CN114768803B - Catalyst for synthesizing full deuterated methanol, preparation method and application thereof - Google Patents

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

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CN114768803B
CN114768803B CN202210491133.8A CN202210491133A CN114768803B CN 114768803 B CN114768803 B CN 114768803B CN 202210491133 A CN202210491133 A CN 202210491133A CN 114768803 B CN114768803 B CN 114768803B
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CN114768803A (en
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杨晓丽
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Nanjing Ningdeuterium Biotechnology Co ltd
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Nanjing Ningdeuterium Biotechnology Co ltd
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    • C07C29/156—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof
    • C07C29/157—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof
    • C07C29/158—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing iron group metals, platinum group metals or compounds thereof containing platinum group metals or compounds thereof containing rhodium or compounds thereof
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Abstract

The invention relates to a catalyst for synthesizing full deuterated methanol, a preparation method and application thereof. The catalyst mainly comprises an oxide carrier and a metal component, wherein the carrier component is at least two of cerium oxide, zirconium oxide, chromium oxide and zinc oxide, and the metal component is 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 preparation method of the catalyst is simple and reliable, has the advantages of higher activity, deuterated methanol selectivity and the like, and the deuteration rate of the product can reach 99.9 percent.

Description

Catalyst for synthesizing full deuterated methanol, preparation method and application thereof
Technical Field
The invention relates to a catalyst for synthesizing full 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 a 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 medicine, photoelectric display and nuclear magnetic resonance detection. For example, after replacing hydrogen in the drug molecule with deuterium, metabolic sites can be blocked, and the generation of toxic metabolites can be reduced. 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 for monitoring the changes of species and molecular structures in the reaction process, and provides important technical support for exploring reaction mechanisms and product distribution. The common deuterium methanol preparation method utilizes hydrogen-deuterium (H-D) exchange reaction, and researchers deuterate 1-methoxy-1, 3-cyclohexadiene to prepare deuterium methanol, but the method cannot ensure complete deuterium substitution of hydrogen atoms, and the complexity and the diversity of the prepared product bring difficulties to post-treatment, use and the like.
On the other hand, the large amount of fossil fuel has led to a trend of energy supply and a trend of greenhouse gas CO 2 The rapid increase in emissions, in turn, causes an increasingly severe energy crisis and environmental problems. Currently, CO is to 2 The method is used for capturing and converting the carbon into chemicals with high added value, is highly valued internationally, and provides an important way for recycling the carbon. Based on the method, the patent adopts carbon dioxide and deuterium as raw materials, and deuterated methanol is prepared through thermocatalysis; and a catalyst for the process and a method for preparing the same are provided, in which an oxide active component is mixed to prepare a catalyst having excellent catalytic performance.
At present, methods for preparing deuterated methanol are reported in the prior art, for example, chinese patent CN 112321388A, CN 112675875A and CN 11116313A, CN108250041B, CN109078638A all disclose methods for preparing deuterated methanol by taking deuterium gas and carbon monoxide gas as raw materials, wherein Chinese patent CN 112321388A mainly describes the characteristics of reaction, and the other describes 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 catalyst in the Chinese patent CN108250041B is one or a combination of more of gold oxide, platinum oxide and rhodium oxide; chinese patent CN109078638A discloses cuzncelio as the catalyst, and chinese patent CN 112675875A also uses cuzncelo as the catalyst.
However, no prior art has disclosed a method for preparing deuterated methanol from deuterium and carbon dioxide gas, nor has the prior art disclosed a catalyst applicable to the preparation of full 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 full deuterated methanol, a preparation method and application thereof.
The first aim of the invention is to provide a catalyst for synthesizing the full deuterated methanol, which can be well applied to the reaction of preparing the full deuterated methanol by deuterium and carbon dioxide, and has the characteristics of high activity and high selectivity, and the deuteration rate of the generated full deuterated methanol is as high as 99.9%.
The second aim of the invention is to provide a preparation method of the catalyst for preparing the full deuterated methanol by using deuterium and carbon dioxide, which is simple and reliable and has universality.
A third object of the present invention is to provide an application of the above catalyst, specifically, to use the above catalyst to catalyze a reaction of preparing deuterated methanol by using deuterium and carbon dioxide as raw materials.
In order to achieve the above object of the present invention, the present invention adopts the following technical scheme:
