CN114768803A - Catalyst for synthesizing fully deuterated methanol, preparation method and application thereof - Google Patents

Catalyst for synthesizing fully deuterated methanol, preparation method and application thereof Download PDF

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CN114768803A
CN114768803A CN202210491133.8A CN202210491133A CN114768803A CN 114768803 A CN114768803 A CN 114768803A CN 202210491133 A CN202210491133 A CN 202210491133A CN 114768803 A CN114768803 A CN 114768803A
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CN114768803B (en
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杨晓丽
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Nanjing Ningdeuterium Biotechnology Co ltd
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Abstract

The invention relates to a catalyst for synthesizing fully deuterated methanol, a preparation method and application thereof. The catalyst mainly comprises an oxide carrier and metal components, wherein the carrier components are at least two of cerium oxide, zirconium oxide, chromium oxide and zinc oxide, and the metal components are one of iron, copper, palladium, platinum and rhodium. The catalyst is prepared by preparing a carrier precursor by a coprecipitation method, obtaining a carrier by a roasting method, and then loading a metal component by a deposition-precipitation method. Wherein the mass content of the metal component in the catalyst is 0.5-10%. The catalyst has the advantages of simple and reliable preparation method, higher activity, deuterated methanol selectivity and the like, and the deuteration rate of the product can reach 99.9 percent.

Description

Catalyst for synthesizing fully deuterated methanol, preparation method and application thereof
Technical Field
The invention relates to a catalyst for synthesizing fully deuterated methanol, a preparation method and application thereof, and belongs to the technical field of chemical synthesis.
Background
Deuterium is a stable form of nonradioactive isotope of hydrogen in nature, and has larger atomic mass than hydrogen, so that a C-D bond is more stable than a C-H bond, and the deuterium is widely applied to biological medicines, photoelectric display and nuclear magnetic resonance detection. For example, substitution of deuterium for hydrogen in a drug molecule can block metabolic sites and reduce the production of toxic metabolites. The deuterated methanol is an important chemical raw material and a deuterated drug intermediate, can be used for preparing industrial deuterated drugs and macromolecular deuterium labeled compounds, can be used as a nuclear magnetic resonance hydrogen spectrum detection reagent and an isotope tracer to monitor species and molecular structure changes in the reaction process, and provides important technical support for exploring reaction mechanisms and product distribution. The commonly used preparation method of the deuterium methanol is to utilize hydrogen-deuterium (H-D) exchange reaction, and researchers can also prepare the deuterium methanol by deuterating 1-methoxy-1, 3-cyclohexadiene, but the method can not ensure the complete deuterium substitution of hydrogen atoms, and the complex diversity of the prepared product brings difficulty to post-treatment, use and the like.
On the other hand, the heavy use of fossil fuels has led to a tightening of energy supplies and the greenhouse gas CO2The sudden increase in emissions has led to increasingly severe energy crisis and environmental problems. Currently, CO is mixed2The capture and conversion of the chemical with high added value are highly valued internationally, and an important way is provided for the recycling of the carbon. Based on the method, carbon dioxide and deuterium gas are used as raw materials, and the deuterated methanol is prepared through thermocatalysis; a catalyst used in the process and a preparation method thereof are provided, and the catalyst with excellent catalytic performance is prepared by mixing oxide active components.
Currently, there are also reports of methods for preparing deuterated methanol in the prior art, for example, chinese patents CN 112321388A, CN 112675875A, CN 11116313A, CN108250041B and CN109078638A both disclose methods for preparing deuterated methanol from deuterium and carbon monoxide as raw materials, wherein chinese patent CN 112321388 a mainly introduces the characteristics of the reaction, and others introduce the composition and preparation method of the catalyst; the catalyst used in the Chinese patent CN 11116313A is at least one of zinc oxide, copper oxide, aluminum oxide and platinum oxide, and the Chinese patent CN108250041B catalyst is one or a combination of more of gold oxide, platinum oxide and rhodium oxide; chinese patent CN109078638A discloses CuZnCeAlO as catalyst, and chinese patent CN 112675875 a also discloses CuZnAlO as catalyst.
