CN110152704B - Metal-free solid catalyst for synthesizing linear carbonate and preparation method thereof - Google Patents
Metal-free solid catalyst for synthesizing linear carbonate and preparation method thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention belongs to the field of solid catalyst preparation, and particularly relates to a metal-free solid catalyst for synthesizing linear carbonate and a preparation method thereof. The catalyst uses graphite phase carbon nitride (g-C) 3 N 4 ) Stripping, protonating with ammonia water, pyridine or pyrrole, filtering, washing and drying to obtain deprotonated stripped g-C 3 N 4 A catalyst. The catalyst is simple to prepare and operate, does not introduce any metal ions, has high activity when being used for synthesizing linear carbonate by the transesterification of ethylene carbonate, is simple to recover, and does not cause metal ion pollution to reaction products.
Description
Technical Field
The invention belongs to the field of preparation of solid catalysts, and particularly relates to a preparation method of a metal-free solid catalyst for synthesizing linear carbonate by an ester exchange reaction of ethylene carbonate and methanol or ethanol.
Background
Linear carbonates, represented by dimethyl carbonate (DMC) and diethyl carbonate (DEC), are a class of chemical raw materials with a wide range of applications. Because of containing a plurality of functional groups, the linear carbonic ester is widely applied to organic synthesis reactions such as alkylation, carbonylation and the like, thereby replacing toxic dimethyl sulfate, methyl chloroformate and the like; or with alcohol, ester and amino alcohol, etc. to synthesize fine chemical products such as resin, pesticide, food additive, etc. DMC can replace trichloroethylene, benzene or xylene and the like as a paint coating, a cleaning solvent and the like. DMC and DEC can also be used as gasoline additive to replace methyl tert-butyl ether (MTBE), improve octane and oxygen content, enhance combustion efficiency, and reduce CO and nitrogen compounds emissions.
The conventional methods for industrially producing linear carbonates are mainly phosgene method and methanol oxidative carbonylation method. The phosgene method has high toxicity and is gradually eliminated. The methanol oxidation carbonylation method takes methanol, carbon monoxide and oxygen as raw materials, is a clean production process, but the method has low yield of preparing linear carbonate, and the carbon monoxide is an explosive and extremely toxic gas, so that potential safety hazards exist. In contrast, the transesterification method is a novel production process for producing linear carbonates, which is obtained by transesterification of cyclic carbonates and alcohols (formula 1).
The raw materials used in the ester exchange method are easy to obtain, low in toxicity and cost, low in corrosion of equipment and high in DMC and DEC yield. In addition, the reaction process is clean and pollution-free, and belongs to an environment-friendly process. Meanwhile, the byproduct ethylene glycol is also an important chemical raw material. At present, most enterprises in China adopt the method to produce DMC and DEC. The core problem of the process lies in the development of high-efficiency catalysts. At present, the catalyst body used for the transesterification reactionMany are available, and the most active is ionic liquid. Although the ionic liquid has high catalytic activity, the biggest problem is that the catalytic reaction in which the ionic liquid participates is a homogeneous system, and a lot of difficulties exist in the aspects of product separation and purification. Sunlians et al (ACS Applied Materials)&Interfaces,2013,5: 9823-. Watanabe et al (Microporous)&Mesoporous Materials,1998,22: 399- 2.5 Al-NO 3 ) Used as a catalyst for transesterification. Although the solid catalysts described above overcome the problem of catalyst recovery after the reaction, the catalysts described above all have metal salts involved, and the products of their transesterification (i.e., linear carbonates) are easily contaminated with metal ions. On the other hand, when the linear carbonate is applied to a battery electrolyte, extremely strict requirements are imposed on the content of metal ions in the linear carbonate.
In recent years, graphite phase carbon nitride (g-C) 3 N 4 ) The metal-free material has attracted people's attention in the fields of heterogeneous catalysis, photocatalysis, etc. In terms of composition and structure, g-C 3 N 4 The main unit is tris-s-triazine, and a large number of amino functional groups exist at the edge of a graphite-like layer. Thus g-C 3 N 4 Is a typical solid base material. Ordinary g-C obtained by direct roasting of dicyanodiamine, melamine or urea 3 N 4 The specific surface of the material is very low and the alkali strength of the material is weak. If the ordinary g-C is used directly 3 N 4 As a catalyst, its catalytic activity is low. The subject group reported g-C 3 N 4 Supported metal halide and metal oxide materials can be used to catalyze the transesterification of cyclic carbonates to synthesize linear carbonates (chinese patents 201410606485.9 and 201610415575.9). Although the introduction of metal halides and metal oxides enhances the g-C 3 N 4 Finally, the catalytic activity of the catalyst is improved, but the problem of metal ion pollution is also existed.