a catalyst for synthesizing full-deuterated methanol is applied to the reaction of preparing full-deuterated methanol from deuterium and carbon dioxide, and mainly comprises an oxide carrier and a metal component, wherein the carrier component is at least two of cerium oxide, zirconium oxide, chromium oxide and zinc oxide, and the metal component is 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 dropwise adding a certain amount of alkali solution into the solution in the step 1) under the stirring state until the pH value is 9, and continuing stirring and ageing for 3-10 h;
3) Filtering and washing the suspension in the step 2) until the pH value of the filtrate is neutral, and finally transferring the filtrate into a baking 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 a 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 hours; then filtering and washing the mixture until the pH value of the filtrate is neutral, transferring the mixture into a vacuum drying oven, and drying the mixture at 60 ℃ for 12 hours; and then placing the sample in a muffle furnace for roasting to obtain the catalyst.
Further, the oxide nitrate precursor used in the 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 roasting temperature in the step 3) is 300-600 ℃, the roasting time is 2-12h, and the heating rate is 1-10 ℃/min.
Further, the metal component precursor salt in the step 4) is one of ferric nitrate, cupric nitrate, palladium nitrate, tetramine platinum nitrate and rhodium nitrate.
Further, 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 。
Further, the muffle furnace roasting temperature in the step 5) is 200-600 ℃, the roasting time is 2-8h, and the heating rate is 1-10 ℃/min.
The invention also provides a method for preparing deuterated methanol by using the catalyst, wherein the method takes deuterium and carbon dioxide gas as raw materials, and the method comprises the following specific steps: d with the volume content of 5-100% 2 Ar is alsoRaw gas at airspeed of 100-5000h -1 Reducing the catalyst for 1-12h under the normal pressure condition with the temperature of 200-500 ℃; introducing the reduced catalyst into a catalyst with the molar ratio of 3D 2 /CO 2 The gas is heated at a pressure of 1-8MPa, a temperature of 200-800 ℃ and a space velocity of 500-10000h -1 Under the condition of (2) to produce 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 high 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 in the reaction of carbon dioxide and deuterium, has higher activity and deuterated methanol selectivity, and has good stability. The deuteration rate of the deuterated methanol generated by the reaction is up to 99.9 percent, and the method has good application value.
2) Unlike other patent with deuterium and CO, the present invention prepares deuterated methanol with carbon dioxide and deuterium as material, and this solves the problem of inhomogeneous deuterated product, and this method not only provides one new preparation process of deuterated methanol, but also is greenhouse gas CO 2 Provides a way for the conversion and utilization of the deuterium-substituted methanol, so that the preparation method of the deuterium-substituted methanol has a certain innovation. Currently, there is no article or patent that suggests a method for preparing deuterated methanol by taking carbon dioxide and deuterium as raw materials, and no alternative scheme exists. The invention takes carbon dioxide as raw material, converts the carbon dioxide into chemicals with high added value, and relieves greenhouse gas CO 2 The energy crisis and environmental problems that are raised provide a opportunity.
Drawings
FIG. 1 is a deuterated methanol prepared by catalysis with the catalyst of example 1 1 HNMR spectra.
FIG. 2 is a deuterated methanol prepared by catalysis with the catalyst of example 1 2 DNMR spectra.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
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 to the mixed solution under stirring -1 Until the pH is 9, and the stirring and aging are continued for 3 hours. Filtering and washing the suspension until the pH value of the filtrate is neutral, transferring to a 120 ℃ oven for drying treatment for 12 hours, placing the sample in a muffle furnace, heating to 450 ℃ at a speed of 5 ℃/min, and roasting for 5 hours to obtain CeZrO x A carrier. A platinum tetrammine nitrate solution containing 10mg of Pt was weighed and dispersed in 50mL of an aqueous solution, followed by adding 1g of CeZrO to the solution x And (5) carrying out uniform stirring. Dropwise adding 0.5mol L into the solution -1 Until the pH was 8, stirring was continued for 2h. Then filtering and washing the mixture until the pH value of the filtrate is neutral, transferring the mixture into a vacuum drying oven, and drying the mixture at 60 ℃ for 12 hours; then placing the sample in a muffle furnace, heating to 250 ℃ at a speed of 5 ℃/min, and roasting for 2 hours to obtain the Pt/CeZrO x A 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 to the mixed solution under stirring -1 Until the pH is 9, and the stirring and aging are continued for 6 hours. Filtering and washing the suspension until the pH value of the filtrate is neutral, finally transferring the filtrate into a baking oven at 120 ℃ for drying treatment for 12 hours, placing the sample into a muffle furnace, heating to 450 ℃ at a speed of 5 ℃/min, and roasting for 5 hours to obtain CeZnO x A carrier. A palladium nitrate solution containing 20mg of Pd was weighed and dispersed in 50mL of an aqueous solution, followed by adding 1g of CeZnO to the solution x And (5) carrying out uniform stirring. Dropwise adding 0.1mol L into the solution -1 Until the pH was 8, stirring was continued for 3h. Then filtering and washing the mixture until the pH value of the filtrate is neutral, transferring the mixture into a vacuum drying oven, and drying the mixture at 60 ℃ for 12 hours; subsequently, the sample is placed in a