However, there is no prior art disclosing a method for preparing deuterated methanol using deuterium and carbon dioxide gas as raw materials, nor is there a prior art disclosing a catalyst applicable to the preparation of deuterated methanol from deuterium and carbon dioxide.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a catalyst for synthesizing deuterium-substituted methanol, a preparation method and application thereof.
The first purpose of the invention is to provide a catalyst for synthesizing the deuterium-substituted methanol, the catalyst can be well applied to the reaction of preparing the deuterium-substituted methanol by deuterium gas and carbon dioxide, and has the characteristics of high activity and high selectivity, and the deuteration rate of the generated deuterium-substituted methanol is as high as 99.9%.
The second purpose of the invention is to provide a preparation method of the catalyst for preparing the deuterium-substituted methanol from deuterium gas and carbon dioxide, wherein the preparation method is simple and reliable and has universality.
The third objective of the present invention is to provide an application of the above catalyst, specifically to a method for catalyzing a reaction of preparing deuterated methanol from deuterium and carbon dioxide gas as raw materials by using the above catalyst.
In order to achieve the above purpose of the present invention, the present invention adopts the following technical scheme:
the catalyst is mainly composed of an oxide carrier and metal components, wherein the carrier components are at least two of cerium oxide, zirconium oxide, chromium oxide and zinc oxide, and the metal components are one of iron, copper, palladium, platinum and rhodium. Wherein the mass content of the metal component is 0.5-10%, preferably 1-5%.
The invention also provides a method for preparing the catalyst, which comprises the following steps:
1) dissolving two or more oxide nitrate precursors in water to prepare a mixed solution;
2) slowly dripping a certain alkali solution in the step 1) under the stirring state until the pH value is 9, and continuously stirring and aging for 3-10 h;
3) filtering and washing the suspension obtained in the step 2) until the pH value of the filtrate is neutral, and finally transferring the filtrate to a drying oven at 120 ℃ for drying treatment for 12 hours; placing the sample in a muffle furnace for roasting to obtain an oxide carrier;
4) dispersing precursor salt of a metal component in an aqueous solution, adding an oxide carrier into the solution, and uniformly stirring;
5) dropwise adding an alkaline solution into the solution in the step 4) until the pH value is 8-9, and continuously stirring for 2-8 h; then filtering and washing the filtrate until the pH value of the filtrate is neutral, and transferring the filtrate to a vacuum drying oven to be dried for 12 hours at 60 ℃; and then, placing the sample in a muffle furnace for roasting to obtain the catalyst.
Further, the oxide nitrate precursor used in step 1) is one of cerium nitrate, zirconium nitrate, chromium nitrate and zinc nitrate.
Further, the alkali solution in the step 2) is one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate and ammonia water, and the concentration is 0.01-1mol L-1。
Further, the muffle furnace in the step 3) has the roasting temperature of 300-.
Further, the metal component precursor salt in the step 4) is one of ferric nitrate, cupric nitrate, palladium nitrate, platinum tetraammine nitrate and rhodium nitrate.
Further, in the step 5)The alkali solution is one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate, and has a concentration of 0.01-1mol L-1。
Further, the muffle furnace in the step 5) has the roasting temperature of 200-.
The invention also provides a method for preparing deuterated methanol by using the catalyst, which takes deuterium and carbon dioxide gas as raw materials and comprises the following specific steps: d with the volume content of 5-100 percent2Reduction gas of Ar at the space velocity of 100--1Reducing the catalyst for 1-12h under the normal pressure condition of 200-500 ℃; introducing the reduced catalyst into D with the molar ratio of 32/CO2Gas under the pressure of 1-8MPa, the temperature of 200--1To prepare the deuterated methanol.
Compared with the prior art, the invention has the following beneficial effects:
1) the preparation method of the catalyst is simple and has strong reliability. The catalyst is prepared by preparing a carrier precursor by a coprecipitation method, obtaining a carrier by a roasting method, and then loading a metal component by a deposition-precipitation method. Wherein the mass content of the metal component is 0.5-10%. The catalyst can be used for the reaction of carbon dioxide and deuterium gas, and has high activity, high deuterated methanol selectivity and high stability. The deuteration rate of the deuterated methanol generated by the reaction is as high as 99.9 percent, and the method has good application value.