Disclosure of Invention
The invention aims to solve the technical problems of difficult recovery, metal ion pollution and the like of the catalyst used in the conventional process for synthesizing linear carbonate.
In order to solve the problems, the invention uses g-C 3 N 4 Is a platform material, and is firstly subjected to secondary roasting to prepare the stripped g-C 3 N 4 The material is deprotonated by ammonia water, pyridine or pyrrole to synthesize stripped and deprotonated metal-free g-C 3 N 4 The catalyst and the application thereof in the process of synthesizing the linear carbonate have positive experimental effects.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a solid metal-free catalyst for synthesizing linear carbonate is prepared from g-C through secondary calcining, stripping, deprotonation treatment by ammonia water, pyridine or pyrrole 3 N 4 A material.
The metal-free solid catalyst for synthesizing linear carbonate according to the present invention is prepared specifically according to the following steps.
(1) Using dicyanodiamine, melamine or urea organic amine as precursor, roasting at 550 deg.C for 2-4 h to obtain g-C 3 N 4 A material.
(2) The step (1) g to C 3 N 4 After grinding, the material is continuously roasted for 2h at the temperature of 550 ℃ to obtain the stripped g-C 3 N 4 Material (eg-C) 3 N 4 )；
(3) 0.5 to 1 part by mass of eg-C 3 N 4 And 20 parts by mass of an aqueous ammonia solution, pyridine or pyrrole solution (0.1-2 mol. L) -1 ) Rapidly stirring for 8-12 h at 30-140 ℃ in a high-pressure reaction kettle;
(4) the suspension is isolated as a solid, washed with water to pH 7 and then dried at 80-120 deg.C overnight to yield metal-free g-C for the transesterification synthesis of linear carbonates 3 N 4 A catalyst.
In the present invention, eg-C described in step (3) 3 N 4 The mass of (b) is preferably 0.6 parts by mass; the preferable stirring time is 10 hours; the deprotonating agent is preferablyIs ammonia water; the concentration of ammonia water is preferably 0.3 mol.L -1 The temperature of the alkali treatment is preferably 120 ℃.
In the present invention, the drying temperature in the step (4) is preferably 100 ℃.
The catalyst is used for synthesizing linear carbonate by taking methanol or ethanol and Ethylene Carbonate (EC) as raw materials, and the specific application method comprises the following steps: the catalyst reaction device is a 50-200 mL stainless steel high-pressure reaction kettle which is provided with a program temperature control device and a magnetic stirring device. The reaction conditions were as follows: the catalyst dosage is 0.2 part by mass, the EC is 2.2 parts by mass, the methanol or the ethanol is 8 parts by mass, the reaction temperature is 110-130 ℃, the reaction filling gas is nitrogen, and the reaction time is 4 hours. After the reaction, the reaction system was centrifuged. The results of the analysis were detected by gas chromatography (SP6890) equipped with a FID detector.
The invention is further described below with reference to the accompanying drawings.
Drawings
FIG. 1 shows the general g-C obtained by direct calcination of dicyanodiamine, melamine or urea 3 N 4 Materials and N of CAT-1 catalyst prepared in example 1 2 Adsorption and desorption isotherms.
FIG. 2 is a general g-C 3 N 4 And X-ray photoelectron spectrum of CAT-1.
FIG. 3 is g-C 3 N 4 The basic building blocks of (a) are combined with the XPS spectra corresponding to different N species.
Detailed Description
The invention will be further described in the following examples, but it is to be understood that these examples are illustrative only and are not to be construed as limiting the practice of the invention.
Example 1
Using dicyanodiamine as a precursor, roasting for 3 hours at the temperature of 550 ℃ to obtain g-C 3 N 4 A material. Mixing the above g-C 3 N 4 After grinding, the material is continuously roasted for 2h at the temperature of 550 ℃ to obtain the stripped g-C 3 N 4 Material eg-C 3 N 4 . 0.6 part by mass of eg-C 3 N 4 And 20 parts by mass of aqueous ammonia (0.3 mol. L) -1 ) Adding into a high-pressure reaction kettle. The reaction was stirred at 120 ℃ for 10 h. After the reaction is finished, the metal-free solid catalyst CAT-1 for synthesizing the linear carbonate can be obtained by separating, washing with water until the pH value is 7 and drying at 100 ℃ overnight.
FIG. 1 shows the general g-C obtained by direct calcination of dicyanodiamine, melamine or urea 3 N 4 Materials and N of CAT-1 catalyst prepared in example 1 2 Adsorption and desorption isotherms. General g-C 3 N 4 To N 2 The adsorption amount of (A) is very low, and compared with CAT-1, the adsorption amount of (A) is remarkably improved. This indicates that CAT-1 is more common than g-C 3 N 4 Has more abundant pore structure. Common g-C calculated from BET equation 3 N 4 And CAT-1 has specific surface areas of 9 and 85m, respectively 2 g -1 Further illustrating that the latter have a higher specific surface. In heterogeneous catalytic reactions, a higher specific surface is beneficial for exposing more active sites to the catalyst, thus improving its catalytic activity.
