CN116966902A - Method for preparing methanol and derivatives thereof by photocatalysis of methane and catalyst used by method - Google Patents
Method for preparing methanol and derivatives thereof by photocatalysis of methane and catalyst used by method Download PDFInfo
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- CN116966902A CN116966902A CN202310687811.2A CN202310687811A CN116966902A CN 116966902 A CN116966902 A CN 116966902A CN 202310687811 A CN202310687811 A CN 202310687811A CN 116966902 A CN116966902 A CN 116966902A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 120
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 22
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000002360 preparation method Methods 0.000 claims abstract description 32
- 229910052724 xenon Inorganic materials 0.000 claims abstract description 12
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021603 Ruthenium iodide Inorganic materials 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 3
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 125000003827 glycol group Chemical group 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical group [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 239000007789 gas Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000005286 illumination Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 5
- 238000002256 photodeposition Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VMVNZNXAVJHNDJ-UHFFFAOYSA-N methyl 2,2,2-trifluoroacetate Chemical compound COC(=O)C(F)(F)F VMVNZNXAVJHNDJ-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000012485 toluene extract Substances 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
-
- 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
Abstract
The invention belongs to the field of chemical industry, and particularly relates to a method for preparing methanol by activating methane with a ruthenium-containing catalyst. The invention discloses a preparation method of a ruthenium-supported catalyst, which comprises the following steps: pretreating activated carbon to obtain pretreated activated carbon serving as a carrier; and loading noble metal ruthenium on a carrier to obtain the ruthenium-loaded catalyst. The invention also provides a method for preparing methanol/methanol derivatives by photocatalysis of methane, which comprises the following steps: the method comprises the following steps: the ruthenium-loaded catalyst is put into an autoclave, then a reaction solvent and an oxidant are added, firstly methane is used for replacing air in the autoclave, then methane is continuously introduced until the pressure reaches 0.5-2 MPa, the autoclave is sealed, a short-arc xenon lamp is used for providing a light source, and the reaction is carried out at room temperature, so that the methanol/methanol derivative is obtained. The method for preparing the methanol has the characteristics of simple process, mild condition, high yield and the like.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a method for preparing methanol by activating methane with a ruthenium-containing catalyst.
Background
With the continuous development of social and economic technologies, people pay more attention to the effective utilization of energy. Methane is a major component of resources such as natural gas and shale gas, and has a huge stock in nature, and the conversion of methane into methanol with a high added value is a concern. The current production route commonly used in industry is the indirect method. Methane is first converted into synthesis gas (CO and H) 2 ) The synthesis gas is then further converted to methanol. The steam reforming scheme for indirectly synthesizing methanol needs to be carried out under the condition of high temperature and high pressure, and has high production cost and maintenance cost. Therefore, the development of the catalyst can directly convert methane into methanol under mild conditions, and has wide application prospect.
The supported catalyst has the characteristics of high active site, good selectivity and the like. Richard reported a WO doped with La 3 The material, methane is converted into methanol under the ultraviolet radiation condition, but the conversion rate of methane is very low and is only 10 percent (Photocatalytic conversion of methane). Hameed et al prepared Ag modified WO 3 The material is used for preparing methanol from methane. Research shows that the addition of noble metal element Ag can strengthen photon absorption capacity, speed up the generation of hydroxyl radical and raise the generation rate of methanol obviously (Photocatalytic conversion of methane into methanol: performance of silver impregnated WO) 3 ). Ruthenium is used as one member of noble metals, has the advantages of good reaction activity, low price and the like, and has good activation effect when applied to various activation reactions. Patent CN115212875A discloses a method for dry reforming methane by photocatalysis of ruthenium doped on porous titanium silicon material, compared with other noble metal doped catalysts, the doped ruthenium metal has more active sites, and methane can be successfully converted into H by irradiation for 2 hours under a 300W xenon lamp 2 And CO, the catalyst preparation process of the method is complex, and the catalytic activity of the method for preparing methanol by oxidizing methane is not clear. Patent CN112876338B discloses a ZrO supported catalyst 2 Preparation of ruthenium catalyst and method for preparing methanol and formic acid by catalyzing methane in liquid phase by loading ruthenium on ZrO treated with sulfuric acid 2 The carrier can be at a lower levelTemperature [ ]<The reaction is carried out for a long time at 100 ℃ to obtain the product, but the reaction pressure is higher, the effect is good at 5Mpa, and the maximum yield is lower<25umol)。
In summary, the direct conversion of methane into methanol under mild conditions needs to overcome the problem that the common reaction route has high reaction temperature and pressure, low conversion rate, low reaction rate and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing methanol and derivatives thereof by using mild and efficient photocatalytic methane and a catalyst used by the method.
