown in figure 3, and the peak of 283.6eV and 286.8eV proves that the surface of the carbon quantum dot A contains rich C-C bonds and C-O bonds through peak-splitting fitting of C1s peak; the peak at 398.97eV shows that the surface of the carbon quantum A contains rich C-N bonds through the peak-by-peak fitting of the N1s peak. The surface modification of the carbon quantum dot A is provided with acidic and alkyl functional groups.
Example 2
The embodiment of the invention provides a functional carbon quantum dot, which is prepared by the following steps:
s1, adding 0.1mol of aspartic acid and 0.7mol of tetraethyl silicate into a 100mL three-necked flask, heating to 120 ℃, and reacting for 30min to obtain a uniform and transparent eutectic solvent;
s2, placing 10g of the prepared eutectic solvent into a crucible, heating to 160 ℃ by using an electric furnace, pretreating for 15min, then placing the pretreated substance into a muffle furnace, reacting for 3.5h at 400 ℃, and grinding after the reaction is finished to obtain the functional carbon quantum dot B.
Example 3
The embodiment of the invention provides a functional carbon quantum dot, which is prepared by the following steps:
s1, adding 0.1mol of glutamic acid and 0.2mol of isopropyl silicate into a 100mL three-necked flask, heating to 100 ℃, and reacting for 60min to obtain a uniform and transparent eutectic solvent;
s2, placing 10g of the prepared eutectic solvent into a crucible, heating to 140 ℃ by using an electric furnace, pretreating for 20min, then placing the pretreated substance into a muffle furnace, reacting for 5h at 300 ℃, and grinding after the reaction is finished to obtain the functional carbon quantum dot C.
Example 4
The embodiment of the invention provides a functional carbon quantum dot, which is prepared by the following steps:
s1, adding 0.1mol of glutamic acid and 0.3mol of tetrabutyl silicate into a 100mL three-necked flask, heating to 80 ℃, and reacting for 90min to obtain a uniform and transparent eutectic solvent;
s2, placing 10g of the prepared eutectic solvent into a crucible, heating to 100 ℃ by using an electric furnace, pretreating for 25min, then placing the pretreated substance into a muffle furnace, reacting for 3h at 330 ℃, and grinding after the reaction is finished to obtain the functional carbon quantum dot D.
Example 5
The embodiment of the invention provides a functional carbon quantum dot, which is prepared by the following steps:
s1, adding 0.1mol of aspartic acid and 0.5mol of tetrabutyl silicate into a 100mL three-necked flask, heating to 125 ℃, and reacting for 65min to obtain a uniform and transparent eutectic solvent;
s2, placing 10g of the prepared eutectic solvent into a crucible, heating to 200 ℃ by using an electric furnace, pretreating for 5min, then placing the pretreated substance into a muffle furnace, reacting for 2h at 500 ℃, and grinding after the reaction is finished to obtain the functional carbon quantum dot E.
Example 6
The embodiment of the invention provides an application of a functional carbon quantum dot in preparation of n-butyl acetate, which specifically comprises the following steps:
adding 0.15g of the functional carbon quantum dot A prepared in the embodiment 1, 6mL of n-butyl alcohol and 4mL of acetic acid into a reactor, heating to 95 ℃ and magnetically stirring to react for 1.5h, cooling to room temperature after the reaction is finished, filtering to obtain the recovered functional carbon quantum dot A, taking a reaction product, carrying out gas chromatography quantitative analysis, and calculating the yield of the n-butyl acetate to be 98.9%.
The exothermic heat during the reaction was measured by using an adiabatic acceleration calorimeter, and as shown in FIG. 4, the exothermic heat of the reaction by the above reaction without adding carbon quantum dots was 95.09KJ, the exothermic heat of the reaction after adding the above carbon quantum dots was 74.16KJ, and the heat of the reaction was reduced by 22%.
As can be seen from fig. 4, after the functional carbon quantum dot a was added, the esterification reaction of n-butanol and acetic acid was shortened by 8% compared with the time to reach the maximum reaction rate without adding the carbon quantum dot.
