CN111514878B - Preparation method of catalyst for synthesizing glycerol carbonate - Google Patents
Preparation method of catalyst for synthesizing glycerol carbonate Download PDFInfo
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- CN111514878B CN111514878B CN202010400164.9A CN202010400164A CN111514878B CN 111514878 B CN111514878 B CN 111514878B CN 202010400164 A CN202010400164 A CN 202010400164A CN 111514878 B CN111514878 B CN 111514878B
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Abstract
The invention provides a preparation method of a catalyst for synthesizing glycerol carbonate, which comprises the following steps: step 1: in the dipping process, metal oxide is taken as a carrier, and a metal salt solution is added, wherein the metal salt solution contains any two of Zn, Zr, Ba and Li; stirring for 12-48 h in the presence of excessive deionized water to obtain a mixed solution; step 2: in the process of impregnation post-treatment, the mixed solution obtained in the step 1 is subjected to rotary evaporation at the temperature of 60-70 ℃, dried at the temperature of 65-80 ℃ for 12-48 h, and roasted at the temperature of 550-700 ℃ for 3-5 h. The catalyst prepared by the method has a supported structure, so that the catalyst has strong stability and high mechanical strength. In addition, the supported metal oxide has the characteristic of strong alkalinity, and can provide more alkaline sites. Lattice doping can also occur between the catalyst and a carrier, and the catalyst has high catalytic activity on the reaction of synthesizing carbonic acid glyceride by exchanging glyceride. The catalyst prepared by the method has the characteristics of high catalytic activity and strong stability.
Description
Technical Field
The invention relates to the technical field of synthesis of glycerol carbonate. In particular to a preparation method of a metal oxide carrier loaded double-metal oxide catalyst and a performance research of synthesizing carbonic acid glyceride by an ester exchange reaction.
Background
In recent years, the international petroleum resource output state is frequently disorganized, so that the problem of shortage of fossil energy reserves is increasingly urgent. The stable supply of energy is very important in both production and life. All countries in the world actively explore alternative energy sources of fossil energy, and the preparation of energy sources by taking renewable biomass as a raw material becomes an important direction.
Biodiesel is a renewable energy source with properties very close to fossil fuels. In addition, it has the advantages of biodegradability, no toxicity, low sulfur content and the like, and is an ideal alternative energy source. However, biodiesel production is typically accompanied by the production of 10 wt% by-product glycerol. The vigorous development of the biodiesel industry results in an excess supply of glycerin and a substantial decrease in price. The research of converting the glycerol into other high value-added chemicals shows a significant meaning.
One of the effective ways to reuse glycerol is to use it to prepare glycerol carbonate. The glycerol carbonate is an important glycerol derivative, has the characteristics of good biodegradability, low toxicity and high boiling point, and is widely applied to a plurality of fields of foods, medicines, cosmetics, coatings, new materials, new energy sources and the like. The common preparation methods comprise urea alcoholysis method and ester exchange method. The method for preparing glycerol carbonate by using glycerol and dimethyl carbonate as raw materials and performing ester exchange through catalysis is favored because of the advantages of high purity of main products, mild reaction conditions and the like.
There are three major catalytic systems reported for this reaction: (1) a metal oxide catalyst; (2) a supported metal oxide catalyst; (3) a metal salt catalyst; (4) an ionic liquid catalyst; (5) an enzyme catalyst. However, the metal salt catalyst and the ionic liquid catalyst are difficult to recover, and the ionic liquid catalyst and the enzyme catalyst have the problem of relatively high cost, so that the latter three catalysts are limited in practical application. Devi (Devi P, Das U, Dalai A K. production of glycerol carbonate using a novel Ti-SBA-15catalyst [ J ]. Chemical Engineering Journal, 2018, 346: 477-488) et al investigated the loading of Ti onto the silica framework of SBA-15 for the catalytic glyceride exchange to produce glycerol carbonate with a yield of 82% and a selectivity of 87%, but the catalytic conversion was not high. The preparation of glycerol carbonate by using mixed oxide CaO-PbO to catalyze glyceride exchange is researched by using Kanlijia (Kanlijia, Zhao Xinqiang, Anhualiang and the like, CaO-PbO to catalyze transesterification to synthesize glycerol carbonate [ J ]. petrochemical industry, 2011, 40 (2): 140:. 145), and the like, wherein the yield of the glycerol carbonate reaches 97.8%, but the catalyst is not strong in stability.
Therefore, it is necessary to find a catalyst with high activity and strong stability to study the glyceride exchange reaction. Compared with a non-supported catalyst, the supported catalyst has the advantages of high mechanical strength and strong stability, Ba is one of alkaline earth metals, BaO has extremely strong alkalinity, and the stronger the alkalinity of metal oxides, the more alkaline sites are correspondingly, and the better the catalytic glycerol conversion effect is.