In order to solve the technical problems, the invention provides a preparation method of a ruthenium-supported catalyst (the ruthenium-supported catalyst is prepared by a photo-deposition method), which comprises the following steps:
1) Preparing active carbon serving as a carrier:
pretreating activated carbon to obtain pretreated activated carbon serving as a carrier;
2) Loading noble metal ruthenium on a carrier:
firstly, mixing water and an organic solvent to form a mixed solvent, wherein the volume ratio of the water to the organic solvent is 1-8:1;
mixing titanium dioxide with the pretreated active carbon obtained in the step 1) according to the weight ratio of 1 (1+/-0.1) to obtain a mixed carrier;
dispersing the carrier after the mixed treatment in a mixed solvent, and then adding ruthenium metal salt for uniform mixing, wherein the weight ratio of ruthenium in the ruthenium metal salt to the carrier after the mixed treatment is 0.1-5% (namely, the loading amount of active center ruthenium element is 0.1-5% by mass);
then stirring reaction (room temperature) is carried out under the irradiation of a light source, the reaction time is 6+/-2 hours, ruthenium is loaded on the surface of the carrier after the mixing treatment, the reaction product is frozen and solidified, and then vacuum freeze drying is carried out, so that the ruthenium loaded catalyst (namely, the active carbon loaded ruthenium metal photocatalyst) is obtained.
Description: during the irradiation process of the light source, ruthenium metal salt can form metal ruthenium; the carrier after the mixing treatment does not react in the irradiation process of the light source, so that the weight is kept unchanged.
As an improvement of the preparation method of the ruthenium-supported catalyst of the present invention:
the ruthenium metal salt is ruthenium trichloride, ruthenium iodide, ruthenium acetate (preferably RuCl) 3 ·3H 2 O)。
Further improvement of the preparation method of the ruthenium-supported catalyst of the present invention:
the weight ratio of ruthenium in the ruthenium metal salt to the carrier after the mixed treatment is 1-5% (optimally 1%).
Further improvement of the preparation method of the ruthenium-supported catalyst of the present invention:
the organic solvent is glycol, ethanol, propanol, acetone, and dioxane.
In general: every 50mgTiO 2 Mixing 20-40 ml of mixed solvent.
As a further improvement of the preparation method of the ruthenium-supported catalyst of the present invention, step 1) is:
adding 1g of active carbon powder (active carbon with carbon content more than or equal to 90 percent) into 50+/-2 mL of concentrated sulfuric acid (sulfuric acid solution with mass concentration of 95-98 percent), and uniformly stirring under an ice bath (stirring time is 2+/-0.5 h); adding 5+/-0.5 g potassium permanganate, then reacting for 1+/-0.1 h at 30+/-5 ℃, then adding 50+/-5 mL deionized water, heating to 80+/-10 ℃ for reacting for 2+/-0.2 h, and after the reaction is finished, cooling to room temperature, adding 50+/-5 mL deionized water and 5+/-0.5 mL hydrogen peroxide solution with mass concentration of 28-32%; then carrying out suction filtration, and washing the solid obtained by suction filtration with deionized water (repeatedly washing until the pH value reaches neutrality); adding water into the washed solid for ultrasonic dispersion (the ultrasonic dispersion time is about 2+/-0.5 h), and finally performing vacuum freeze drying (the freeze drying time is about 10+/-1 h) to obtain the pretreated activated carbon.
The invention also provides a method for preparing methanol/methanol derivatives by photocatalysis of methane, which comprises the following steps: the ruthenium-supported catalyst prepared by any one of the methods comprises the following steps:
putting ruthenium-supported catalyst (omega% = 0.1-5%) into an autoclave (100 mL autoclave with a window), then adding a reaction solvent and an oxidant, replacing air in the autoclave by methane, continuously introducing methane until the pressure reaches 0.5-2 MPa, sealing the autoclave, providing a light source by a short-arc xenon lamp, and reacting at room temperature for 4-16 hours; thereby obtaining methanol/methanol derivatives;
ruthenium catalyst: the amount ratio of the oxidant=1 mg:1-1.5 g.