2) Different from other patents which adopt deuterium gas and carbon monoxide, the invention takes carbon dioxide and deuterium gas as raw materials to prepare deuterated methanol, namely, the problem of inhomogenous deuterated products is solved, and the method not only provides a novel deuterated methanol preparation method, but also provides greenhouse gas CO2The conversion and utilization of the method provide a way, so the proposed preparation method of the deuterated methanol has certain innovativeness. At present, no article or patent exists for the method for preparing deuterated methanol by taking carbon dioxide and deuterium as raw materialsNo alternatives exist. The invention takes carbon dioxide as a raw material, converts the carbon dioxide into chemicals with high added values and aims at relieving greenhouse gas CO2The resulting energy crisis and environmental problems provide a trigger.
Drawings
FIG. 1 is a diagram of the catalytic preparation of deuterated methanol using the catalyst of example 11HNMR spectrogram.
FIG. 2 is a diagram of deuterated methanol catalytically prepared using the catalyst of example 12DNMR spectra.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
4.34g of cerium nitrate and 4.29g of zirconium nitrate were weighed and dissolved in 100mL of water to prepare a mixed solution. Slowly dropwise adding 0.1mol L of the mixed solution into the mixed solution under stirring-1The ammonia solution until pH 9, stirring and aging were continued for 3 h. Filtering and washing the suspension until the pH of the filtrate is neutral, transferring the suspension to a 120 ℃ oven for drying treatment for 12h, placing a sample in a muffle furnace, heating at a speed of 5 ℃/min to 450 ℃ and roasting for 5h to obtain CeZrOxAnd (3) a carrier. A platinum tetraammine nitrate solution containing 10mg of Pt was weighed and dispersed in 50mL of an aqueous solution, and 1g of CeZrO was added to the solutionxAnd (5) uniformly stirring the carrier. 0.5mol L of the above solution was added dropwise-1Until the pH was 8, stirring was continued for 2 h. Then filtering and washing the filtrate until the pH value of the filtrate is neutral, and transferring the filtrate to a vacuum drying oven for drying treatment at 60 ℃ for 12 hours; then placing the sample in a muffle furnace, heating to 250 ℃ at the speed of 5 ℃/min, and roasting for 2h to obtain the Pt/CeZrOxA catalyst.
Example 2
4.34g of cerium nitrate and 2.97g of zinc nitrate were weighed and dissolved in 100mL of water to prepare a mixed solution. Slowly dropwise adding 0.5mol L of the mixed solution into the mixed solution under stirring-1Until the pH value is 9, stirring and aging are continued for 6 h. Filtering and washing the suspension until the pH of the filtrate is neutral, and transferring to a temperature of 120 DEG CDrying in a baking oven for 12h, placing the sample in a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min, and roasting for 5h to obtain CeZnOxAnd (3) a carrier. A palladium nitrate solution containing 20mg of Pd was weighed out and dispersed in 50mL of an aqueous solution, and 1g of CeZnO was added to the solutionxAnd (5) uniformly stirring the carrier. 0.1mol L of the above solution was added dropwise-1Until the pH is 8, stirring is continued for 3 h. Then filtering and washing the filtrate until the pH value of the filtrate is neutral, and transferring the filtrate to a vacuum drying oven for drying treatment at 60 ℃ for 12 hours; then placing the sample in a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and roasting for 2h to obtain the Pd/CeZnOxA catalyst.
Example 3
3.57g of chromium nitrate and 2.97g of zinc nitrate were weighed and dissolved in 100mL of water to prepare a mixed solution. Slowly dropwise adding 0.5mol L of the mixed solution into the mixed solution under stirring-1Until the pH is 9, stirring and aging are continued for 6 h. Filtering and washing the suspension until the pH of the filtrate is neutral, transferring the filtrate to a 120-DEG C oven for drying treatment for 12h, placing a sample in a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, and roasting for 4h to obtain CrZnOxAnd (3) a carrier. A rhodium nitrate solution containing 10mg of Rh was weighed out and dispersed in 50mL of an aqueous solution, and 1g of CrZnO was added to the solutionxAnd (5) uniformly stirring the carrier. 0.3mol L of alkaline solution is added into the solution-1Until the pH was 8, stirring was continued for 3 h. Then filtering and washing the filtrate until the pH value of the filtrate is neutral, and transferring the filtrate to a vacuum drying oven for drying treatment at 60 ℃ for 12 hours; then placing the sample in a muffle furnace, heating to 300 ℃ at the speed of 5 ℃/min, and roasting for 2h to obtain Rh/CrZnOxA catalyst.