Disclosure of Invention
The technical problem is as follows: the invention provides a preparation method and application of a bimetallic supported catalyst for synthesizing glycerol carbonate. The catalyst has high activity, high selectivity, high stability and good recycling performance.
The technical scheme is as follows: the preparation method of the catalyst for synthesizing the glycerol carbonate is prepared according to the following steps:
step 1: impregnation process
Taking a metal oxide as a carrier, and adding a metal salt solution, wherein the metal salt solution contains any two of Zn, Zr, Ba and Li; stirring for 12-48 h in the presence of excessive deionized water to obtain a mixed solution;
step 2: post-dip treatment process
And (3) carrying out rotary evaporation on the mixed solution obtained in the step (1) at the temperature of 60-70 ℃, drying at the temperature of 65-80 ℃ for 12-48 h, and roasting at the temperature of 550-700 ℃ for 3-5 h.
Wherein the content of the first and second substances,
the metal oxide in the step 1 is titanium oxide and gamma-Al2O3One or more of cerium oxide or zirconium oxide.
The metal salt solution in the step 1 is any two of zinc nitrate, zirconium nitrate, barium nitrate or lithium nitrate aqueous solution.
The catalyst for synthesizing the glycerol carbonate is characterized in that the total load of any two of Zn, Zr, Ba and Li on the carrier is 1-20 wt% of the mass of the carrier.
The molar ratio of any two of Zn, Zr, Ba and Li in the catalyst for synthesizing the glycerol carbonate is 3: 1; 2: 1; 1: 1; 1: 2; 1: 3.
The catalyst for synthesizing the glycerol carbonate is applied to the reaction of glycerol and any one or more of dimethyl carbonate, diethyl carbonate and propylene carbonate as raw materials for synthesizing the glycerol carbonate.
Has the advantages that: the catalyst prepared by the method has a supported structure, so that the catalyst has strong stability and high mechanical strength. In addition, the supported metal oxide has the characteristic of strong alkalinity, and can provide more alkaline sites. Lattice doping can also occur between the catalyst and a carrier, and the catalyst has high catalytic activity on the reaction of synthesizing carbonic acid glyceride by exchanging glyceride.
Detailed Description
The preparation method of the catalyst for synthesizing the glycerol carbonate is prepared according to the following steps:
step 1: impregnation process
Weighing a certain amount of metal oxide as a carrier, and adding a metal salt solution, wherein the metal salt solution contains any two of Zn, Zr, Ba and Li; stirring for 12-48 h in the presence of excessive deionized water.
Step 2: post-dip treatment process
And (3) carrying out rotary evaporation on the mixed solution obtained in the step (1) at the temperature of 60-70 ℃, drying at the temperature of 65-80 ℃ overnight, and roasting at the temperature of 550-700 ℃ for 4-5 h.
Wherein the content of the first and second substances,
the metal oxide in the step 1 is titanium oxide and gamma-Al2O3Any one of cerium oxide and zirconium oxide.
The metal salt solution in the step 1 is any two of zinc nitrate, zirconium nitrate, barium nitrate and lithium nitrate aqueous solutions.
The total loading amount of the two metals on the carrier in the supported catalyst in the step 1 is 1-20 wt% of the mass of the carrier.
The molar ratio of two metals in the supported catalyst in the step 1 is 3: 1; 2: 1; 1: 1; 1: 2; 1: 3.
and step 1, weighing the mass of the soluble metal salt according to the required total loading of the two metals and the molar ratio of the two metal atoms.
The glycerol carbonate catalyst synthesized by glycerol ester exchange prepared by the invention can catalyze glycerol and various esters to carry out various ester exchange reactions, and the adopted ester is one or more of dimethyl carbonate, diethyl carbonate and propylene carbonate.
The present invention is further illustrated by the following examples, which are intended to be illustrative only and not to limit the scope of the invention. All the technical solutions obtained by means of equivalent substitution or equivalent transformation are within the scope of the present invention.
Example 1:
1) 5g of cerium oxide, 0.9380g of barium nitrate and 0.0825g of lithium nitrate were weighed into a 100mL round-bottomed flask, 50mL of deionized water was poured therein, and the solid powder was thoroughly mixed therewith and stirred at room temperature for 24 hours.
2) And (2) carrying out vacuum rotary evaporation on the mixed solution obtained in the step 1) at 70 ℃, drying at 85 ℃ for 6h, roasting at 600 ℃ for 5h, and cooling to obtain the bimetallic supported catalyst.
