CN112823879B - Application of cerium-based catalyst in preparation of dimethyl carbonate through direct conversion of carbon dioxide and methanol - Google Patents

Application of cerium-based catalyst in preparation of dimethyl carbonate through direct conversion of carbon dioxide and methanol Download PDF

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CN112823879B
CN112823879B CN201911150805.3A CN201911150805A CN112823879B CN 112823879 B CN112823879 B CN 112823879B CN 201911150805 A CN201911150805 A CN 201911150805A CN 112823879 B CN112823879 B CN 112823879B
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李杲
郑凯
李志敏
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention provides an application of a cerium-based catalyst in preparing dimethyl carbonate by directly converting carbon dioxide and methanol, wherein the cerium-based catalyst comprises the following active components: mxCe1‑xOy(x is more than or equal to 0 and less than or equal to 0.2 and y is more than or equal to 1.9 and less than or equal to 2), and M is a metal element, wherein M is Mn, Cu, Ti, Bi, Zr, Fe, Al, Mg and the like. The invention provides a method for using a cerium-based nano-composite catalyst material in a reaction for preparing dimethyl carbonate, which is simple to operate and has universality. Compared with the existing particle catalyst technology, the catalyst has the advantages of higher specific surface area, lower pressure drop, excellent mechanical stability and thermal stability, and is particularly suitable for continuous reaction operation. Under the condition of not using any dehydrating agent and under the reaction condition of 140 ℃, the conversion rate of the methanol can reach 24.3 percent, and the selectivity of the dimethyl carbonate can reach 78.6 percent.

Description

Application of cerium-based catalyst in preparation of dimethyl carbonate through direct conversion of carbon dioxide and methanol
Technical Field
The invention belongs to the technical field of nano catalytic materials, and particularly relates to an application of a cerium-based catalyst in direct conversion of carbon dioxide and methanol into dimethyl carbonate.
Background
Dimethyl carbonate (DMC) is considered an environmentally friendly solvent and reagent due to its low toxicity, high biodegradability and special reactivity. Dimethyl carbonate has proven to be an effective substitute for halogen and sulfate reagents, and is suitable for carbonation, hydrochlorination and the likeAn important chemical reaction. Traditionally, dimethyl carbonate is synthesized by methanol phosphating, methanol oxidative carbonization and esterification, leaving serious environmental problems. In this regard, direct synthesis of dimethyl carbonate from the reaction of methanol with carbon dioxide has attracted considerable attention. However, despite the green nature of the reaction, CO2The high activation energy barrier and the thermodynamic limitations of the reaction result in a low yield of dimethyl carbonate. The previous results show that2Has good catalytic performance in the dehydration reaction, thereby opening up the possibility of the application of the oxide in the synthesis of the dimethyl carbonate. However, the exposed CeO2The specific surface area is generally low, the durability to the calcination process at high temperature is poor, and the catalyst is easily and rapidly deactivated during the catalytic reaction (less than 10 hours).
Based on particulate CeO2The use of the catalyst in the direct synthesis of dimethyl carbonate is severely limited by the low conversion of methanol (e.g. 2-5%). This is mainly due to the accumulation of water formed, which cannot be removed in time during the catalytic process in the fixed bed reactor, shifting the equilibrium to the left of the reaction (Le Chatelier principle). Therefore, a dehydrating agent (e.g., 2-cyanide) is necessary to achieve high methanol conversion. However, dehydrating agents are generally expensive and not environmentally friendly, and therefore it is very worthwhile and desirable to develop in the "green chemistry" concept a production process for the synthesis of dimethyl carbonate which is economically efficient, less toxic and which does not require dehydrating agents.