As an improvement of the method for preparing methanol/methanol derivatives by photocatalytic methane according to the present invention: every 1-1.5 g of oxidant is mixed with 10+/-2 mL of reaction solvent.
As a further improvement of the method for preparing methanol/methanol derivatives by photocatalytic methane according to the invention, the oxidizing agent is: h 2 O 2 、K 2 S 2 O 8 、NaClO。
As a further improvement of the process for the photocatalytic methane preparation of methanol/methanol derivatives according to the invention: the reaction solvent is as follows: h 2 O、CF 3 COOH (trifluoroacetic acid), acetic acid.
According to the catalytic activation method of methane, a supported catalyst which takes transition metal ruthenium as an active center atom is developed, and methane is activated under mild conditions to prepare methanol/methanol derivatives. Under the reaction condition of normal temperature and 0.5-2 MPa, methane is converted into methanol by utilizing illumination.
The reaction equation for preparing methanol by photocatalysis of methane is as follows:
the inventor establishes a technical development route for efficiently converting methane into methanol/methanol derivatives by directly utilizing ruthenium metal catalyst at normal temperature by taking methane, trifluoroacetic acid and the like as raw materials and reaction solvents through comparing the characteristics of different reaction routes. One of the key technical difficulties is the development of efficient monoatomic catalysts.
The method for preparing methanol/methanol derivatives by photocatalysis of methane has the following technical advantages:
1. the supported ruthenium catalyst prepared by the invention has high activity, the preparation method is relatively simple, and the efficiency of preparing methanol by activating methane is high.
2. In the methanol generation process, methane is used as a raw material, the raw material sources are wide, the reaction can be realized at room temperature under illumination, the energy cost is saved, and the production process is environment-friendly.
3. The method for preparing the methanol has the characteristics of simple process, mild condition, high yield and the like.
4. Compared with CN112876338B, the catalyst consumption, reaction temperature and reaction pressure are greatly reduced, but the catalyst has excellent reaction efficiency.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
activated carbon powder, activated carbon powder with carbon content not less than 90% (passing through 100 mesh sieve).
Catalyst preparation example 1 preparation of activated carbon Supported ruthenium catalyst (1%) by photo-deposition method
1) 1g of activated carbon powder is added into 48mL of concentrated sulfuric acid (sulfuric acid solution with the mass concentration of 95 percent) and stirred in an ice bath (0 ℃ C.) for 2 hours until being uniformly mixed; adding 5g of potassium permanganate, and transferring the mixture to a water bath kettle at 30 ℃ for mixed reaction for 1h; adding 50mL of deionized water into the mixture, heating to 80 ℃ for reaction for 2 hours, adding 50mL of deionized water after the reaction is finished and the temperature is reduced to room temperature, and adding 5mL of hydrogen peroxide solution (the mass concentration is 30%); filtering, and washing the solid obtained by filtering with deionized water (50 mL) for multiple times until the pH value is close to neutral; after adding 20mL of water to the washed solid, performing ultrasonic dispersion (the ultrasonic dispersion time is about 2 hours), and then placing the solid into a vacuum freeze drying box to dry for 10 hours at-50 ℃ to-20 ℃ (the solid is dried to constant weight), so as to obtain the pretreated activated carbon.
2) Mixing water and ethylene glycol in a ratio of 8:1 (v/v) to obtain a mixed solvent;
50mg of pretreated activated carbon obtained in step 1) and 50mg of TiO 2 The mixture is used as a carrier after the mixing treatment, and the carrier after the mixing treatment is dispersed in 30ml of mixed solventIn the process, stirring is started until the activated carbon and the TiO are mixed 2 Uniformly dispersing to obtain a dispersion liquid;
about 2.58mg of RuCl was added to the dispersion 3 ·3H 2 O (ruthenium content 1 mg), then placing the mixture in a light source for irradiation (the light source uses a 500W spherical short-arc xenon lamp, the wavelength range of the light source is 300-1100 nm, the light source is positioned at the height of 5-10 cm above the dispersion liquid), stirring and reacting for 6h at room temperature, then placing the mixture in a refrigerator (-20 ℃) for freezing and solidifying the mixture into solid, and finally performing vacuum freezing and drying for 24h at-50 ℃ to-20 ℃ (the mixture is dried to constant weight at the moment), thus obtaining 101.0mg of the active carbon supported ruthenium catalyst with the mass fraction of 1.0%.