The recovered functional carbon quantum dot A is repeatedly synthesized into the synthetic butyl acetate, the yield of the n-butyl acetate can still reach 98.7% after recycling for 5 times, and the reaction heat can be reduced by 20.8%.
Example 7
The embodiment of the invention provides an application of a functional carbon quantum dot in preparing ethyl acetate, which specifically comprises the following steps:
adding 0.15g of the functional carbon quantum dot A prepared in the embodiment 1, 6mL of ethanol and 4mL of acetic acid into a reactor, heating to 95 ℃ and magnetically stirring to react for 1.5h, cooling to room temperature after the reaction is finished, filtering to obtain the recovered functional carbon quantum dot A, taking a reaction product, carrying out gas chromatography quantitative analysis, and calculating the yield of ethyl acetate to be 99.5%.
The exothermic heat during the reaction was measured by using an adiabatic acceleration calorimeter, and the exothermic heat of the reaction according to the above reaction without adding carbon quantum dots was 70.62KJ, and the exothermic heat of the reaction after adding the above carbon quantum dots was 52.97KJ, and the heat of the reaction was reduced by 25%.
The recovered functional carbon quantum dot A is repeatedly synthesized into the ethyl acetate, the yield of the ethyl acetate can still reach 98.2 percent after recycling for 5 times, and the reaction heat can be reduced by 21.3 percent.
Example 8
The embodiment of the invention provides an application of a functional carbon quantum dot in preparation of ethyl octanoate, which specifically comprises the following steps:
adding 0.15g of the functional carbon quantum dot A prepared in the embodiment 1, 6mL of ethanol and 4mL of n-octanoic acid into a reactor, heating to 95 ℃ and magnetically stirring to react for 1.5h, cooling to room temperature after the reaction is finished, filtering to obtain the recovered functional carbon quantum dot A, taking a reaction product to perform gas chromatography quantitative analysis, and calculating the yield of the ethyl octanoate to be 99.2%.
The exothermic heat during the reaction was measured by using an adiabatic acceleration calorimeter, and the exothermic heat of the reaction according to the above reaction without adding carbon quantum dots was 83.25KJ, and the exothermic heat of the reaction after adding the above carbon quantum dots was 68.68KJ, and the heat of the reaction was reduced by 17.5%.
The recovered functional carbon quantum dot A is repeatedly synthesized into the ethyl octanoate, the yield of the ethyl octanoate can still reach 97.6% after recycling for 5 times, and the reaction heat can be reduced by 15.8%.
Example 9
The embodiment of the invention provides an application of a functional carbon quantum dot in preparation of n-butyl acetate, which specifically comprises the following steps:
adding 0.15g of the functional carbon quantum dot B prepared in the embodiment 2, 6mL of n-butyl alcohol and 4mL of acetic acid into a reactor, heating to 95 ℃ and magnetically stirring to react for 1.5h, cooling to room temperature after the reaction is finished, filtering to obtain the recovered functional carbon quantum dot B, taking a reaction product, carrying out gas chromatography quantitative analysis, and calculating the yield of the n-butyl acetate to be 96.9%.
The exothermic heat during the reaction was measured by using an adiabatic acceleration calorimeter, and the exothermic heat of the reaction according to the above reaction without adding carbon quantum dots was 95.09KJ, and the exothermic heat of the reaction after adding the above carbon quantum dots was 78.68KJ, and the heat of reaction was reduced by 17.3%.
The recovered functional carbon quantum dot B is repeatedly synthesized into n-butyl acetate, the yield of n-butyl acetate can still reach 93.1% after recycling for 5 times, and the reaction heat can be reduced by 14.9%.
Example 10
The embodiment of the invention provides an application of a functional carbon quantum dot in preparing ethyl acetate, which specifically comprises the following steps:
adding 0.12g of the functional carbon quantum dot C prepared in the embodiment 3, 5mL of ethanol and 4mL of acetic acid into a reactor, heating to 95 ℃ and magnetically stirring to react for 1.5h, cooling to room temperature after the reaction is finished, filtering to obtain the recovered functional carbon quantum dot C, taking a reaction product, carrying out gas chromatography quantitative analysis, and calculating the yield of ethyl acetate to be 95.8%.