Disclosure of Invention
The invention provides a cerium-based nano composite material catalyst for a reaction of directly converting carbon dioxide and methanol into dimethyl carbonate. The chemical formula can be represented as: mxCe1-xOy(x is more than or equal to 0 and less than or equal to 0.2 and y is more than or equal to 1.9 and less than or equal to 2), wherein y represents the stoichiometric number of O and is obtained by balancing the valence of metal elements in the molecular formula. M is a metal element, wherein M is Mn, Cu, Ti, Bi, Zr, Fe, Al, Mg and the like, and the method is simple to operate and universal and is used for synthesizing a series of cerium-based nanocomposite materials. The invention relates to a nano composite material catalyst M for directly converting carbon dioxide and methanol into dimethyl carbonatexCe1-xOy(x is more than or equal to 0 and less than or equal to 0.2 and y is more than or equal to 1.9 and less than or equal to 2), compared with the prior granular catalyst technology, the catalyst has higher specific surface area, lower pressure drop and excellent mechanical stability and thermal stability, and is particularly suitable for continuous reaction operation. Under the condition of no dehydrating agent and 140 ℃, the conversion rate of the methanol can reach 24.3 percent, and the selectivity of the dimethyl carbonate can reach 78.6 percent.
Based on the technical scheme, the following steps are preferred: the preparation method of the cerium-based nano composite catalyst comprises the following steps: cerium salt and metal salt compound are dissolved in deionized water, and certain amount of alkali is added and maintained at 90 deg.c for several hr. Filtering and collecting the precipitate, washing, drying and calcining the obtained precipitate to obtain MxCe1-xOyParticles. The obtained MxCe1-xOyAdding deionized water into the powder, grinding to obtain slurry, coating the slurry on a carrier, drying and calcining to obtain the required catalyst. Bimetallic composite oxide MxCe1-xOyThe particles were characterized by X-ray diffractometry and transmission electron microscopy. The evaluation experiment of the catalyst activity is carried out on a continuous fixed bed reactor, and the qualitative and quantitative results of the gas components are carried out by gas chromatographic analysis. The specific preparation process of the catalyst of the invention is as follows:
(1) dissolving a Ce precursor and an M precursor in deionized water to obtain a salt solution A, wherein the total concentration of the Ce salt and the M precursor in the salt solution A is 0.01-0.1 mol/L; dissolving alkali in deionized water to obtain an alkali solution B, wherein the concentration of the alkali solution B is 0.6-1.0 mol/L; in the salt solution A, the molar ratio of the Ce precursor to the M precursor is 8-9.5: 2-0.5;
(2) mixing a salt solution A and an alkali solution B, wherein the molar ratio of the alkali solution B to the solute of the salt solution A is 3:1, stirring for 4-6h at 90-100 ℃, filtering, washing and drying;
(3) calcining the product dried in the step (2) at the temperature of 300-500 ℃ for 4-6h to obtain an active component;
(4) mixing and grinding the obtained active component and deionized water to obtain active component slurry, coating the active component slurry on a carrier, and drying;
(5) and (3) calcining the dried product in the step (4) at the temperature of 300-500 ℃ for 4-6h to obtain the cerium-based catalyst.
Based on the technical scheme, preferably, the Ce precursor is cerium nitrate, cerium sulfate, cerium chloride and the like; the M metal precursor is nitrate, sulfate, chloride and the like of corresponding metal.
Based on the technical scheme, the drying temperature in the step (2) and the drying temperature in the step (5) are preferably 80-120 ℃, and the drying time is preferably 12-24 h.
Based on the above technical scheme, preferably, the alkali in the step (1) is urea, ammonia water, sodium carbonate, sodium hydroxide, potassium hydroxide, or the like.
The catalyst of the invention is an integrally formed catalyst, and a carrier is coated with sufficient active components and sintered and formed after being fully coated.
The reaction temperature is 100-180 ℃, the reaction pressure is 2-3MPa, the feed composition molar ratio of the methanol to the carbon dioxide is 2:1-1:1, and the space velocity of the reaction is 2600-3000 ml/g catalyst/h.