FIG. 2 is a general g-C 3 N 4 And the X photoelectron spectrum of CAT-1. The N1 s orbital diagram can be used for analyzing the bonding mode and the content of nitrogen elements in the catalyst. Wherein the binding energies of 398.5, 399.4 and 401.1eV correspond to g-C 3 N 4 Sp of meso-tris-triazine 2 Hybridized nitrogen, nitrogen bridging the tris-s-triazine and nitrogen at the edges of the graphite-like layer (figure 3). Wherein the first nitrogen is non-basic. While the second nitrogen is much more basic than the last nitrogen. Therefore, it is a catalytically active site in a base-catalyzed reaction such as transesterification. The peak integral calculation analysis of fig. 2 shows that: the second nitrogen being in the general g-C 3 N 4 And CAT-1 in 22% and 34%, respectively. Further evidence that the catalytic activity of the catalyst of the invention is higher than that of the common g-C 3 N 4 A material.
Example 2
Melamine is taken as a precursor, and is roasted for 2 hours at the temperature of 550 ℃ to prepare g-C 3 N 4 A material. Mixing the above g-C 3 N 4 After grinding, the material is continuously roasted for 2h at the temperature of 550 ℃ to obtain the stripped g-C 3 N 4 Material eg-C 3 N 4 . 0.5 part by mass of eg-C 3 N 4 And 20 parts by mass of aqueous ammonia (0.1 mol. L) -1 ) Adding into a high-pressure reaction kettle. The reaction was stirred at 30 ℃ for 8 h. After the reaction is finished, the metal-free solid catalyst CAT-2 for synthesizing the linear carbonate can be obtained by separating, washing with water until the pH value is 7 and drying at 80 ℃ overnight.
Example 3
Roasting urea as precursor at 550 deg.c for 4 hr to obtain g-C 3 N 4 A material. Mixing the above g-C 3 N 4 After the material is ground, the material is continuously roasted for 2 hours at the temperature of 550 ℃ to obtain the stripped g-C 3 N 4 Material eg-C 3 N 4 .1 part by mass of eg-C 3 N 4 And 20 parts by mass of aqueous ammonia (2 mol. L) -1 ) Adding into a high-pressure reaction kettle. The reaction was stirred at 140 ℃ for 12 h. After the reaction is finished, the metal-free solid catalyst CAT-3 for synthesizing the linear carbonate can be obtained by separating, washing with water until the pH value is 7 and drying at 120 ℃ overnight.
Example 4
Dicyanodiamine is used as a precursor, and is roasted for 3 hours at the temperature of 550 ℃ to prepare the g-C 3 N 4 A material. Mixing the above g-C 3 N 4 After grinding, the material is continuously roasted for 2h at the temperature of 550 ℃ to obtain the stripped g-C 3 N 4 Material eg-C 3 N 4 . 0.6 part by mass of eg-C 3 N 4 And 20 parts by mass of aqueous ammonia (1 mol. L) -1 ) Adding into a high-pressure reaction kettle. The reaction was stirred at 90 ℃ for 10 h. After the reaction is finished, the metal-free solid catalyst CAT-4 for synthesizing the linear carbonate can be obtained by separating, washing with water until the pH value is 7 and drying at 90 ℃ overnight.
Example 5
Using dicyanodiamine as a precursor, roasting for 3 hours at the temperature of 550 ℃ to obtain g-C 3 N 4 A material. Mixing the above g-C 3 N 4 After grinding, the material is continuously roasted for 2h at the temperature of 550 ℃ to obtain the stripped g-C 3 N 4 Material eg-C 3 N 4 . 0.8 part by mass of eg-C 3 N 4 20 parts by mass of pyrrole (0.3 mol. L) was added -1 ) Adding into a high-pressure reaction kettle. Stirring was carried out at 120 ℃ for 10 h. After the reaction is finished, the metal-free solid catalyst CAT-5 for synthesizing the linear carbonate can be obtained by separating, washing with water until the pH value is 7 and drying at 100 ℃ overnight.
Example 6
Using dicyanodiamine as a precursor, roasting for 3 hours at the temperature of 550 ℃ to obtain g-C 3 N 4 A material. Mixing the above g-C 3 N 4 After grinding, the material is continuously roasted for 2h at the temperature of 550 ℃ to obtain the stripped g-C 3 N 4 Material eg-C 3 N 4 . 0.6 part by mass of eg-C 3 N 4 To 20 parts by mass of pyridine (0.3 mol. L) was added -1 ) Adding into a high-pressure reaction kettle. Stirring was carried out at 120 ℃ for 10 h. After the reaction is finished, the metal-free solid catalyst CAT-6 for synthesizing the linear carbonate can be obtained by separating, washing with water until the pH value is 7 and drying at 100 ℃ overnight.
