CN111167512A - Novel photo-thermal catalyst for synthesizing methanol by oxidizing methane and preparation method thereof - Google Patents

Novel photo-thermal catalyst for synthesizing methanol by oxidizing methane and preparation method thereof Download PDF

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CN111167512A
CN111167512A CN202010141428.3A CN202010141428A CN111167512A CN 111167512 A CN111167512 A CN 111167512A CN 202010141428 A CN202010141428 A CN 202010141428A CN 111167512 A CN111167512 A CN 111167512A
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catalyst
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hydroxide
colloid
oxide
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CN111167512B (en
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吴功德
王晓丽
阚建飞
张君
郑锋
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Suzhou Weiner New Material Technology Co Ltd
Nanjing Institute of Technology
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Nanjing Institute of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
    • B01J31/0275—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 also containing elements or functional groups covered by B01J31/0201 - B01J31/0269
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention provides a novel photo-thermal synergistic catalyst for synthesizing methanol by directly oxidizing methane and a preparation method thereof, wherein the catalyst takes a thermal catalyst formed by cheap metal hydrotalcite as a carrier, and a Bi-based photocatalyst is loaded to form the photo-thermal synergistic catalyst; the cheap metal comprises 1-3 of transition metals of Cr, Mn, Fe, Co, Ni, Cu and Zn, 0-1 of alkaline earth metals of Ba, Ca and Mg and metal Al. The invention has the following beneficial effects: (1) the prepared catalyst shows high activity in the reaction of synthesizing methanol by directly oxidizing methane, the reaction time is 2-96 hours under the conditions of low temperature and low pressure, the conversion rate of methane can reach 25% at most, and the selectivity of methanol can reach 95% at most. (2) The catalyst has simple preparation process, low cost, high activity and unique hydrothermal stability; (3) the obtained catalyst has the advantages of both light and heat catalysts, and can be used for directly oxidizing methane to synthesize methanol under mild conditions.

Description

Novel photo-thermal catalyst for synthesizing methanol by oxidizing methane and preparation method thereof
Technical Field
The invention relates to a novel photo-thermal synergistic catalyst for synthesizing methanol by directly oxidizing methane and a preparation method thereof, belonging to the field of new materials and technologies.
Background
Methane is a main component of carbon-containing resources such as natural gas, shale gas, methane, combustible ice and the like, has higher hydrogen-carbon ratio compared with coal and petroleum, can be used as fuel and for producing hydrogen, carbon monoxide, acetylene, hydrocyanic acid, formaldehyde and the like, and is considered as a novel clean energy and a high-quality chemical raw material with great development potential in the 21 st century. However, CH4Is also an effective greenhouse gas, and has a greenhouse effect of more than 20 times as much as carbon dioxide in the earth's atmosphere. Thus will be CH4The catalyst is converted into a product with high added value, so that the high-efficiency utilization of the product can be realized, and the catalyst has important academic value and profound environmental protection significance.
CH4Can be converted into CH by direct oxidation, non-oxidative coupling and oxidative coupling3OH, aromatic compound, C2+Products (ethylene, ethane, etc.) and the like. Wherein CH3OH is an important platform molecule and can be used for preparing hundreds of chemical products, namely CH4Preparation of CH by direct oxidation3OH is also considered to be the most economical and promising CH4The method is efficiently utilized, but two major problems to be solved are faced in the process: firstly, methane C-H activation is difficult, and secondly, product CH3OH is susceptible to further deep oxidation. So that a high-efficiency activated CH is constructed4And inhibit CH3Bifunctional catalytic systems for deep OH oxidation have been extremely challenging to date.
For nearly twenty years, CH4Preparation of CH by direct oxidation3Various catalytic oxidation systems for OH are constantly reported; among them, homogeneous catalyst systems represented by the Periana reaction system have unprecedented catalytic effects (CH)4Conversion of 81% CH3OH selectivity of over 90%), but its highly corrosive and expensive catalytic system is notIs suitable for industrial popularization (Science, 1998, 280(29): 560-564). The Martin and Tang subject group breaks through the traditional research thought, and takes FeO as the raw material under the normal temperature and the normal pressure with the assistance of sunlight (simulation) x /TiO2Is a catalyst, H2O2Is an oxidant, CH within 3 h4The conversion rate can reach 15 percent, the total alcohol selectivity can reach 97 percent, wherein CH3The selectivity of OH is as high as 90%, and the catalyst has excellent cycle stability (Naturecatalyst, 2018, 1: 889-896), but H2O2The price of the commodity is higher than CH3OH inhibits the industrial application prospect, so the problem of direct oxidation of methane to synthesize methanol by developing a cheap and efficient catalyst is urgently needed to be solved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a novel photo-thermal synergistic catalyst for synthesizing methanol by directly oxidizing methane and a preparation method thereof.