The evaluation method of the using condition and the using result of the catalyst comprises the following steps: the catalyst dosage is 500mg, the reaction temperature is 100 ℃ and 180 ℃, the reaction pressure is 2-3MPa, the feeding composition ratio of methanol/carbon dioxide is 2/1 (molar ratio), and the space velocity is 2880 ml/g catalyst/h. The reaction product was directly analyzed by gas chromatography. After the reaction system was stabilized, the average of the concentrations of the reactants and products was obtained by sampling several times, and the conversion of methanol (conv.) and the selectivity of dimethyl carbonate (sel.) were calculated by the following formula:
Figure BDA0002283482120000021
Figure BDA0002283482120000022
cirepresenting the substance i (i ═ DMC, DME, HCHO, CO),CH3OH) wherein DMC represents dimethyl carbonate, DME represents dimethyl ether, HCHO represents formaldehyde, CH3OH represents methanol and CO represents carbon monoxide.
Advantageous effects
(1) The invention provides a method for doping a doped metal (M) into CeO2To form MxCe1-xOyThe composite material is used in the reaction of synthesizing dimethyl carbonate to eliminate CeO2Limitation of (2), e.g. Zr-doping with CeO2Nanorod ZrxCe1-xO2Has a higher concentration of oxygen voids (Ov) than CeO2CO is more readily activated by interaction with Ov2Thereby forming a carbonic diester intermediate and further obtaining dimethyl carbonate.
(2) The catalyst has higher specific surface area, lower pressure drop, excellent mechanical stability and thermal stability, and is particularly suitable for continuous reaction operation. And the product water and the dimethyl carbonate in the reaction process can be timely taken away from the reaction system, so that the catalytic efficiency is improved. Under the condition of no dehydrating agent and 140 ℃, the conversion rate of the methanol is 24.3 percent, and the selectivity of the dimethyl carbonate can reach 78.6 percent.
Drawings
FIG. 1 is an X-ray diffraction chart of the catalytically active components prepared in examples 1 to 4 and pure cerium oxide.
FIG. 2 is a transmission electron microscope photograph of the catalytically active components prepared in examples 1 to 4 and pure cerium oxide and a statistical view of the particle size distribution of example 1.
FIG. 3 is a graph (a) showing the catalytic activity of the catalysts prepared in examples 1 to 4 at 140 ℃ for direct preparation of dimethyl carbonate from carbon dioxide and methanol, and a graph (b) showing the catalytic activity of the catalyst prepared in example 1 as a function of temperature.
FIG. 4 shows the catalytically active components Bi prepared in examples 5 to 8xCe1-xOyX-ray diffraction pattern of (a).
FIG. 5 shows the catalytically active components Bi prepared in examples 5 to 8xCe1-xOyTransmission electron microscopy images of (5) and Activity of exampleComponent Bi0.1Ce0.9O1.95Particle size distribution statistical chart.
FIG. 6 is a graph comparing the catalytic activity of the catalysts corresponding to examples 5-8 at 140 ℃ for the direct preparation of dimethyl carbonate from carbon dioxide and methanol.
FIG. 7 shows catalyst B prepared in example 50.1Ce0.9O1.95Is plotted against temperature.
FIG. 8 is a graph of stability tests for the catalyst of example 5, with the two curves in the top half of the graph being the dimethyl carbonate selectivity curve and the bottom half being the methanol conversion curve.