Catalyst preparation example 2 preparation of activated carbon Supported ruthenium catalyst (0.1%) by photo-deposition method
1) The same as in step 1) in catalyst preparation example 1;
2) Will "about 2.58mgRuCl 3 ·3H 2 O (ruthenium content 1 mg) "change to" about 0.258mgRuCl 3 ·3H 2 O (ruthenium content 0.1 mg) ", the remainder being identical to step 2) in catalyst preparation example 1; 100.1mg of active carbon supported ruthenium catalyst with the mass fraction of 0.1% is obtained.
Catalyst preparation example 3 preparation of activated carbon Supported ruthenium catalyst (3%) by photo-deposition method
1) The same as in step 1) in catalyst preparation example 1;
2) Will "about 2.58mgRuCl 3 ·3H 2 O (ruthenium content 1 mg) "changed to" about 14.29mg ruthenium iodide (ruthenium content 3 mg) ", the rest being equivalent to step 2) in catalyst preparation example 1; 103.0mg of active carbon supported ruthenium catalyst with the mass fraction of 3.0% is obtained.
Preparation of catalyst 4, preparation of activated carbon Supported ruthenium catalyst by photo deposition (5%)
1) The same as in step 1) in catalyst preparation example 1;
2) Will "about 2.58mgRuCl 3 ·3H 2 O (ruthenium content 1 mg) "changed to" about 13.76mg ruthenium acetate (ruthenium content 5 mg) ", the rest being equivalent to step 2) in catalyst preparation example 1; 105.0mg of active carbon supported ruthenium catalyst with the mass fraction of 5.0% is obtained.
Example 1, a method for preparing a methanol derivative by photocatalytic methane, the following steps are sequentially performed:
1) 1mg of activated carbon-supported ruthenium catalyst (1%) was added to a reactor containing 10mL of CF 3 100mL of COOH (trifluoroacetic acid) was placed in a window autoclave, and 1.35g of K was added 2 S 2 O 8 After sealing, methane is introduced to replace the gas in the autoclave; the reaction temperature is set to be normal temperature (room temperature), then methane is continuously introduced until the pressure in the autoclave is 1MPa (about 0.04 mol), and the reaction is stirred for 12 hours under the illumination of a xenon lamp (the illumination of a 500W xenon lamp is used, the wavelength range of the light source is 300-1100 nm, and the xenon lamp is positioned at the height of 5-10 cm above a window of the autoclave).
2) After the reaction time set in step 1) was reached, the autoclave was cooled to-10℃and the gas (methane) in the autoclave was collected by an air bag, 5mL of toluene extract liquid reaction product (toluene extract) was added to the autoclave, and the product (toluene extract) was detected by GC and methanol derivative (methyl trifluoroacetate) was mainly produced with a small amount of formaldehyde, and the results were shown in Table 1.
Example 2, a method for preparing methanol by photocatalytic methane, the following steps are sequentially performed:
1) 1mg of activated carbon-supported ruthenium catalyst (0.1%) was added to a reactor equipped with 10mLH 2 Adding 1mL of hydrogen peroxide (the mass concentration is 30%) into 100mL of O autoclave with a window, sealing, and introducing methane to replace the gas in the autoclave; the reaction temperature was set at room temperature, and then methane was continuously introduced until the pressure in the autoclave became 0.5MPa (about 0.02 mol), and the reaction was stirred under the irradiation of a xenon lamp for 16 hours.
2) Equivalent to step 2) of example 1, the product was checked by GC to produce methanol as the main component and a small amount of formaldehyde as shown in Table 1.
Example 3, a method for preparing a methanol derivative by photocatalytic methane, the following steps are sequentially performed:
1) 1mg of activated carbon-supported ruthenium catalyst (3%) was added to a reactor containing 10mL of acetic acid CH 3 100mL of COOH with a window is put into an autoclave, 1mL of hydrogen peroxide (the mass concentration is 30%) is added, and methane is introduced into the autoclave for replacing the gas in the autoclave after sealing; the reaction temperature is set to be normal temperature, and then methane is continuously introducedUntil the pressure in the autoclave is 1MPa, stirring and reacting for 12h under the illumination of a xenon lamp.