3) 0.117g of the catalyst prepared by the above method was placed in a 250mL round bottom flask, 2.3g of glycerol and 4.5g of dimethyl carbonate were added, mixed well, and an appropriate amount of magnetite was added. The neck of the round bottom flask is connected with a spherical condenser pipe, and condensed water is introduced. Starting stirring, adjusting the rotating speed of the magnetic stirrer to a proper size, and heating to 85 ℃ in an oil bath for reaction for 10 hours. The catalyst was removed from the resulting feed solution, and the product composition was analyzed by gas chromatography, giving a yield of 72.6% of glycerol carbonate.
Example 2:
1) 5g of cerium oxide, 0.9303g of barium nitrate and 0.1227g of lithium nitrate were weighed into a 100mL round-bottomed flask, 50mL of deionized water was poured therein, and the solid powder was thoroughly mixed therewith and stirred at room temperature for 24 hours.
2) And (2) carrying out vacuum rotary evaporation on the mixed solution obtained in the step 1) at 70 ℃, drying at 85 ℃ for 6h, roasting at 600 ℃ for 5h, and cooling to obtain the bimetallic supported catalyst.
3) 0.117g of the catalyst prepared by the above method was placed in a 250mL round bottom flask, 2.3g of glycerol and 4.5g of dimethyl carbonate were added, mixed well, and an appropriate amount of magnetite was added. The neck of the round bottom flask is connected with a spherical condenser pipe, and condensed water is introduced. Starting stirring, adjusting the rotating speed of the magnetic stirrer to a proper size, and heating to 85 ℃ in an oil bath for reaction for 10 hours. The catalyst was removed from the resulting feed solution, and the product composition was analyzed by gas chromatography, whereby the yield of glycerol carbonate was 89.79%.
Example 3:
1) 5g of cerium oxide, 0.9078g of barium nitrate and 0.2395g of lithium nitrate were weighed into a 100mL round-bottomed flask, 50mL of deionized water was poured therein, and the solid powder was thoroughly mixed therewith and stirred at room temperature for 24 hours.
2) And (2) carrying out vacuum rotary evaporation on the mixed solution obtained in the step 1) at 70 ℃, drying at 85 ℃ for 6h, roasting at 600 ℃ for 5h, and cooling to obtain the bimetallic supported catalyst.
3) 0.117g of the catalyst prepared by the above method was placed in a 250mL round bottom flask, 2.3g of glycerol and 4.5g of dimethyl carbonate were added, mixed well, and an appropriate amount of magnetite was added. The neck of the round bottom flask is connected with a spherical condenser pipe, and condensed water is introduced. Starting stirring, adjusting the rotating speed of the magnetic stirrer to a proper size, and heating to 85 ℃ in an oil bath for reaction for 10 hours. The catalyst was removed from the resulting feed solution, and the product composition was analyzed by gas chromatography, whereby the yield of glycerol carbonate was 93.26%.
Example 4:
1) 5g of cerium oxide, 0.8661g of barium nitrate and 0.4569g of lithium nitrate were weighed into a 100mL round-bottomed flask, 50mL of deionized water was poured therein, and the solid powder was thoroughly mixed therewith and stirred at room temperature for 24 hours.
2) And (2) carrying out vacuum rotary evaporation on the mixed solution obtained in the step 1) at 70 ℃, drying at 85 ℃ for 6h, roasting at 600 ℃ for 5h, and cooling to obtain the bimetallic supported catalyst.
3) 0.117g of the catalyst prepared by the above method was placed in a 250mL round bottom flask, 2.3g of glycerol and 4.5g of dimethyl carbonate were added, mixed well, and an appropriate amount of magnetite was added. The neck of the round bottom flask is connected with a spherical condenser pipe, and condensed water is introduced. Starting stirring, adjusting the rotating speed of the magnetic stirrer to a proper size, and heating to 85 ℃ in an oil bath for reaction for 10 hours. The catalyst in the obtained feed liquid is removed, the composition of the product is analyzed by gas chromatography, and the yield of the glycerol carbonate is 93.06%.
Example 5:
1) 5g of cerium oxide, 0.8280g of barium nitrate and 0.6552g of lithium nitrate were weighed into a 100mL round-bottomed flask, 50mL of deionized water was poured therein, and the solid powder was thoroughly mixed therewith and stirred at room temperature for 24 hours.
2) And (2) carrying out vacuum rotary evaporation on the mixed solution obtained in the step 1) at 70 ℃, drying at 85 ℃ for 6h, roasting at 600 ℃ for 5h, and cooling to obtain the bimetallic supported catalyst.
