CN112830877B

CN112830877B - Application of supported monatomic noble metal catalyst in unsaturated hydrocarbon carboxymethylation reaction

Info

Publication number: CN112830877B
Application number: CN201911154324.XA
Authority: CN
Inventors: 王爱琴; 王安; 任煜京; 张磊磊; 张涛
Original assignee: Dalian Institute of Chemical Physics of CAS
Current assignee: Dalian Institute of Chemical Physics of CAS
Priority date: 2019-11-22
Filing date: 2019-11-22
Publication date: 2022-03-29
Anticipated expiration: 2039-11-22
Also published as: CN112830877A

Abstract

The invention discloses an application of a load type single-atom noble metal catalyst in unsaturated hydrocarbon carboxymethylation reaction, wherein the active component is any one or more of Ru, Rh, Ir, Pt, Pd, Ag and Au, the load capacity of the active metal is 0.05-1.5%, the carrier is any one of chromium sulfide, manganese sulfide, iron sulfide, cobalt sulfide, nickel sulfide, copper sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide and titanium sulfide, and the catalyst is prepared by the following steps: mixing the carrier and the active metal, and roasting at a certain temperature. The catalyst is used for preparing a methyl ester compound by the carboxymethylation of unsaturated hydrocarbon, and has good activity and selectivity. Compared with a system in which a homogeneous nickel carbonyl or palladium-phosphine complex is used as a catalyst and strong corrosive sulfuric acid or sulfonic acid is added as an auxiliary agent, the heterogeneous reaction process provided by the invention has the advantages of environmental friendliness, simplicity in operation, recyclability and the like.

Description

Application of supported monatomic noble metal catalyst in unsaturated hydrocarbon carboxymethylation reaction

Technical Field

The invention relates to an application of a load type single-atom noble metal catalyst in unsaturated hydrocarbon carboxymethylation reaction

Background

The unsaturated hydrocarbon carboxymethylation reaction is a green, simple and high atom economy method for preparing methyl ester compounds, such as methyl methacrylate (i.e. organic glass). However, the industry is still using homogeneous nickel carbonyl or palladium-phosphine complexes as catalysts on a large scale and requires strongly corrosive sulfuric or sulfonic acids as auxiliaries. Such as byNi(CO)₄,Co₂(CO)₈Or Pd (PPh)₃Etc. as main catalyst, and trifluoromethanesulfonic acid and phenylmethanesulfonic acid as auxiliaries. Such catalysts are difficult to recover and separate and corrode equipment. Researchers find that the conversion rate of the reaction can be improved by adding pyridine into the catalytic system respectively, but the catalytic system is not economical and environment-friendly, and the defects of a homogeneous catalyst cannot be overcome. Therefore, there is a strong need for a heterogeneous catalyst with high activity and environmental friendliness for such reactions.

Many patents and literature describe metal sulfide catalysts.

Document 1(Nature nanotechnology 2018,411:417) prepared Pt/MoS by injection substitution theory₂The monatomic catalyst is applied to the carbon dioxide reaction, and is found to have ultrahigh activity and selectivity and good industrial value. Meanwhile, the authors found that when the Pt loading is increased, the adjacent Pt atoms have a synergistic catalytic effect, and the effect changes CO₂The energy barrier to hydrogenation, thereby altering the reaction path and altering its selectivity.

Document 2(Nature chemistry,2017,810:816) produced Co-MoS by an electrostatic adsorption method₂The monatomic catalyst showed excellent activity and stability in the reaction of preparing toluene by hydrodeoxygenation of 4-cresol, and compared with the catalyst not doped with Co, the authors increased the interaction between Co and the support, so that the Co center had excellent activity in this reaction.

Reference 3(Nature Communications,2014, sep,17) prepared Pd-MoS₂A catalyst exhibiting catalytic activity and stability comparable to Pt electrodes in electrocatalytic HER reactions

Document 4(Adv Funct Mater,2014,24,2155-2162) synthesizes a series of metal sulfides (FeS)₂,CoS₂,NiS₂Etc.), the results show that the transition metal sulfides have good electrocatalytic activity in the electrocatalytic reaction.

Document 5(Energy Environ Sci,2015,8:1594-₂A monoatomic catalyst, the catalysisThe catalyst shows catalytic activity equivalent to that of Pt in HER reaction, and the methanol poisoning resistance of the catalyst is obviously improved.

Disclosure of Invention

The catalyst shows high activity and selectivity in unsaturated hydrocarbon carboxy methyl esterification reaction, and has mild reaction condition, low cost and industrial application prospect.

The invention also aims to provide a method for preparing the supported monatomic metal catalyst, which has simple process flow and easy process control.