The exothermic heat during the reaction was measured by using an adiabatic acceleration calorimeter, and the exothermic heat of the reaction according to the above reaction without adding carbon quantum dots was 70.62KJ, and the exothermic heat of the reaction after adding the above carbon quantum dots was 59.67KJ, and the heat of reaction was reduced by 15.5%.
The recovered functional carbon quantum dots C are repeatedly synthesized into the ethyl acetate, the yield of the ethyl acetate can still reach 92.7% after recycling for 5 times, and the reaction heat can be reduced by 12.8%.
The application of the carbon quantum dots prepared in examples 4 to 5 to examples 6 to 10 can achieve a technical effect substantially equivalent to that of the carbon quantum dots prepared in examples 1 to 3.
In order to better illustrate the technical solutions of the present invention, the following is further contrasted by way of comparative examples and examples of the present invention.
Comparative example 1
This comparative example provides a carbon quantum dot, which is identical to example 1 in terms of raw materials and preparation methods, except that tetraethyl silicate in example 1 is replaced with an equivalent amount of ethyl acetate, and the other materials are identical. Carbon quantum dot A1 was prepared in the same manner as in example 1.
As shown in fig. 5, a TEM image of the carbon quantum dot A1 prepared in this comparative example shows that the carbon quantum dot A1 has a large particle diameter, a small number, and a non-uniform particle diameter distribution. Compared with example 1, it is demonstrated that silicate compounds play an important role in the synthesis of carbon quantum dots, which is advantageous in controlling the particle size and uniformity of the carbon quantum dots.
(1) The prepared carbon quantum dot A1 is used for preparing n-butyl acetate, and specifically comprises the following steps:
and adding 0.15g of the prepared functional carbon quantum dot A, 6mL of n-butanol and 4mL of acetic acid into a reactor, heating to 95 ℃ and magnetically stirring to react for 1.5h, cooling to room temperature after the reaction is finished, filtering, taking a reaction product, carrying out gas chromatography quantitative analysis, and calculating the yield of n-butyl acetate to be 55%.
The exothermic heat during the reaction is measured by using an adiabatic acceleration calorimeter, and the exothermic heat of the reaction performed according to the reaction without adding carbon quantum dots is 95.09KJ, the exothermic heat of the reaction after adding the carbon quantum dots is 92.34KJ, the reaction heat is reduced by 2.9%, and the function of obviously absorbing the reaction heat is avoided.
(2) The prepared carbon quantum dot A1 is used for preparing ethyl acetate, and specifically comprises the following steps:
adding 0.12g of the prepared functional carbon quantum dot A, 6mL of ethanol and 4mL of acetic acid into a reactor, heating to 95 ℃ and magnetically stirring to react for 1.5h, cooling to room temperature after the reaction is finished, filtering, taking a reaction product, carrying out gas chromatography quantitative analysis, and calculating the yield of ethyl acetate to be 48%.
The exothermic heat in the reaction process is measured by using an adiabatic acceleration calorimeter, and the exothermic heat of the reaction performed according to the reaction without adding the carbon quantum dots is 70.62KJ, the exothermic heat of the reaction after adding the carbon quantum dots is 69.14KJ, the reaction heat is reduced by 2.1%, and the function of obviously absorbing the reaction heat is avoided.
(3) The application of the prepared carbon quantum dot A1 in preparing ethyl octanoate specifically comprises the following steps:
and adding 0.15g of the prepared functional carbon quantum dot A, 6mL of ethanol and 4mL of n-octanoic acid into a reactor, heating to 95 ℃, magnetically stirring and reacting for 1.5h, cooling to room temperature after the reaction is finished, filtering, taking a reaction product, carrying out gas chromatography quantitative analysis, and calculating the yield of the ethyl octanoate to be 53%.
The exothermic heat during the reaction was measured by using an adiabatic acceleration calorimeter, and the exothermic heat of the reaction according to the above reaction without adding carbon quantum dots was 83.25KJ, the exothermic heat of the reaction after adding the above carbon quantum dots was 82.17KJ, and the heat of the reaction was reduced by 1.3%.