The technical scheme of the invention is as follows:
a novel photo-thermal synergistic catalyst for synthesizing methanol by directly oxidizing methane takes a thermal catalyst formed by cheap metal hydrotalcite as a carrier, and a Bi-based photocatalyst is loaded to form the photo-thermal synergistic catalyst;
the cheap metal comprises 1-3 of transition metals of Cr, Mn, Fe, Co, Ni, Cu and Zn, 0-1 of alkaline earth metals of Ba, Ca and Mg and metal Al;
the Bi-based photocatalytic material is BiOX or BiX3、BiVO4、Bi2MoO6、Bi2WO6、Bi(NO3)3X is Cl, Br, I or F;
the surface of the hydrotalcite-like compound is subjected to hydrophobic organic modification, and the surface modifier is a silane coupling agent;
wherein the supported Bi-based photocatalytic material accounts for 5-20% of the total mass of the catalyst.
The invention also provides a preparation method of the novel photo-thermal synergistic catalyst for synthesizing methanol by directly oxidizing methane, which comprises the following steps:
(1) preparing a mixed colloidal aqueous solution of transition metal oxide, alkaline earth metal hydroxide and aluminum hydroxide, and controlling the molar ratio of divalent metal ions to trivalent metal ions to be 2-5: 1, controlling the total concentration of metal ions to be 2.0-5.0 mol/L, controlling the pH value to be 9-11 by using alkali liquor, stirring for 1-10 hours at room temperature, putting the mixture into an autoclave, carrying out hydrothermal treatment at 80-120 ℃ for 12-48 hours, and cooling to room temperature;
(2) adding a certain amount of Bi salt ethanol solution into the colloid obtained in the step (1), stirring for 1-3 hours at 20-60 ℃, continuously controlling the pH value of the colloid to be 9-11 by using alkali liquor without adding or adding 1-2 of ammonium vanadate, ammonium molybdate or ammonium tungstate, and continuously carrying out hydrothermal treatment for 6-12 hours at 80-120 ℃; then filtering or centrifugally dewatering the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at the temperature of 60-100 ℃ to prepare the corresponding hydrotalcite Bi-loaded composite material;
(3) and adding the obtained catalyst into 0.05-0.1 mol/L silane coupling agent toluene solution, performing ultrasonic oscillation for 6-12 hours, and performing freeze centrifugal drying to obtain the surface-modified hydrotalcite-like loaded Bi catalytic material, namely the novel photo-thermal synergistic catalyst.
Further, in the step (1), the transition metal oxide is 1 to 3 kinds of chromium oxide, manganese oxide, ferrous oxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide.
Further, in the step (1), the alkaline earth metal hydroxide is 0 to 1 kind of hydroxide selected from barium hydroxide, calcium hydroxide and magnesium hydroxide.
Further, in the steps (1) and (2), the alkali solution is any one of sodium hydroxide, potassium hydroxide, ammonium hydroxide and urea solution.
In the step (2), the Bi salt is any one of bismuth trihalide and bismuth nitrate.
Further, in the step (3), the silane coupling agent is 1-2 of mercaptopropyl trimethoxysilane, n-propyl trimethoxysilane, phenyl trimethoxysilane, p-sulfoacid phenylpropyl methoxysilane and aminopropyl trimethoxysilane.
Compared with the prior art, the invention mainly provides two aspects of technical innovation:
(1) develops a cheap, efficient and green product and process, thereby synthesizing the photo-thermal synergistic catalyst with a regular structure under the condition of no three-waste emission;
(2) by utilizing the synergistic effect of the photo-thermal active center, a cheap and efficient catalytic system is developed for synthesizing methanol by directly oxidizing methane.
On one hand, the invention provides a new idea for preparing a BiOX/HT cheap catalytic system, strives to realize zero emission of anion waste liquid in the preparation process, improves atom economy and realizes energy conservation and emission reduction; on the other hand, can be an environment-friendly oxidant H2O2In situ generation of greenhouse gas CH4Direct oxidation synthesis of CH3OH builds an environment-friendly and efficient catalytic system. The smooth implementation of the two aspects can not only avoid the generation of three wastes in the preparation process of the catalyst from the source, but also inhibit the emission of greenhouse gases; but also can search out a green and high-efficiency energy conversion way. In addition, the method also provides an important reference basis for preparing the Bi-based photocatalytic material with more excellent performance in the field of photocatalytic degradation of pollutants.