Example 4
57g of chromium nitrate and 4.29g of zirconium nitrate were weighed out and dissolved in 100mL of water to prepare a mixed solution. Slowly dropwise adding 0.5mol L of the mixed solution into the mixed solution under stirring-1Until the pH is 9, the aging is continued for 8h with stirring. Filtering and washing the suspension until the pH of the filtrate is neutral, transferring the filtrate to a 120 ℃ oven for drying treatment for 12h, placing the sample in a muffle furnace, heating to 500 ℃ at a speed of 3 ℃/min, and roasting4h to obtain CrZrOxAnd (3) a carrier. 0.43g of iron nitrate nonahydrate powder was weighed out and dispersed in 150mL of an aqueous solution, and 1g of CrZrO was added to the solutionxAnd (5) uniformly stirring the carrier. 0.5mol L of water was added dropwise to the above solution-1Until the pH was 9, stirring was continued for 8 h. Then filtering and washing the filtrate until the pH value of the filtrate is neutral, and transferring the filtrate to a vacuum drying oven to be dried for 12 hours at 60 ℃; then placing the sample in a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min, and roasting for 5h to obtain Fe/CrZrOxA catalyst.
Example 5
4.34g of cerium nitrate, 2.97g of zinc nitrate and 4.29g of zirconium nitrate were weighed and dissolved in 150mL of water to prepare a mixed solution. Slowly dropwise adding 1mol L of the mixed solution into the mixed solution under stirring-1Until the pH is 9, stirring and aging are continued for 10 h. Filtering and washing the suspension until the pH of the filtrate is neutral, transferring the filtrate to a 120-DEG C oven for drying treatment for 12h, placing a sample in a muffle furnace, heating to 500 ℃ at the speed of 3 ℃/min, and roasting for 6h to obtain CeZnZrOxAnd (3) a carrier. 0.293g of copper nitrate trihydrate powder was weighed out and dispersed in 150mL of aqueous solution, and 1g of CeZnZrO was added to the solutionxAnd (5) uniformly stirring the carrier. 0.5mol L of water was added dropwise to the above solution-1Sodium carbonate solution until pH 9, stirring was continued for 5 h. Then filtering and washing the filtrate until the pH value of the filtrate is neutral, and transferring the filtrate to a vacuum drying oven for drying treatment at 60 ℃ for 12 hours; then placing the sample in a muffle furnace, heating to 450 ℃ at the speed of 5 ℃/min, and roasting for 4h to obtain Cu/CeZnZrOxA catalyst.
Example 6 preparation of deuterated methanol Using the catalysts of examples 1-5 and using deuterium gas and carbon dioxide gas as starting materials
The catalysts obtained in examples 1-5 were pelletized, granulated and sieved, and 5.0g of a catalyst having a particle size of 20-40 mesh (380-830 μm) was packed in a fixed bed stainless steel reactor. Firstly, the catalyst is subjected to in-situ reduction treatment, and the reducing gas is D2Purity is more than 99 percent, and volume space velocity is 500h-1The heating rate is 5 ℃/min, the reduction temperature is 380 ℃, the reduction time is 5h, and the pressure is normal pressure. Catalysis after reductionIntroducing a mixed gas of deuterium gas and carbon dioxide with a molar ratio of 3 into a catalyst bed layer for reaction, wherein the pressure is 6MPa, and the volume space velocity is 1800h-1The reaction temperature was 310 ℃. The raw material gas and the reaction product are analyzed by Agilent 8890B type gas chromatography and the result of the reaction is taken for 30 h. And collecting a crude product of the deuterated methanol from the gas product flowing out of the reaction tube through a cold hydrazine device, and further rectifying to obtain a target product of the deuterated methanol.