3) 0.117g of the catalyst prepared by the above method was placed in a 250mL round bottom flask, 2.3g of glycerol and 4.5g of dimethyl carbonate were added, mixed well, and an appropriate amount of magnetite was added. The neck of the round bottom flask is connected with a spherical condenser pipe, and condensed water is introduced. Starting stirring, adjusting the rotating speed of the magnetic stirrer to a proper size, and heating to 85 ℃ in an oil bath for reaction for 10 hours. The catalyst was removed from the resulting feed solution, and the product composition was analyzed by gas chromatography, whereby the yield of glycerol carbonate was 94.18%.
Example 6:
1) 5g of cerium oxide, 0.7931g of barium nitrate and 0.8369g of lithium nitrate were weighed into a 100mL round-bottomed flask, 50mL of deionized water was poured therein, and the solid powder was thoroughly mixed therewith and stirred at room temperature for 24 hours.
2) And (2) carrying out vacuum rotary evaporation on the mixed solution obtained in the step 1) at 70 ℃, drying at 85 ℃ for 6h, roasting at 600 ℃ for 5h, and cooling to obtain the bimetallic supported catalyst.
3) 0.117g of the catalyst prepared by the above method was placed in a 250mL round bottom flask, 2.3g of glycerol and 4.5g of dimethyl carbonate were added, mixed well, and an appropriate amount of magnetite was added. The neck of the round bottom flask is connected with a spherical condenser pipe, and condensed water is introduced. Starting stirring, adjusting the rotating speed of the magnetic stirrer to a proper size, and heating to 85 ℃ in an oil bath for reaction for 10 hours. The catalyst was removed from the resulting feed solution, and the product composition was analyzed by gas chromatography, whereby the yield of glycerol carbonate was 93.39%.
Claims (3)
1. A preparation method of a catalyst for synthesizing glycerol carbonate is characterized in that the catalyst is prepared according to the following steps:
step 1: impregnation process
Taking cerium oxide as a carrier, adding a barium nitrate and lithium nitrate aqueous solution, and stirring for 12-48 hours in the presence of excessive deionized water to obtain a mixed solution;
step 2: post-dip treatment process
Carrying out rotary evaporation on the mixed solution obtained in the step 1 at the temperature of 60-70 ℃, drying at the temperature of 65-80 ℃ for 12-48 h, and roasting at the temperature of 550-700 ℃ for 3-5h, wherein the molar ratio of Ba to Li in the catalyst for synthesizing the glycerol carbonate is 3: 1; 2: 1; 1: 1; 1: 2; 1:3.
2. The process for preparing a catalyst for synthesizing glycerol carbonate according to claim 1, wherein in said catalyst for synthesizing glycerol carbonate, the total loading of Ba and Li on said carrier is 1 wt% to 20 wt% of the mass of the carrier.
3. The use of the catalyst prepared by the method of claim 1 for synthesizing glycerol carbonate, wherein the catalyst is used for synthesizing glycerol carbonate by using glycerol and one or more of dimethyl carbonate, diethyl carbonate and propylene carbonate as reaction raw materials.
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Citations (4)
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| CN101041130A (en) * | 2007-04-12 | 2007-09-26 | 上海三瑞化学有限公司 | Catalysts for solid base for producing biodiesel |
| CN102186837A (en) * | 2008-10-17 | 2011-09-14 | 巴斯夫欧洲公司 | Method and catalysts for producing cyclic carbonates |
| CN102199493A (en) * | 2010-03-23 | 2011-09-28 | 华东理工大学 | Environmentally-friendly preparation method for biological diesel oil under catalysis of solid base |
| CN103191768A (en) * | 2013-03-22 | 2013-07-10 | 南京工业大学 | Mesoporous solid strong-alkaline catalyst and preparation method and application of catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101041130A (en) * | 2007-04-12 | 2007-09-26 | 上海三瑞化学有限公司 | Catalysts for solid base for producing biodiesel |
| CN102186837A (en) * | 2008-10-17 | 2011-09-14 | 巴斯夫欧洲公司 | Method and catalysts for producing cyclic carbonates |
| CN102199493A (en) * | 2010-03-23 | 2011-09-28 | 华东理工大学 | Environmentally-friendly preparation method for biological diesel oil under catalysis of solid base |
| CN103191768A (en) * | 2013-03-22 | 2013-07-10 | 南京工业大学 | Mesoporous solid strong-alkaline catalyst and preparation method and application of catalyst |
Non-Patent Citations (1)
| Title |
|---|
| "Tandem Synthesis of Glycidol via Transesterification of Glycerol with DMC over Ba-Mixed Metal Oxide Catalysts";Sharda E. Kondawar et al.;《ACS Sustainable Chemistry & Engineering》;20161213;第5卷;第1763-1774页 * |
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