In order to achieve the purpose, the invention adopts the technical scheme that:

the active component of the supported monatomic noble metal catalyst is any one or mixture of two of common noble metals of Ru, Rh, Ir, Pt, Pd, Ag and Au, and the carrier is any one or more than two of chromium sulfide, manganese sulfide, iron sulfide, cobalt sulfide, nickel sulfide, copper sulfide, zinc sulfide, molybdenum sulfide, tungsten sulfide and titanium sulfide. Wherein the loading amount of the active metal is 0.05-1.5%.

The preparation process of the loaded monatomic noble metal catalyst is as follows:

1) dissolving a soluble precursor of the noble metal in deionized water, and adding an inorganic or organic complexing reagent to obtain a noble metal complex solution;

wherein the concentration of the noble metal in the noble metal precursor solution is 0.1-100mg/ml, and the preferred concentration is 0.5-5 mg/ml; the ratio of the amounts of substance of active metal to complexing agent is 0.02 to 10, preferably 0.1 to 4.

The soluble precursor of the noble metal is one or more than two of chloride, nitrate and organic complex of the precursor; the inorganic complexing reagent is as follows: one or a mixture of more than two of ammonia water, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium sulfate, ammonium sulfite, ammonium phosphate, ammonium phosphite or other inorganic nitrogen-containing reagents in any ratio, wherein the organic complexing reagent is one or a mixture of more than two of ethylenediamine, diethylamine, ethanolamine, aniline, acetamide, EDTA, triphenylphosphine, triethyl phosphate, cystine, cysteine or other organic N, P, S-containing reagents in any ratio;

2) mixing noble metal complex solution with carrier, stirring at 10-100 deg.C for 10-600 min, filtering, drying at 60-120 deg.C for 8-12 hr to obtain noble metal catalyst precursor, and adding He, Ar and N₂、H₂、O₂Or in any one or more than two of air atmosphere, and roasting for 5-500min at 200-800 ℃.

The reaction is carried out in a solvent, the solvent is methanol or a mixture of methanol and one or more than two of ethanol, isopropanol, tert-butyl alcohol and toluene in any ratio, and the volume concentration of the methanol in the solvent is 5-100%; methanol is simultaneously used as a reaction substrate. The unsaturated hydrocarbon is any one of C2-C5 alkene, alkyne and dialkene, and the molar ratio of the catalyst active component to the reaction substrate is 1 x 10^-4To 1. The preferred reaction temperature is 120-200 ℃, the preferred initial pressure of the unsaturated hydrocarbon and carbon monoxide in the reaction vessel is 0.5-1.5Mp at room temperature, and the preferred reaction time is 1-6 h.

The catalyst can be recycled for more than 2 times, the conversion rate and the selectivity are not obviously reduced, and the catalyst is easy to separate from a reaction solution.

The activity test method of the catalyst provided by the invention comprises the following steps:

the reactor is a high-pressure reaction kettle, the reaction substrate, the internal standard and the solvent are prepared into reaction liquid with certain concentration, a certain amount of reaction liquid is taken by a pipette for reaction each time, the initial pressure of the unsaturated hydrocarbon and the carbon monoxide in the reaction kettle at room temperature is 0.5-1.5Mpa, the reaction temperature is 120-200 ℃, and the reaction time is not less than 1 hour. After the reaction was completed, the reaction mixture was cooled to room temperature, and then a sample was taken for gas chromatography.

The invention has the following effects:

1. the product obtained by the esterification reaction of unsaturated hydrocarbon carboxyl methyl is an industrially important organic monomer, such as synthetic organic glass, high-grade optical lens, water-based paint, high-grade mould and the like. The invention provides a supported high-dispersion noble metal catalyst which has high activity and selectivity for the reaction.

2. The invention provides a load type single atom noble metal catalyst which can be recycled for a plurality of times in the unsaturated hydrocarbon carboxymethyl esterification reaction without obviously reducing the activity.

3. The invention provides a load type single atom noble metal catalyst which is easy to separate from a reaction solution after reaction and is simple and convenient to operate.

In a word, the invention realizes the high-efficiency and high-selectivity conversion of unsaturated hydrocarbon, carbon monoxide and methanol to prepare ester compounds, compared with an industrial homogeneous catalyst system, the catalyst provided by the invention is green and friendly in the reaction process, saves the cost, and is expected to be applied in industry.

Drawings

FIG. 1 is a Pt-MoS of a supported monatomic noble metal prepared in example 1₂Spherical aberration electron microscope pictures of the catalyst.

Detailed Description

The present invention will be further described with reference to the accompanying drawings and detailed description, but the invention is not limited thereto.