The performances of the deuterated methanol target products prepared by the catalysis of the catalysts of the examples 1 to 5 are respectively analyzed: after the reaction tail gas is cooled by a cold trap, the gas product enters two gas chromatographs (respectively provided with a TCD detector and an FID detector) connected in series for analysis, and the liquid product is collected for gas chromatography-mass spectrometry (GC-MS) analysis. The deuterated methanol prepared by the catalyst of the example 1 is separated and purified, and then the deuteration rate is analyzed by a nuclear magnetic resonance technical means.
The results of the measurements are shown in table 1, fig. 1 and fig. 2.
Table 1: performance results of the catalyst on the reaction for preparing deuterated methanol
Figure BDA0003631882010000061
Figure BDA0003631882010000071
As can be seen from table 1, fig. 1 and fig. 2: the catalyst has higher carbon dioxide deuterium addition activity and deuterated methanol selectivity, and the deuteration rate of the collected deuterated methanol can reach more than 99.9 percent.
The above description is only an example of the present invention and is not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention in the specification or other related fields can be directly or indirectly applied to the present invention, and the same shall be included in the scope of the present invention.

Claims (10)

1. The catalyst is mainly composed of an oxide carrier and metal components, wherein the carrier components are at least two of cerium oxide, zirconium oxide, chromium oxide and zinc oxide, and the metal components are one of iron, copper, palladium, platinum and rhodium.
2. The catalyst according to claim 1, wherein the metal component is contained in the catalyst in an amount of 0.5 to 10% by mass.
3. A process for preparing a catalyst according to claim 1 or 2, comprising the steps of:
1) dissolving two or more oxide nitrate precursors in water to prepare a mixed solution;
2) slowly dripping a certain alkali solution in the step 1) under the stirring state until the pH value is 9, and continuously stirring and aging for 3-10 h;
3) filtering and washing the suspension obtained in the step 2) until the pH value of the filtrate is neutral, and finally transferring the filtrate to a drying oven at 120 ℃ for drying treatment for 12 hours; placing the sample in a muffle furnace for roasting to obtain an oxide carrier;
4) dispersing metal component precursor salt in an aqueous solution, then adding an oxide carrier into the solution, and uniformly stirring;
5) dropwise adding an alkaline solution into the solution in the step 4) until the pH value is 8-9, and continuously stirring for 2-8 h; then filtering and washing the filtrate until the pH value of the filtrate is neutral, and transferring the filtrate to a vacuum drying oven to be dried for 12 hours at 60 ℃; and then, placing the sample in a muffle furnace for roasting to obtain the catalyst.
4. The method as claimed in claim 3, wherein the oxide nitrate precursor used in step 1) is one of cerium nitrate, zirconium nitrate, chromium nitrate and zinc nitrate.
5. The method according to claim 3, wherein the alkali solution in step 2) is one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate and ammonia water, and the concentration is 0.01-1mol L-1。
6. The method as claimed in claim 3, wherein the muffle furnace in step 3) is baked at a temperature of 300 ℃ and 600 ℃, the baking time is 2-12h, and the temperature rise rate is 1-10 ℃/min.
7. The method of claim 3, wherein the metal component precursor salt in step 4) is one of ferric nitrate, cupric nitrate, palladium nitrate, platinum tetraamine nitrate, and rhodium nitrate.
8. The method according to claim 3, wherein the alkali solution in the step 5) is one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate, and the concentration is 0.01-1mol L-1。
9. The method as claimed in claim 3, wherein the muffle furnace in step 5) has a roasting temperature of 200-600 ℃, a roasting time of 2-8h and a heating rate of 1-10 ℃/min.
10. The method for preparing deuterated methanol by using the catalyst as recited in claim 1 or 2, wherein said method uses deuterium gas and carbon dioxide gas as raw materials, and comprises the following specific steps: D2/Ar reducing gas with the volume content of 5-100 percent is used for reaction at the space velocity of 100-5000h-1Reducing the catalyst for 1-12h under the normal pressure condition of 200-500 ℃; introducing the reduced catalyst into D with the molar ratio of 32/CO2Gas under the pressure of 1-8MPa, the temperature of 200--1To prepare the deuterated methanol.
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