As can be seen from the specific embodiments of the present invention, the present invention has the following beneficial effects:
(1) the prepared catalyst shows high activity in the reaction of synthesizing methanol by directly oxidizing methane, the reaction time is 2-96 hours under the conditions of low temperature and low pressure, the conversion rate of methane can reach 25% at most, and the selectivity of methanol can reach 95% at most.
(2) The catalyst has simple preparation process, low cost, high activity and unique hydrothermal stability;
(3) the obtained catalyst has the advantages of both light and heat catalysts, and can be used for directly oxidizing methane to synthesize methanol under mild conditions.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Reaction and detection conditions: in a 100L photothermal reactor with xenon lamp light source, 30L water is used as solvent, 100 g of the prepared catalyst is added, and reaction mixed gas containing 1.6% of CH is introduced4, 6.6% O265% of Ar and 26.8% of He, controlling the temperature of a reactor at 30-90 ℃, controlling the pressure at normal pressure-3.0 MPa, connecting the reactor with a gas chromatographic analysis (TCD detector, TDX-1 chromatographic column) on line to form a gas composition, filtering a solid catalyst after the reaction is finished, and analyzing a liquid composition by using a gas chromatographic (FID detector, DV-17 chromatographic column).
Example 1
48 mol of MnO and 12 mol of Ca (OH)2And 30 mol of Al (OH)3Preparing 45L colloid with deionized water; and adding NH4Controlling the pH value of the mixed solution to be 9.0 by OH; vigorously stirred at room temperature for 1.0 hour, transferred into an autoclave, hydrothermally treated at 80 ℃ for 12 hours, and then cooled to room temperature. Then adding 45L of 0.4 mol/L bismuth trichloride ethanol solution, stirring for 1 hour at 20 ℃, adding ammonium vanadate with the same mole number as that of bismuth trichloride, and adding NH4Controlling the pH value of the mixed solution to be 9.0 by OH, and continuously transferring the mixed solution into an autoclave for hydrothermal treatment for 6 hours at the temperature of 80 ℃. And then filtering and dehydrating the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at 60 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material. 100 g of the obtained material is added into 1L of toluene solution of 0.1mol/L mercaptopropyl trimethoxy silane, ultrasonic waves are vigorously shaken for 6 hours, and freeze centrifugal drying is carried out, thus obtaining the mercaptopropyl trimethoxy modified hydrotalcite-like supported bismuth vanadate catalytic material, namely a novel photo-thermal synergistic catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, and the reaction is carried out for 2 hours at the temperature of 30 ℃ under normal pressure, so that the conversion rate of the obtained methane is 1.0 percent, and the selectivity of the methanol is 95 percent.
Example 2
48 mol of CoO, 12 mol of Zn (OH)2And 30 mol of Al (OH)3Preparing 18L colloid by using deionized water; adding KOH to control the pH value of the mixed solution to be 11; vigorously stirring at room temperature for 10 hr, transferring into high-pressure autoclave, and heating at 120 deg.CAfter 48 hours of treatment, cool to room temperature. Then 18L of 0.15 mol/L bismuth trifluoride ethanol solution is added, the mixture is stirred for 3 hours at 20 ℃, the pH value of the mixture is controlled to be 11 by KOH, and the mixture is transferred into an autoclave for hydrothermal treatment for 12 hours at 120 ℃. And then filtering and dehydrating the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at 100 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material. 100 g of the obtained material is added into 1L of toluene solution of aminopropyl trimethoxy silane with the concentration of 0.1mol/L, ultrasonic wave is vigorously shaken for 12 hours, and then the mixture is frozen, centrifuged and dried to obtain the aminopropyl trimethoxy modified hydrotalcite-like bismuth oxyfluoride catalytic material, namely a novel photo-thermal synergistic catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, the reaction is carried out at 90 ℃ and 3 Mpa for 96 hours, the conversion rate of the obtained methane is 25 percent, and the selectivity of the methanol is 55 percent.