muffle furnace and is heated to 300 ℃ at a speed of 5 ℃/min for roasting2h to obtain Pd/CeZnO x A 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 to the mixed solution under stirring -1 Until the pH is 9, and the stirring and aging are continued for 6 hours. Filtering and washing the suspension until the pH value of the filtrate is neutral, finally transferring the filtrate into a baking oven at 120 ℃ for drying treatment for 12 hours, placing the sample into a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, and roasting for 4 hours to obtain CrZnO x A carrier. A rhodium nitrate solution containing 10mg of Rh was weighed and dispersed in 50mL of an aqueous solution, followed by adding 1g of CrZnO to the solution x And (5) carrying out uniform stirring. To the above solution was added dropwise 0.3mol L of an alkaline solution -1 Until the pH was 8, stirring was continued for 3h. Then filtering and washing the mixture until the pH value of the filtrate is neutral, transferring the mixture into a vacuum drying oven, and drying the mixture at 60 ℃ for 12 hours; then placing the sample in a muffle furnace, heating to 300 ℃ at a speed of 5 ℃/min, and roasting for 2 hours to obtain Rh/CrZnO x A catalyst.
Example 4
57g of chromium nitrate and 4.29g of zirconium nitrate were weighed and dissolved in 100mL of water to prepare a mixed solution. Slowly dropwise adding 0.5mol L to the mixed solution under stirring -1 Until the pH is 9, and the stirring and aging are continued for 8 hours. Filtering and washing the suspension until the pH value of the filtrate is neutral, transferring to a 120 ℃ oven for drying treatment for 12 hours, placing the sample in a muffle furnace, heating to 500 ℃ at a speed of 3 ℃/min, and roasting for 4 hours to obtain CrZrO x A carrier. 0.43g of iron nitrate nonahydrate powder was weighed out and dispersed in 150mL of an aqueous solution, followed by adding 1g of CrZrO to the solution x And (5) carrying out uniform stirring. Dropwise adding 0.5mol L into the solution -1 Until the pH was 9, stirring was continued for 8h. Then filtering and washing the mixture until the pH value of the filtrate is neutral, transferring the mixture into a vacuum drying oven, and drying the mixture at 60 ℃ for 12 hours; then placing the sample in a muffle furnace, heating to 450 ℃ at a speed of 5 ℃/min, and roasting for 5 hours to obtain Fe/CrZrO x A 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 to the mixed solution under stirring -1 Until the pH is 9, and the stirring and aging are continued for 10 hours. Filtering and washing the suspension until the pH value of the filtrate is neutral, transferring to a 120 ℃ oven for drying treatment for 12 hours, placing the sample in a muffle furnace, heating to 500 ℃ at a speed of 3 ℃/min, and roasting for 6 hours to obtain CeZnZrO x A carrier. 0.293g of copper nitrate trihydrate powder is weighed and dispersed in 150mL of aqueous solution, and 1g of CeZnZrO is added into the solution x And (5) carrying out uniform stirring. Dropwise adding 0.5mol L into the solution -1 Until the pH was 9, stirring was continued for 5h. Then filtering and washing the mixture until the pH value of the filtrate is neutral, transferring the mixture into a vacuum drying oven, and drying the mixture at 60 ℃ for 12 hours; then placing the sample in a muffle furnace, heating to 450 ℃ at a speed of 5 ℃/min, and roasting for 4 hours to obtain Cu/CeZnZrO x A catalyst.
Example 6 preparation of deuterated methanol Using the catalysts of examples 1-5 and Using deuterium gas and carbon dioxide gas as raw materials
The catalysts prepared in examples 1 to 5 were separately subjected to pelleting and sieving, and 5.0g of the catalyst having a particle size of 20 to 40 mesh (380 to 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 D 2 Purity is more than 99%, and volume space velocity is 500h -1 The temperature rising rate is 5 ℃/min, the reduction temperature is 380 ℃, the reduction time is 5h, and the pressure is normal pressure. Introducing deuterium gas and carbon dioxide mixed gas with the molar ratio of 3 into the reduced catalyst bed layer for reaction, wherein the pressure is 6MPa, and the volume space velocity is 1800h -1 The reaction temperature was 310 ℃. The raw material gas and the reaction product were analyzed by Agilent 8890B-type gas chromatography, taking the result at 30h of reaction. The gaseous product flowing out of the reaction tube is collected into the crude product of deuterated methanol by a hydrazine cooling device, and then the crude product of deuterated methanol is further rectified to obtain the target product of deuterated methanol.
The properties of deuterated methanol target products prepared by catalysis with the catalysts of examples 1-5 were analyzed: after the reaction tail gas is cooled by a cold trap, the gas product enters two gas chromatographs (which are respectively provided with a TCD detector and a FID detector) connected in series for analysis, and the liquid product is collected for gas chromatography-mass spectrometry (GC-MS) analysis. Deuterated methanol prepared by catalysis of the catalyst of example 1 is separated and purified, and then the deuteration rate is analyzed by adopting a nuclear magnetic resonance technology.
The results of the detection are shown in Table 1, FIG. 1 and FIG. 2.
Table 1: reaction performance results of catalyst on preparation of deuterated methanol
As can be seen from table 1, fig. 1 and fig. 2: the catalyst has relatively high carbon dioxide deuterium adding activity and deuterium methyl alcohol selectivity, and the deuterium methyl alcohol deuterium methyl rate collected can reach more than 99.9%.
The foregoing is merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention or direct or indirect application in other related technical fields are included in the scope of the present invention.