2) Equivalent to step 2) of example 1, the product was checked by GC for the formation of a small amount of formaldehyde based on the methanol derivative (ethyl acetate) and the results are given in Table 1.
Example 4, a method for preparing a methanol derivative by photocatalytic methane, the following steps are sequentially performed:
1) 1mg of activated carbon-supported ruthenium catalyst (3%) was added to a reactor containing 10mLCF 3 About 1mL of LNaClO solution (containing 1.25g of NaClO) was added to a 100mL autoclave of COOH, and methane was introduced into the autoclave after sealing to displace the gas in the autoclave; the reaction temperature is set to be normal temperature, then methane is continuously introduced until the pressure in the autoclave is 1MPa, and the reaction is stirred for 8 hours under the illumination of a xenon lamp.
2) Equivalent to step 2) of example 1, the product was checked by GC for the formation of a small amount of formaldehyde based on the methanol derivative (methyl trifluoroacetate) and the results are shown in Table 1.
Example 5, a method for preparing a methanol derivative by photocatalytic methane, the following steps are sequentially performed:
1) 1mg of the supported ruthenium catalyst (5%) is added into a 100mL autoclave filled with 10mL of acetic acid, 1mL of hydrogen peroxide (mass concentration is 30%) is added, and methane is introduced after sealing to replace the gas in the autoclave; the reaction temperature is set to be normal temperature, then methane is continuously introduced until the pressure in the autoclave is 2MPa, and the reaction is stirred for 4 hours under the illumination of a xenon lamp.
2) The same procedure as in step 2) of example 1 was repeated, and the product was subjected to GC detection and was mainly methanol derivative (ethyl acetate) and a small amount of formaldehyde was formed, and the results are shown in Table 1.
TABLE 1
The selective calculation formula is
Taking example 1 as an example, the target product is a nail alcohol derivative (methyl trifluoroacetate), and the total product is a nail alcohol derivative and formaldehyde.
The yield is calculated as
Comparative example 1 the total volume of the mixed solvent was maintained as shown in Table 2, except that the mixed solvent in step 2) of catalyst preparation example 1 was changed to be equivalent to that of catalyst preparation example 1.
The resulting catalyst was substituted for the ruthenium catalyst of example 1, the remaining conditions were the same as in example 1, the selectivity results were not much different from example 1, and the yield results are shown in Table 2.
TABLE 2
| Mixed solvent (v/v) | Yield (mu mol h) -1 ·g -1 Cat ) | |
| Example 1 | Water: ethylene glycol=8:1 | 6.4 |
| Comparative example 1 | Water: ethylene glycol=5:1 | 4.3 |
| Water: ethylene glycol=1:1 | 3.6 | |
| Water: ethanol=8:1 | 4.9 | |
| Water: propanol=8:1 | 5.1 | |
| Water: acetone=8:1 | 3.3 | |
| Water: dioxane = 8:1 | 4.2 |
Comparative example 2, changing the activated carbon in step 1) of the catalyst preparation example 1 to graphene/carbon powder, i.e., respectively pre-treating the graphene and the carbon powder, thereby respectively obtaining pre-treated graphene and pre-treated carbon powder; the pretreated graphene/pretreated carbon powder is used for replacing the pretreated activated carbon, and the rest is the same as the catalyst preparation example 1.
The resulting catalyst was substituted for the ruthenium catalyst in example 1, the remaining conditions were the same as in example 1, and the results are shown in Table 3.
TABLE 3 Table 3
| Carrier body | Selectivity (%) | Yield (mu mol h) -1 ·g -1 Cat ) | |
| Example 1 | Activated carbon | 89％ | 6.4 |
| Comparative example 2 | Graphene | 62％ | 2.7 |
| Carbon powder | 56％ | 1.3 |
Comparative example 3 TiO in step 2) of catalyst preparation example 1 2 SiO is changed into 2 The remainder was identical to catalyst preparation 1.
The resulting catalyst was substituted for the ruthenium catalyst in example 1, and the other conditions were the same as in example 1, except that no methanol derivative was detected after the reaction was completed.