Detailed Description
Example 1
36 mmol of analytically pure (NH)4)2Ce(NO3)6With 4 millimolar analytically pure Ti (SO)4)2Dissolved in deionized water, the mixed solution was introduced into a 1000 ml beaker, and 120mmol of urea was dissolved in 200 ml of deionized water with continuous stirring. The solution system was heated to 90 degrees celsius and held for 5 hours, filtered and the precipitate collected. The precipitate was washed with 2000 ml of deionized water and 300 ml of absolute ethanol. Drying the precipitate in a drying oven at 80 ℃ overnight, and calcining the precipitate in a muffle furnace at 400 ℃ for 4 hours in air to obtain Ti0.1Ce0.9O2Particles of Ti0.1Ce0.9O2See fig. 1 for X-ray diffraction pattern and fig. 2c for transmission electron microscopy), see fig. 2f for particle size distribution statistics). The obtained Ti0.1Ce0.9O2Adding deionized water into the powder to grind to obtain slurry coated on a honeycomb cordierite ceramic carrier (64 grids/cm)-2 Pore size 10 mm, pore depth 25 mm), the loading of the coating was about 0.5 g. Finally, the coated catalyst was dried at 80 degrees celsius for more than 12 hours and calcined in a 400 degree celsius muffle furnace for 4 hours to form a monolithic catalyst. The reaction is carried out under the conditions that the feeding composition ratio of methanol/carbon dioxide is 2/1 (mol), the total space velocity is 2880 ml gcat-1 h-1, the temperature is 100-3a) And b), results were obtained with a methanol conversion of 24.3% and a selectivity to dimethyl carbonate of 78.6%, respectively.
Example 2
The same conditions as in example 1 were used except that the feed ratio was changed to 38 mmol of analytically pure ceric ammonium nitrate and 2 mmol of analytically pure titanium sulfate. Ti0.05Ce0.95O2See fig. 1 for X-ray diffraction pattern and fig. 2b for transmission electron microscopy). The results of the gas chromatography analysis are shown in fig. 3a), the conversion of methanol is 21.6% and the selectivity of dimethyl carbonate is 80.5%.
Example 3
The conditions were the same as in example 1 except that the feed ratio was changed to 34 mmol of analytically pure ceric ammonium nitrate and 6 mmol of analytically pure titanium sulfate, and Ti was added0.15Ce0.85O2See fig. 1 for X-ray diffraction pattern and fig. 2d for transmission electron microscopy pattern). The results of the gas chromatography analysis are shown in fig. 3a), the conversion of methanol is 22.1% and the selectivity of dimethyl carbonate is 76.2%.
Example 4
The conditions were the same as in example 1 except that the charge ratio was changed to 8.0 parts of analytically pure ceric ammonium nitrate and 2.0 parts of analytically pure titanium sulfate, and Ti was added0.2Ce0.8O2See fig. 1 for X-ray diffraction pattern and fig. 2b for transmission electron microscopy). The results of the gas chromatography analysis are shown in fig. 3a), the conversion of methanol is 21.4% and the selectivity of dimethyl carbonate is 74.7%.
Example 5
36 mmol (in terms of molar amount, the same shall apply hereinafter) of analytically pure ammonium cerium nitrate and 4 mmol of analytically pure bismuth nitrate were dissolved in deionized water, and the mixed solution was introduced into a 1000 ml beaker to obtain a solution a, and 120mmol of urea was dissolved in 200 ml of deionized water to obtain a solution B. Gradually dropwise adding the solution B into the solution A, stirring while dropwise adding, measuring the pH value of the solution, controlling the pH value of the solution to be more than or equal to 9, heating the solution system to 90 ℃, keeping the temperature for 5 hours, filtering and collecting precipitates. The precipitate was washed with 2000 ml of deionized water and 500 ml of absolute ethanol. The precipitate was placed in a drying oven at 80 ℃Drying overnight under the condition of temperature, and then calcining for 4 hours in a muffle furnace at 500 ℃ in air to obtain Bi0.1Ce0.9O1.95Particles. The X-ray diffraction pattern and the transmission electron microscope pattern of the active nanoparticles are shown in fig. 4 and fig. 5(c), the loading method of the catalyst and the activity test conditions of the catalyst are the same as those in example 1, and the test result is shown in fig. 6 after the analysis of the gas chromatograph, the conversion rate of methanol is 20.93%, and the selectivity of dimethyl carbonate is 83.5%.