Claims (7)

1. The method for preparing the full deuterated methanol is characterized by taking deuterium and carbon dioxide as raw materials and comprises the following specific steps: d with the volume content of 5-100% 2 Ar reducing gas at airspeed of 100-5000h -1 Reducing the catalyst at 200-500 deg.c and normal pressure of 1-12h; introducing the reduced catalyst into a catalyst with the molar ratio of 3D 2 /CO 2 The gas is at a pressure of 1-8MPa, a temperature of 200-800 ℃ and a space velocity of 500-10000h -1 Under the condition of (1) carrying out synthesis reaction to prepare the full deuterated methanol;
the catalyst consists of an oxide carrier and a metal component, wherein the carrier component is at least two of cerium oxide, zirconium oxide, chromium oxide and zinc oxide, and the metal component is one of iron, copper, palladium, platinum and rhodium;
the mass content of the metal component in the catalyst is 0.5% -10%.
2. The method for preparing the full deuterated methanol according to claim 1, wherein the method for preparing the catalyst comprises the following steps:
1) Dissolving nitrate precursors of at least two oxide carriers in water to prepare a mixed solution;
2) Slowly dropwise adding a certain amount of alkali solution into the solution in the step 1) under the stirring state until the pH value is 9, and continuing stirring and ageing for 3h-10 hours;
3) Filtering and washing the suspension in the step 2) until the pH value of the filtrate is neutral, and finally transferring the filtrate to a baking oven at 120 ℃ for drying treatment 12h; placing the sample in a muffle furnace for roasting to obtain an oxide carrier;
4) Dispersing a 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 2h-8h; then filtering and washing the mixture until the pH value of the filtrate is neutral, transferring the mixture into a vacuum drying oven, and drying the mixture at 60 ℃ for 12h; and then placing the sample in a muffle furnace for roasting to obtain the catalyst.
3. The method for preparing perdeuterated methanol according to claim 2, wherein the alkali solution in step 2) of the catalyst preparation method is one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate and ammonia solution, and the concentration is 0.01-1mol L -1 。
4. The method for preparing perdeuterated methanol according to claim 2, wherein the muffle furnace baking temperature in step 3) of the catalyst preparation method is 300-600 ℃, the baking time is 2-12h, and the heating rate is 1-10 ℃/min.
5. The method for preparing perdeuterated methanol according to claim 2, wherein the metal component precursor salt in step 4) of the catalyst preparation method is one of ferric nitrate, cupric nitrate, palladium nitrate, tetramine platinum nitrate, rhodium nitrate.
6. The method for preparing perdeuterated methanol according to claim 2, wherein the alkaline solution in step 5) of the catalyst preparation method is one of sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium carbonate, and ammonium bicarbonate solution, and the concentration is 0.01-1mol L -1 。
7. The method for preparing perdeuterated methanol according to claim 2, wherein the muffle furnace baking temperature in step 5) of the catalyst preparation method is 200-600 ℃, the baking time is 2-8h, and the heating rate is 1-10 ℃/min.
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