CN104801299A - Plant reduction preparation method of ruthenium-on-carbon catalyst, ruthenium-on-carbon catalyst and application - Google Patents
Plant reduction preparation method of ruthenium-on-carbon catalyst, ruthenium-on-carbon catalyst and application Download PDFInfo
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Abstract
The invention discloses a plant reduction preparation method of a ruthenium-on-carbon catalyst, the ruthenium-on-carbon catalyst and an application. The plant reduction preparation method of the ruthenium-on-carbon catalyst comprises steps as follows: (1) a ruthenium precursor aqueous solution and carbon supports are evenly mixed, and a carbon support solution capable of adsorbing ruthenium ions is obtained; (2) a Chinese arborvitae twig and leaf extract and the carbon support solution capable of adsorbing the ruthenium ions are mixed to have a reduction reaction, and a catalyst precursor is obtained through treatment; (3) the catalyst precursor is roasted, and the ruthenium-on-carbon catalyst is prepared. The plant reduction preparation method has the advantages of environment-friendliness, mild reduction condition, simple process, low cost and the like, and compared with traditional chemical methods, the biological reduction method is broader in application prospect. The ruthenium loading amount in the prepared ruthenium-on-carbon catalyst is in a range of 0.01-5wt%. The ruthenium-on-carbon catalyst catalyzes an aromatic ring structure or carbon-carbon double bond saturation hydrogenation reaction, and the yield of hydrogenation products can be higher than 99%.
Description
Technical field
The present invention relates to load ruthenium catalyst field, particularly relate to a kind of plant reduction preparation method of carbon supported ruthenium catalyst, carbon supported ruthenium catalyst and application.
Background technology
Hydrogenation reaction containing unsaturated carbon carbon bond compound catalyst used is generally metal carrying catalyst, and conventional metal carrying catalyst has nickel system, ruthenium system and platinum group.Along with deepening continuously of studying ruthenium catalyst, load ruthenium catalyst also becomes the focus of research in the application of other industrial circles.Ruthenium element is the precious metal element that in the earth's crust, content is minimum, its load can be increased on a support material specific area and the decentralization of metallic, and then improves the utilization rate of ruthenium particle, reduces the cost of catalyst.
The reaction that load ruthenium catalyst participates in is mostly structure-sensitive, mainly occurs in ruthenium particle surface.Therefore, the ruthenium presoma being carried on carrier surface usually needs first to be reduced into ruthenium simple substance and just has catalytic activity later.The method of reducing that ruthenium nano-particle is conventional mainly contains gas phase reduction process and liquid phase reduction, and conventional reducing agent generally comprises hydrogen, hydrazine hydrate, boron hydride and polyalcohol.Reducing agent and method of reducing can change particle diameter, pattern, the performance such as stability and dispersiveness of carrier surface ruthenium nano-particle, and then have an impact to the activity of catalyst.
The preparation method of load ruthenium catalyst has many kinds, common mainly contains co-precipitation, infusion process and sol-gel process, preparation method directly affects the character of catalyst, structure and catalytic activity, simultaneously due to the difference of the performances such as different materials Acidity of Aikalinity inherently, mechanical strength and pore size, suitable preparation method is selected to have great importance to the performance improving load ruthenium catalyst.Above preparation method's technique is loaded down with trivial details, and the reactivity of Kaolinite Preparation of Catalyst is low and service life is short, limits the application in the industry of these methods.
Application number be 201210470139.3 Chinese patent application disclose a kind of preparation method of producing cyclohexane by benzene hydrogenation noble ruthenium catalyst, described catalyst consists of active component and carrier; Described active component is noble ruthenium salt, and be the one in ruthenium trichloride and nitric acid ruthenium, ruthenium load capacity is 0.01 ~ 3wt%; Described carrier is the one of aluminium oxide, silica or aluminium oxide-silicon oxide complex carrier; Adopt equi-volume impregnating to prepare producing cyclohexane by benzene hydrogenation noble ruthenium catalyst, comprise the following steps: soluble precious-metal ruthenium salting liquid is mixed with maceration extract by (1); (2) by step (1) maceration extract incipient impregnation to spherical or bar shaped carrier, room temperature immersion 8-12h; (3) step (2) catalyst is carried out drying and roasting; (4) calcined catalyst is reduced in a hydrogen atmosphere obtain benzene hydrogenation noble ruthenium catalyst.This preparation method's technique is loaded down with trivial details, and use hydrogen reducing to obtain the experiment condition harshness of catalyst, the catalyst reaction activity of preparation is low and service life is short.
Summary of the invention
The invention provides a kind of plant reduction preparation method of carbon supported ruthenium catalyst, the present invention adopts Chinese arborvitae twig extract reduction ruthenium presoma, and decentralization and the stability of obtained carbon supported ruthenium catalyst are higher, good catalytic activity.