Example 6
The conditions were the same as in example 5 except that the feed ratio was changed to 38 mM analytically pure ceric ammonium nitrate and 2 mM analytically pure bismuth nitrate, and Bi was added0.05Ce0.95O1.97The X-ray diffraction pattern of (a) is shown in fig. 4, the transmission electron micrograph is shown in fig. 5(c), and the results of the gas chromatograph analysis are shown in fig. 6, the conversion of methanol is 13.58%, and the selectivity of dimethyl carbonate is 85.3%.
Example 7
The conditions were the same as in example 5 except that the feed ratio was changed to 34 mmol of analytically pure ceric ammonium nitrate and 6 mmol of analytically pure bismuth nitrate, and Bi was added0.15Ce0.85O1.92The X-ray diffraction pattern of (a) is shown in fig. 4, the transmission electron microscope pattern is shown in fig. 5(d), the analysis by gas chromatography shows the test results in fig. 6, and the results by gas chromatography respectively show that the conversion of methanol is 11.86% and the selectivity of dimethyl carbonate is 75.4%.
Example 8
The conditions were the same as in example 5 except that the feed ratio was changed to 32 mM cerium ammonium nitrate and 4 mM bismuth nitrate0.2Ce0.8O1.90The X-ray diffraction pattern of (a) is shown in fig. 4, the transmission electron microscope pattern is shown in fig. 5(e), the analysis by gas chromatography shows the test results in fig. 6, and the results by gas chromatography respectively show that the conversion of methanol is 9.29% and the selectivity of dimethyl carbonate is 72.4%.

Claims (7)

1. The application of the cerium-based catalyst in the reaction of synthesizing dimethyl carbonate from carbon dioxide and methanol is characterized in that the cerium-based catalyst comprises an active component and a carrier; the molecular formula of the active component is MxCe 1-xOy; wherein x is more than or equal to 0.05 and less than or equal to 0.1; y is more than or equal to 1.9 and less than or equal to 2; and M is bismuth.
2. The application of claim 1, wherein the reaction temperature is 100-180 ℃, the reaction pressure is 2-3MPa, the feeding molar ratio of the methanol/carbon dioxide is 1:1-1:2, and the space velocity of the reaction is 2600-3000 ml/g catalyst/h.
3. Use according to claim 1, wherein the carrier is a honeycomb cordierite ceramic carrier, a homogeneous titania carrier.
4. Use according to claim 1, characterized in that said cerium-based catalyst is prepared by a method comprising the steps of:
(1) dissolving a Ce precursor and an M precursor in deionized water to obtain a salt solution A, wherein the total concentration of the Ce salt and the M precursor in the salt solution A is 0.01-0.1 mol/L; the molar ratio of the Ce precursor to the M precursor is 8-9.5: 2-0.5; dissolving alkali in deionized water to obtain an alkali solution B, wherein the concentration of the alkali solution B is 0.6-1.0 mol/L;
(2) mixing the salt solution A and the alkali solution B, stirring for 4-6h at 90-100 ℃, filtering, washing and drying; the molar ratio of the alkali solution B to the solute in the salt solution A is 3:1,
(3) calcining the product dried in the step (2) at the temperature of 300-500 ℃ for 4-6h to obtain an active component;
(4) mixing and grinding the obtained active component and deionized water to obtain active component slurry, coating the active component slurry on a carrier, and drying;
(5) and (3) calcining the dried product in the step (4) at the temperature of 300-500 ℃ for 4-6h to obtain the cerium-based catalyst.
5. The use according to claim 4, wherein the Ce precursor is cerium nitrate, cerium sulfate, cerium chloride; the M metal precursor is nitrate, sulfate and chloride of corresponding metal.
6. The use of claim 4, wherein the drying temperature in step (2) and step (5) is 80-120 ℃ and the drying time is 12-24 h.
7. The use according to claim 4, wherein the base in step (1) is urea, ammonia, sodium carbonate, sodium hydroxide, potassium hydroxide.
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