Example 1: 0.027g of chloroplatinic acid is dissolved in 5g of deionized water, 0.5g of ethylenediamine organic reagent is added, the mixture is stirred for 1 hour, 1g of molybdenum sulfide is added, the mixture is stirred for 2 hours, filtered and washed, the mixture is placed in a drying oven at 120 ℃, a supported high-dispersion platinum-based catalyst precursor is obtained after drying for 12 hours, the precursor is placed in a quartz tube, and the precursor is treated for 120 minutes at 500 ℃ under Ar condition to obtain 1% Pt/MoS2 catalyst which is used in a dryer for standby. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.

Example 2: dissolving 0.015g of ruthenium chloride in 20g of deionized water, adding 0.5g of 25% ammonia water, stirring for 3h, adding 1g of molybdenum disulfide, stirring for 5h, filtering, washing, placing in a 60 ℃ oven, drying for 8h to obtain a supported high-dispersion ruthenium-based catalyst precursor, placing the precursor in a quartz tube, treating at 600 ℃ for 100min under the He condition to obtain a 1% Ru/MoS2 catalyst, and placing in a dryer for later use. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.

Example 3: 0.027g of chloroplatinic acid is dissolved in 5g of deionized water, 0.5g of ethylenediamine organic reagent is added, the mixture is stirred for 1 hour, 1g of iron sulfide is added, the mixture is stirred for 2 hours, filtered and washed, the obtained product is placed in a drying oven at 120 ℃, a supported high-dispersion platinum-based catalyst precursor is obtained after drying for 12 hours, the precursor is placed in a quartz tube, and the precursor is treated for 120 minutes at 500 ℃ under Ar condition to obtain a 1% Pt/FeS catalyst which is placed in a dryer for standby. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.

Example 4: dissolving 0.015g of chloroplatinic acid in 20g of deionized water, adding 1.5g of ammonium nitrate, stirring for 2 hours, adding 1g of cobalt sulfide, stirring for 1 hour, filtering, washing, placing in a drying oven at 100 ℃, drying for 8 hours to obtain a supported high-dispersion platinum-based catalyst precursor, placing the precursor in a quartz tube, and adding N₂After 240 seconds of treatment at 300 ℃ under the conditions, 1% Pt/CoS2 monatomic catalyst was obtained and was ready for use in the desiccator. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.

Example 5: dissolving 0.017g of palladium chloride in 20g of deionized water, adding 0.2g of ethanolamine organic reagent, stirring for 3H, adding 1g of zinc sulfide, stirring for 4H, filtering, washing, placing in a 90 ℃ oven, drying for 10H to obtain a supported high-dispersion palladium-based catalyst precursor, placing the precursor in a quartz tube, and carrying out H₂Treating at 350 deg.c for 150min to obtain 1% Pd/ZnS catalyst in a drier for further use. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.

Example 6: 0.021g of chloroauric acid is dissolved in 20g of deionized water, 0.8g of triethyl phosphate organic reagent is added, the mixture is stirred for 1 hour, 1g of tungsten sulfide is added, the mixture is stirred for 2 hours, filtered and washed, the obtained product is placed in an oven at 70 ℃ and dried for 7 hours to obtain a supported high-dispersion gold-based catalyst precursor, the precursor is placed in a quartz tube, and the precursor is treated for 300 minutes at 550 ℃ under the air condition to obtain 1% Au/WS₂And (5) putting the catalyst in a dryer for later use. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.

Example 7: 0.027g of chloroplatinic acid is dissolved in 10g of deionized water, 2g of cysteine organic reagent is added, the mixture is stirred for 2 hours, 1g of titanium sulfide is added, the mixture is stirred for 2 hours, filtered and washed, the obtained product is placed in an oven at 80 ℃, the obtained product is dried for 8 hours to obtain a supported high-dispersion platinum-based catalyst precursor, the precursor is placed in a quartz tube, the obtained product is treated for 80 minutes at 400 ℃ under the He condition to obtain a 1% Pt/TiS2 catalyst, and the obtained product is placed in a dryer for standby. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.

Example 8: dissolving 0.027g of chloroplatinic acid in 10g of deionized water, adding 2g of thiourea organic reagent, stirring for 2h, adding 1g of chromium sulfide, stirring for 2h, filtering, washing, placing in an oven at 80 ℃, drying for 8h to obtain a supported high-dispersion platinum-based catalyst precursor, placing the precursor in a quartz tube, and treating at 500 ℃ for 90min under the He condition to obtain 1% Pt/Cr₂S₃And (5) putting the catalyst in a dryer for later use. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.