Example 3
48 mol of NiO and 12 mol of Ba (OH)2And 30 mol of Al (OH)3Preparing 30L of colloid by using deionized water; NaOH is added to control the pH value of the mixed solution to be 10.0; vigorously stirred at room temperature for 6.0 hours, transferred into an autoclave, hydrothermally treated at 100 ℃ for 24 hours, and then cooled to room temperature. Then adding 30L of 0.8 mol/L bismuth tribromide ethanol solution, stirring for 2 hours at 50 ℃, adding ammonium molybdate with the same mole number as that of bismuth trichloride, controlling the pH value of the mixed solution to 10.0 by NaOH, and continuously moving into a high-pressure kettle for hydrothermal treatment for 8 hours at 100 ℃. And then filtering and dehydrating the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at 100 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material. Adding 100 g of the obtained material into 1L of toluene solution of n-propyl trimethoxy silane of 0.1mol/L, oscillating for 10 hours by ultrasonic wave, freezing, centrifuging and drying to obtain the catalytic material of n-propyl trimethoxy modified hydrotalcite-like loaded bismuth vanadate, namely a novel photo-thermal synergistic catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, and the reaction is carried out for 12 hours at 70 ℃ under normal pressure, so that the conversion rate of the obtained methane is 20 percent, and the selectivity of the methanol is 85 percent.
Example 4
Will 24mol CuO、24 mol NiO、12 mol Al(OH)3And 30 mol of Cr2O3Preparing 30L of colloid by using deionized water; adding urea to control the pH value of the mixed solution to be 10.0; vigorously stirred at room temperature for 6.0 hours, transferred into an autoclave, hydrothermally treated at 100 ℃ for 24 hours, and then cooled to room temperature. Then adding 30L of 0.8 mol/L bismuth triiodide ethanol solution, stirring for 2 hours at 50 ℃, adding ammonium tungstate with the same mole number as that of bismuth triiodide, controlling the pH value of the mixed solution to be 10.0 by using urea, and continuously transferring the mixed solution into a high-pressure kettle for hydrothermal treatment for 8 hours at 100 ℃. And then filtering and dehydrating the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at 100 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material. Adding 100 g of the obtained material into 1L of toluene solution containing 0.05mol/L of n-propyl trimethoxy silane and 0.05mol/L of phenyl trimethoxy silane, oscillating the obtained material for 10 hours by ultrasonic waves violently, and carrying out freeze centrifugal drying to obtain the hydrotalcite-like supported bismuth vanadate catalytic material modified by both n-propyl trimethoxy and phenyl trimethoxy, namely the novel photo-thermal synergistic catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, and the reaction is carried out for 12 hours at 70 ℃ under normal pressure, so that the conversion rate of methane is 15 percent, and the selectivity of methanol is 83 percent.
Example 5
24 mol of CuO, 24 mol of FeO and 12 mol of Mg (OH)2And 30 mol of Al (OH)3Preparing 30L of colloid by using deionized water; and adding NH4Controlling the pH value of the mixed solution to be 10.0 by OH; vigorously stirred at room temperature for 6.0 hours, transferred into an autoclave, hydrothermally treated at 100 ℃ for 24 hours, and then cooled to room temperature. Then adding 30L of 0.8 mol/L bismuth nitrate ethanol solution, stirring for 2 hours at 50 ℃, adding ammonium vanadate with the same number of moles as that of the bismuth nitrate, and using NH4And OH controlling the pH value of the mixed solution to be 10.0, and continuously transferring the mixed solution into an autoclave at 100 ℃ for hydrothermal treatment for 8 hours. And then filtering and dehydrating the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at 100 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material. Adding 100 g of the obtained material into 0.05mol/L of 1L toluene solution of p-sulfoacid styrene-acrylic-grade methoxy silane, oscillating for 10 hours by ultrasonic waves, freezing, centrifuging and drying to obtain the p-sulfoacid styrene-acrylic-grade methoxy modified hydrotalcite-like negativeA catalytic material of supported bismuth vanadate, a novel photo-thermal synergistic catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, and the reaction is carried out for 12 hours at 70 ℃ under normal pressure, so that the conversion rate of methane is 18 percent, and the selectivity of methanol is 85 percent.