A plant reduction preparation method for carbon supported ruthenium catalyst, comprises the following steps:
(1) ruthenium precursor water solution and carbon carrier mix and blend, obtains the carbon carrier solution adsorbing ruthenium ion;
(2) there is reduction reaction after the carbon carrier solution mixing of Chinese arborvitae twig extract and absorption ruthenium ion, treatedly obtain catalyst precarsor;
(3) catalyst precarsor obtains carbon supported ruthenium catalyst through roasting.
Ruthenium precursor water solution and carbon carrier first fully mix by the present invention, make Ru (III) ion in ruthenium presoma under electrostatic force uniform load at carbon support, adopt Chinese arborvitae twig extract that Ru (III) the ion original position of carbon support is reduced into ruthenium nano-particle (ruthenium simple substance) again, obtain carbon supported ruthenium catalyst through roasting.
The described ruthenium presoma of step (1) is at least one in ruthenic chloride, nitric acid ruthenium and acetic acid ruthenium, and the ruthenium presoma that the present invention adopts is better water-soluble, easily controls the load capacity of ruthenium in carbon supported ruthenium catalyst.
Preferably, described ruthenium presoma is ruthenic chloride, and preferred ruthenium presoma price is relatively cheap, water-soluble relatively good, and the ruthenium load capacity of obtained catalyst is controlled.
Step (1) described carbon carrier is multi-walled carbon nano-tubes or active carbon, and multi-walled carbon nano-tubes or activated carbon supported ruthenium ion are easily reduced into ruthenium nano-particle by Chinese arborvitae twig extract.
The mol ratio of step (1) ruthenium presoma and carbon carrier is 1:50 ~ 250, the load capacity of the present invention by regulating the mol ratio of ruthenium presoma and carbon carrier can control ruthenium in catalyst.
In the described ruthenium precursor water solution of step (1), the concentration of ruthenium presoma is 0.25 ~ 5mmol/L, and when ruthenium presoma solubility is low, the DeGrain of carbon carrier absorption ruthenium ion, causes load capacity less; During the excessive concentration of ruthenium presoma, carbon carrier can not adsorb ruthenium ion completely, causes ruthenium presoma not to be utilized effectively, and increases the cost of Kaolinite Preparation of Catalyst.
Step (1) ruthenium precursor water solution and carbon carrier mix and blend, carbon carrier is made fully to adsorb ruthenium ion, mixing temperature is 30 ~ 90 DEG C, the mix and blend time is 0.5 ~ 1h, improve temperature within the specific limits, the solubility of ruthenium presoma can be increased, accelerate the speed of carbon carrier absorption ruthenium ion, shorten adsorption time.
Arbor-vitae has another name called Japan cypress, gold zone cypress, is aiphyllium, and its spray, leaf and fruit all can be used as medicine, and cacumen biotae of the present invention is dry branch and the leaf of Cupressaceae plant arbor-vitae.
Step (2) described Chinese arborvitae twig extract contains the extracts such as polysaccharide, phenols, volatile oil and flavonoids.
Ruthenium ion can be reduced into ruthenium nano-particle by the extracts such as the polysaccharide contained in Chinese arborvitae twig extract, phenols, and reducing condition is gentleer; In addition, Cacumen Platycladi extract is attached to catalyst surface as surfactant and protective agent, increases ruthenium nano-particle decentralization on the carbon carrier, improves the stability of carbon supported ruthenium catalyst.
The extracting method of step (2) described Chinese arborvitae twig extract is: add thermal agitation by after the Chinese Arborvitae Twig and Leaf of drying and water mixing, heating-up temperature is 30 ~ 90 DEG C, and mixing time is 2 ~ 5h, and filter and obtain filtrate, gained filtrate is Chinese arborvitae twig extract; The mass ratio of Chinese Arborvitae Twig and Leaf and water is 1: 16 ~ 100.
Described Chinese arborvitae twig extract concentration is 5 ~ 60g/L, when Chinese arborvitae twig extract concentration is low, and the DeGrain of reduction ruthenium ion; Excessive concentration, the extract such as polysaccharide and phenols is saturated in aqueous, and during reduction ruthenium ion, effect change is not obvious.
Preferably, described Chinese arborvitae twig extract concentration is 10 ~ 30g/L, and under preferred concentration, the effect of Chinese arborvitae twig extract reduction ruthenium ion is better.
Chinese arborvitae twig extract concentration of the present invention refers to the quality of Chinese Arborvitae Twig and Leaf and the ratio of Chinese arborvitae twig extract volume.
Step (2) Chinese arborvitae twig extract is 1:1 ~ 3 with the volume ratio of the carbon carrier solution of absorption ruthenium ion, and under this volume ratio, Chinese arborvitae twig extract fully contacts with the carbon carrier of absorption ruthenium ion, can fast reaction speed.
The temperature of step (2) reduction reaction is 30 ~ 90 DEG C, improve reaction temperature within the specific limits, the solubility of Cacumen Platycladi extract can be increased, accelerate reduction reaction speed, but temperature is too high, easily cause the reducing substances inactivation such as polysaccharide and phenols in Chinese arborvitae twig extract.