Example 9: dissolving 0.017g of palladium chloride in 10g of deionized water, adding 2g of ethylenediamine organic reagent, stirring for 2h, adding 1g of copper sulfide, stirring for 2h, filtering, washing, placing in an oven at 80 ℃, drying for 8h to obtain a supported high-dispersion palladium-based catalyst precursor, placing the precursor in a quartz tube, treating at 400 ℃ for 120min under the He condition to obtain a 1% Pd/CuS catalyst, and placing in a dryer for later use. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.

Example 10: 0.015g of rhodium chloride is dissolved in 20g of deionized water, 0.5g of 25% ammonia water is added, stirring is carried out for 3h, 1g of iron sulfide is added, stirring is carried out for 2h, filtering and washing are carried out, the mixture is placed in an oven at 80 ℃, drying is carried out for 8h to obtain a supported high-dispersion rhodium-based catalyst precursor, the precursor is placed in a quartz tube, and the precursor is treated at 550 ℃ for 120min under the He condition to obtain a 1% Rh/FeS catalyst which is placed in a dryer for standby. As can be seen by spherical aberration electron microscopy, the active ingredient is dispersed on the carrier in the form of a single atom.

Application example 1:

a certain amount of monatomic catalyst is taken to be put in a reaction kettle, 5ml of methanol reaction solution is added by a pipette, and the reaction conditions are 1Mpa of ethylene and 1Mpa of carbon monoxide (initial pressure) and 160 ℃.

The specific experimental results are as follows:

TABLE-results of the hydroformylation of ethylene with a different supported monatomic catalyst

TABLE results of different noble metal monoatomic catalysts in the hydromethyl esterification of ethylene

Claims

1. the application of a supported type single-atom noble metal catalyst in unsaturated hydrocarbon carboxymethylation reaction, it is characterized in that: the active component of described loaded type noble metal catalyst is Pt, and the carrier is molybdenum sulfide, wherein, the active metal The loading amount is 0.05%-1.5%; the active metal is dispersed on the carrier in the form of single atoms;

The preparation process of the supported single-atom precious metal catalyst is as follows:

1) Dissolving the soluble precursor of the precious metal in deionized water, adding an inorganic or organic complexing reagent to obtain a precious metal complex solution;

The precious metal concentration in the precious metal precursor solution is 0.1-100 mg/ml; the ratio of the active metal to the amount of the complexing agent is 0.02-10;

The precious metal soluble precursors are one or more of chlorides, nitrates and organic complexes; the inorganic complexing reagents are: ammonia water, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium sulfate, A mixture of one or more of ammonium sulfate, ammonium phosphate, ammonium phosphite or other inorganic nitrogen-containing reagents in any ratio, the organic complexing reagents are ethylenediamine, diethylamine, ethanolamine, aniline, acetamide, EDTA , triphenylphosphine, triethyl phosphate, cystine, cysteine or other organic containing N, P, S and other reagents in one or more arbitrary ratio mixtures;

2) Mix the precious metal complex solution with the carrier, stir at 10-100 °C for 10-600 minutes, filter, and dry at 60-120 °C for 8-12 hours to obtain a precious metal catalyst precursor, which is mixed with He, Ar , N ₂ , H ₂ , O ₂ or any one or more of two atmospheres in air atmosphere, calcining at 200℃-800℃ for 5-500min.

2. The application according to claim 1, wherein the load is 0.1%-1%.

3 . The application according to claim 1 , wherein the precious metal concentration in the precious metal precursor solution is 0.5-5 mg/ml; and the ratio of the active metal to the amount of the complexing agent is 0.1-4. 4 .

4. The application according to any one of claims 1-3, wherein:

In a closed reaction kettle, the catalyst is dispersed in a solvent and filled with carbon monoxide and unsaturated hydrocarbon gas. The initial pressure of carbon monoxide and unsaturated hydrocarbon gas at room temperature is 0.1-10MPa, the reaction temperature is 50-300 ℃, and the reaction time is not long. in 1 hour.

5. according to the described application of claim 4, it is characterized in that:

Wherein the solvent is methanol or methanol and ethanol, isopropanol, tert-butanol, toluene in one or more arbitrary ratio mixtures, the volume concentration of methanol in the solvent is 5-100%; unsaturated hydrocarbons are C2-C5 Any one or two or more of alkenes, alkynes, and dialkenes, and the molar ratio of the catalyst active component to the reaction substrate is between 1×10-4 and 1.

6. The application according to claim 4, wherein the reaction temperature is 120-200 °C, the initial pressure of unsaturated hydrocarbons and carbon monoxide in the reaction kettle is 0.5-1.5 MPa at room temperature, and the reaction time is 1-6 h.