Comparative example 2
This comparative example provides a carbon quantum dot which is identical to example 1 in terms of raw materials and preparation methods, except that glutamic acid in example 1 is replaced with an equal amount of arginine, and the other materials are identical. Carbon quantum dot A2 was prepared in the same manner as in example 1.
The prepared carbon quantum dot A2 is used for preparing ethyl acetate, and specifically comprises the following steps:
adding 0.12g of the prepared functional carbon quantum dot A, 6mL of ethanol and 4mL of acetic acid into a reactor, heating to 95 ℃ and magnetically stirring to react for 1.5h, cooling to room temperature after the reaction is finished, filtering, taking a reaction product to perform gas chromatography quantitative analysis, and calculating the yield of ethyl acetate to be 57%.
The exothermic heat in the reaction process is measured by using an adiabatic acceleration calorimeter, and the exothermic heat of the reaction performed according to the reaction without adding the carbon quantum dots is 70.62KJ, the exothermic heat of the reaction after adding the carbon quantum dots is 69.35KJ, the reaction heat is reduced by 1.8%, and the function of obviously absorbing the reaction heat is avoided.
In conclusion, the carbon quantum dot provided by the invention can simultaneously realize the dual purposes of improving the esterification reaction efficiency and guaranteeing the safety of the esterification reaction process, and has important applicability in the field of chemical production.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The carbon quantum dot with double functions of catalysis and high heat absorption is characterized in that the carbon quantum dot is prepared by taking a eutectic solvent prepared from acidic amino acid and silicate compounds as a precursor through a combustion method.
2. The carbon quantum dot with dual functions of catalysis and high heat absorption according to claim 1, wherein the acidic amino acid is at least one of glutamic acid or aspartic acid; and/or
The silicate compound is at least one of tetraethyl silicate, isopropyl silicate or tetrabutyl silicate.
3. The carbon quantum dot with dual functions of catalysis and high heat absorption as claimed in claim 1 or 2, wherein the molar ratio of the acidic amino acid to the silicate compound is 1:3-1:7.
4. The carbon quantum dot with dual functions of catalysis and high heat absorption as claimed in claim 1 or 2, wherein the preparation method of the eutectic solvent comprises the following steps: and uniformly mixing the acidic amino acid and the silicate compound, heating to 80-120 ℃, and keeping the temperature until the system is uniform and transparent, thus obtaining the eutectic solvent.
5. A method for preparing the carbon quantum dot with double functions of catalysis and high heat absorption as claimed in any one of claims 1 to 4, which is characterized by comprising the following steps: preheating the eutectic solvent to 100-200 ℃, preserving heat for a preset time, and then heating to 300-500 ℃ to perform high-temperature combustion reaction to obtain the carbon quantum dot with double functions of catalysis and high heat absorption.
6. The method for preparing the carbon quantum dot with the dual functions of catalysis and high heat absorption as claimed in claim 5, wherein the preset time is 5-25 min; and/or
The high-temperature combustion reaction time is 2-5 h.
7. The use of the carbon quantum dot with double functions of catalysis and high heat absorption as claimed in any one of claims 1 to 4 in esterification reaction.
8. The method according to claim 7, wherein the carbon quantum dots with double functions of catalysis and high heat absorption are used for preparing esterification reaction of C4-C10 carboxylic ester.
9. A process for preparing a C4 to C10 carboxylate comprising the steps of:
uniformly mixing the carbon quantum dots with the double functions of catalysis and high heat absorption according to any one of claims 1-4 with acid and alcohol corresponding to the preparation of the C4-C10 carboxylic ester, heating to 60-120 ℃, and carrying out heat preservation reaction to obtain the C4-C10 carboxylic ester.
10. The method for preparing C4-C10 carboxylic acid ester according to claim 9, wherein the addition amount of the functional carbon quantum dots is 1% to 5% of the mass of the alcohol; and/or
The reaction time of the heat preservation is 0.5 h-3 h.
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