Comparative example 4 "activated carbon and TiO after pretreatment" in step 2) of catalyst preparation example 1 2 The carrier after the mixing treatment obtained by mixing was "changed to" 100mg ZrO 2 The rest is equivalent to the catalyst preparationPreparation 1.
The resulting catalyst was substituted for the ruthenium catalyst of example 1, and the remaining conditions were identical to those of example 1.
The results obtained were: the selectivity was about 68% and the yield was about 3.5. Mu. Mol.h -1 ·g -1 Cat 。
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (9)
1. The preparation method of the ruthenium-supported catalyst is characterized by comprising the following steps:
1) Preparing active carbon serving as a carrier:
pretreating activated carbon to obtain pretreated activated carbon serving as a carrier;
2) Loading noble metal ruthenium on a carrier:
firstly, mixing water and an organic solvent to form a mixed solvent, wherein the volume ratio of the water to the organic solvent is 1-8:1;
mixing titanium dioxide with the pretreated active carbon obtained in the step 1) according to the weight ratio of 1 (1+/-0.1) to obtain a mixed carrier;
dispersing the carrier after the mixed treatment in a mixed solvent, and then adding ruthenium metal salt for uniform mixing, wherein the weight ratio of ruthenium in the ruthenium metal salt to the carrier after the mixed treatment is 0.1-5%;
then stirring and reacting under the irradiation of a light source for 6+/-2 hours, so that ruthenium is loaded on the surface of the carrier after the mixing treatment, freezing and solidifying the reaction product, and then performing vacuum freeze drying to obtain the ruthenium loaded catalyst.
2. The method for preparing a ruthenium-supported catalyst according to claim 1, wherein:
the ruthenium metal salt is ruthenium trichloride, ruthenium iodide or ruthenium acetate.
3. The method for preparing a ruthenium-supported catalyst according to claim 2, wherein:
the weight ratio of ruthenium in the ruthenium metal salt to the carrier after the mixed treatment is 1-5%.
4. A process for preparing a ruthenium-supported catalyst according to any one of claims 1 to 3, wherein:
the organic solvent is glycol, ethanol, propanol, acetone, and dioxane.
5. The method for preparing a ruthenium-supported catalyst according to any one of claims 1 to 4, wherein the step 1) is:
adding 1g of active carbon powder into 50+/-2 mL of concentrated sulfuric acid, and uniformly stirring under an ice bath; adding 5+/-0.5 g potassium permanganate, then reacting for 1+/-0.1 h at 30+/-5 ℃, then adding 50+/-5 mL deionized water, heating to 80+/-10 ℃ for reacting for 2+/-0.2 h, and after the reaction is finished, cooling to room temperature, adding 50+/-5 mL deionized water and 5+/-0.5 mL hydrogen peroxide solution with mass concentration of 28-32%; then carrying out suction filtration, and washing the solid obtained by suction filtration with deionized water; adding water into the washed solid for ultrasonic dispersion, and finally, performing vacuum freeze drying to obtain the pretreated activated carbon.
6. A method for preparing methanol/methanol derivatives by photocatalysis of methane is characterized in that: ruthenium-supported catalyst prepared by the process according to any one of claims 1 to 5, comprising the steps of:
putting a ruthenium-supported catalyst into an autoclave, then adding a reaction solvent and an oxidant, firstly using methane to replace air in the autoclave, then continuously introducing methane until the pressure reaches 0.5-2 MPa, sealing the autoclave, providing a light source by a short-arc xenon lamp, and reacting at room temperature for 4-16 hours; thereby obtaining methanol/methanol derivatives;
ruthenium catalyst: the amount ratio of the oxidant=1 mg:1-1.5 g.
7. The method for preparing methanol/methanol derivatives by photocatalytic methane according to claim 6, characterized in that: every 1-1.5 g of oxidant is mixed with 10+/-2 mL of reaction solvent.
8. The method for preparing methanol/methanol derivatives by photocatalytic methane according to claim 6 or 7, characterized in that:
the oxidant is as follows: h 2 O 2 、K 2 S 2 O 8 、NaClO。
9. The method for preparing methanol/methanol derivatives by photocatalytic methane according to claim 8, characterized in that:
the reaction solvent is as follows: h 2 O、CF 3 COOH, acetic acid.
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