Comparative example 1
Using dicyanodiamine as a precursor, roasting for 3 hours at the temperature of 550 ℃ to obtain g-C 3 N 4 A material. Mixing the above g-C 3 N 4 After grinding, the material is continuously roasted for 2h at the temperature of 550 ℃ to obtain the stripped g-C 3 N 4 Material (eg-C) 3 N 4 ) And is used for synthesizing a metal-free solid catalyst D-CAT-1 of linear carbonate.
Comparative example 2
Using dicyanodiamine as a precursor, roasting for 3 hours at the temperature of 550 ℃ to obtain g-C 3 N 4 A material. 0.6 part by mass of the above-mentioned g-C 3 N 4 The material and 20 parts by mass of aqueous ammonia (0.3 mol. L) -1 ) Adding into a high-pressure reaction kettle. The reaction was stirred at 120 ℃ for 10 h. After the reaction is finished, the metal-free solid catalyst D-CAT-2 for synthesizing the linear carbonate can be obtained by separating, washing with water until the pH value is 7 and drying at 100 ℃ overnight.
Evaluation conditions of transesterification synthesis of linear carbonate catalyst:
the above catalyst is applied to a synthesis reaction of a linear carbonate represented by DMC. The reaction conditions were as follows: the catalyst dosage is 0.2 part by mass, the EC is 2.2 parts by mass, the methanol or the ethanol is 8 parts by mass, the reaction temperature is 110-. After the reaction, the reaction system was centrifuged. The results of the analysis were checked by gas chromatography (SP6890) equipped with a FID detector. Specific results are shown in table 1.
TABLE 1 catalysts in EC and CH 3 OH (or C) 2 H 5 OH) catalytic Activity of transesterification reactions
After the reaction is finished, washing the catalyst by deionized water and absolute ethyl alcohol, and drying the catalyst at 100 ℃ overnight to obtain the recovered catalyst. CAT-1 catalyst in EC and CH 3 The recycling properties in the transesterification of OH to DMC are shown in Table 2.
TABLE 2 catalyst CAT-1 in EC and CH 3 Cyclic use of OH transesterification
As can be seen from Table 2, the conversion of EC and DMC yield of the catalyst were substantially stable after four recycles, indicating that the catalyst could be reused.
Claims (2)
1. A metal-free solid catalyst for synthesizing linear carbonate is characterized in that the preparation method of the metal-free solid catalyst comprises the following steps:
using dicyanodiamine as a precursor, roasting for 3 hours at the temperature of 550 ℃ to obtain g-C 3 N 4 A material; mixing the above g-C 3 N 4 After grinding, the material is continuously roasted for 2h at the temperature of 550 ℃ to obtain the stripped g-C 3 N 4 Material eg-C 3 N 4 (ii) a 0.6 part by mass of eg-C 3 N 4 And 20 parts by mass of 0.3 mol/L −1 Adding the ammonia water into a high-pressure reaction kettle, and stirring at 120 DEG CReacting for 10h, separating after the reaction is finished, washing with water until the pH value is 7, and drying at 100 ℃ overnight to obtain the metal-free solid catalyst for synthesizing the linear carbonate;
or
Roasting urea as precursor at 550 deg.c for 4 hr to obtain g-C 3 N 4 A material; mixing the above g-C 3 N 4 After grinding, the material is continuously roasted for 2h at the temperature of 550 ℃ to obtain the stripped g-C 3 N 4 Material eg-C 3 N 4 (ii) a 1 part by mass of eg-C 3 N 4 And 20 parts by mass of 2 mol. L −1 Adding the ammonia water into a high-pressure reaction kettle, stirring and reacting for 12 hours at 140 ℃, separating after the reaction is finished, washing with water until the pH value is 7, and drying overnight at 120 ℃ to obtain a metal-free solid catalyst CAT-3 for synthesizing linear carbonate;
the catalyst is used for synthesizing linear carbonate by taking methanol or ethanol and ethylene carbonate as raw materials.
2. The metal-free solid catalyst for synthesizing linear carbonate according to claim 1, wherein the specific method for synthesizing linear carbonate is: according to the raw material dosage of 8 parts by mass of methanol or ethanol and 2.2 parts by mass of ethylene carbonate, 0.2 part by mass of a metal-free solid catalyst is added to react for 4 hours at the reaction temperature of 110-130 ℃ under the condition that the reaction filling gas is nitrogen, so as to synthesize the linear carbonate.
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