Example 6
Mixing 45 mol of CuO, 45 mol of NiO and 30 mol of Al (OH)3Preparing 50L of colloid by using deionized water; and adding NH4Controlling the pH value of the mixed solution to be 10.0 by OH; vigorously stirred at room temperature for 6.0 hours, transferred into an autoclave, hydrothermally treated at 100 ℃ for 24 hours, and then cooled to room temperature. Then adding 50L of 0.8 mol/L bismuth trichloride ethanol solution, stirring for 2 hours at 50 ℃, and adding NH4And OH controlling the pH value of the mixed solution to be 10.0, and continuously transferring the mixed solution into an autoclave at 100 ℃ for hydrothermal treatment for 8 hours. And then centrifugally dehydrating the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at 100 ℃ to prepare the corresponding hydrotalcite-loaded Bi composite material. Adding 100 g of the obtained material into 0.1mol/L of 1L toluene solution of p-sulfoacid styrene-acrylic methoxy silane, oscillating for 10 hours by ultrasonic waves, freezing, centrifuging and drying to obtain the p-sulfoacid styrene-acrylic methoxy modified hydrotalcite-like loaded bismuth oxychloride catalytic material, namely the novel photo-thermal synergistic catalyst. In a 100L photo-thermal reaction kettle with a xenon lamp light source, 30L of water is used as a solvent, 100 g of the prepared catalyst is added, reaction mixed gas is introduced, and the reaction is carried out for 12 hours at 70 ℃ under normal pressure, so that the conversion rate of methane is 21 percent, and the selectivity of methanol is 83 percent.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A novel photo-thermal synergistic catalyst for synthesizing methanol by directly oxidizing methane is characterized in that the catalyst takes a thermal catalyst formed by cheap metal hydrotalcite as a carrier, and a Bi-based photocatalyst is loaded to form the photo-thermal synergistic catalyst;
the cheap metal comprises 1-3 of transition metals of Cr, Mn, Fe, Co, Ni, Cu and Zn, 0-1 of alkaline earth metals of Ba, Ca and Mg and metal Al;
the Bi-based photocatalytic material is BiOX or BiX3、BiVO4、Bi2MoO6、Bi2WO6、Bi(NO3)3X is Cl, Br, I or F;
the surface of the hydrotalcite-like compound is subjected to hydrophobic organic modification, and the surface modifier is a silane coupling agent;
wherein the supported Bi-based photocatalytic material accounts for 5-20% of the total mass of the catalyst.
2. The method for preparing a novel photothermal concerted catalyst for methanol synthesis by direct oxidation of methane according to claim 1, comprising the steps of:
(1) preparing a mixed colloidal aqueous solution of transition metal oxide, alkaline earth metal hydroxide and aluminum hydroxide, and controlling the molar ratio of divalent metal ions to trivalent metal ions to be 2-5: 1, controlling the total concentration of metal ions to be 2.0-5.0 mol/L, controlling the pH value to be 9-11 by using alkali liquor, stirring for 1-10 hours at room temperature, putting the mixture into an autoclave, carrying out hydrothermal treatment at 80-120 ℃ for 12-48 hours, and cooling to room temperature;
(2) adding a certain amount of Bi salt ethanol solution into the colloid obtained in the step (1), stirring for 1-3 hours at 20-60 ℃, continuously controlling the pH value of the colloid to be 9-11 by using alkali liquor without adding or adding 1-2 of ammonium vanadate, ammonium molybdate or ammonium tungstate, and continuously carrying out hydrothermal treatment for 6-12 hours at 80-120 ℃; then filtering or centrifugally dewatering the obtained colloid, washing the colloid to be neutral by water, and drying the colloid at the temperature of 60-100 ℃ to prepare the corresponding hydrotalcite Bi-loaded composite material;
(3) and adding the obtained catalyst into 0.05-0.1 mol/L silane coupling agent toluene solution, performing ultrasonic oscillation for 6-12 hours, and performing freeze centrifugal drying to obtain the surface-modified hydrotalcite-like loaded Bi catalytic material, namely the novel photo-thermal synergistic catalyst.
3. The method according to claim 2, wherein in the step (1), the transition metal oxide is 1 to 3 kinds of chromium oxide, manganese oxide, ferrous oxide, cobalt oxide, nickel oxide, copper oxide, and zinc oxide.
4. The method according to claim 2, wherein in the step (1), the alkaline earth metal hydroxide is 0 to 1 kind of hydroxide selected from the group consisting of barium hydroxide, calcium hydroxide and magnesium hydroxide.
5. The method according to claim 2, wherein in the steps (1) and (2), the alkali solution is any one of sodium hydroxide, potassium hydroxide, ammonium hydroxide and urea solution.
6. The method according to claim 2, wherein in the step (2), the Bi salt is any one of bismuth trihalide and bismuth nitrate.
7. The method according to claim 2, wherein in the step (3), the silane coupling agent is 1 to 2 selected from mercaptopropyltrimethoxysilane, n-propyltrimethoxysilane, phenyltrimethoxysilane, p-sulfophenylallylmethoxysilane and aminopropyltrimethoxysilane.
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CN113976149A (en) * 2021-11-05 2022-01-28 湖南大学 Cobalt-aluminum hydrotalcite/bismuth-rich bismuth oxychloride composite photocatalyst and preparation method and application thereof
CN114618469A (en) * 2020-12-14 2022-06-14 中国科学院大连化学物理研究所 Supported zinc oxide catalyst and preparation method and application thereof

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