The time of step (2) reduction reaction is 1 ~ 5h, and the reaction time is relevant with reaction temperature, concentration of substrate etc.
The object of step (3) roasting is activating catalyst, and sintering temperature is 100 ~ 600 DEG C, and the lower catalyst that causes of sintering temperature activates not exclusively; Sintering temperature is too high easily causes catalysqt deactivation.Preferably, sintering temperature is 400 ~ 600 DEG C.
Step (3) roasting time is 3 ~ 5h, and roasting time is relevant with sintering temperature etc.
The carbon supported ruthenium catalyst that the present invention also provides described plant reduction preparation method to obtain.
In described carbon supported ruthenium catalyst, ruthenium load capacity is 0.01 ~ 5wt%, and carbon supported ruthenium catalyst provided by the invention, when load capacity is lower, catalytic activity is also higher.
In described carbon supported ruthenium catalyst, ruthenium exists with the form of nano particle, the particle diameter of ruthenium nano-particle is 1.5 ~ 5nm, in carbon supported ruthenium catalyst provided by the invention, the particle diameter of ruthenium nano-particle is little and even, can increase the specific area of ruthenium, improves the catalytic efficiency of catalyst.
Present invention also offers the application of carbon supported ruthenium catalyst in aromatic ring structure or the reaction of carbon-carbon double bond saturated hydrogenation.
Described aromatic ring structure is selected from benzene or substituted benzene, and the substituting group of described substituted benzene ring is ester group; Described carbon-carbon double bond is selected from maleic anhydride.
The mass ratio of carbon supported ruthenium catalyst and aromatic ring structure or carbon-carbon double bond compound is 0.01 ~ 0.2:1, hydrogenation reaction pressure 0.5 ~ 7MPa, hydrogenation reaction temperature 20 ~ 300 DEG C, hydrogenation reaction time 0.15 ~ 3h.After reaction terminates, cooled by reactant liquor, product is detected by gas-chromatography (GC-1690, OV-1 capillary column) and analyzes.
The carbon supported ruthenium catalyst catalytic performance that the present invention adopts plant reduction preparation method obtained is excellent, and catalysis benzene prepares cyclohexane, and the yield of cyclohexane reaches more than 99%; Catalysis maleic acid anhydride reactant prepares succinic anhydride, conversion ratio and selective all more than 99%.
Compared with prior art, the present invention has following beneficial effect:
The present invention adopts Chinese arborvitae twig extract reducing metal ruthenium ion to obtain carbon supported ruthenium catalyst, load ruthenium ion in-situ reducing on the carbon carrier can be become ruthenium nano-particle by the extracts such as the polysaccharide contained in Chinese arborvitae twig extract, phenols, and reducing condition is gentleer; In addition, Cacumen Platycladi extract is attached to catalyst surface as surfactant and protective agent, increases ruthenium nano-particle decentralization on the carbon carrier, improves the stability of carbon supported ruthenium catalyst.
Carbon supported ruthenium catalyst catalytic performance prepared by the present invention is excellent, and catalysis benzene prepares cyclohexane, and the yield of cyclohexane reaches more than 99%; Catalysis maleic acid anhydride reactant prepares succinic anhydride, conversion ratio and selective all more than 99%.
The plant reduction preparation method that the present invention adopts has environmental friendliness, and reducing condition is gentle, and process is simple, and low cost and other advantages, compared with traditional chemical routes, this biological reducing method has more application prospect.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope picture of catalyst A (2wt%Ru/CNTs).
Fig. 2 is the transmission electron microscope picture of catalyst R (2wt%Ru/AC).
Detailed description of the invention
Embodiment 1
Step (1): accurately measure 2.372mL ruthenic chloride solution (48.2mM) is solvent with deionized water, is mixed with the ruthenium presoma settled solution of 50mL.
Step (2): the multi-walled carbon nano-tubes carrier (CNTs) of precise 0.6g, joins in step (1) ruthenium presoma settled solution, at 60 DEG C, stirs 1h, allows ruthenium metal ion in the abundant adsorptive liquid of carbon carrier.
Step (3): get 1g Chinese Arborvitae Twig and Leaf in conical flask, add 100mL deionized water, puts into heat collecting type heated at constant temperature agitator (30 DEG C, 200rpm) and floods 4h, and filter after dipping, gained filtrate is Chinese arborvitae twig extract.At 60 DEG C, the carrier of mixing 30mL Chinese arborvitae twig extract and absorption ruthenium ion, Ru (III) is reduced to ruthenium nano-particle, and the recovery time is 5h, and filter, and wash 3 times by 50mL deionized water, at 60 DEG C, vacuum drying 12h, obtains catalyst precarsor.
Step (4): by catalyst precarsor calcination activation 3h under electron tubes type high temperature furnace nitrogen atmosphere, sintering temperature is 500 DEG C, namely obtains carbon supported ruthenium catalyst A, and ruthenium load capacity is 2wt%, and Electronic Speculum transmission plot as shown in Figure 1.
Carbon supported ruthenium catalyst A catalysis benzene ring hydrogenation: add 0.05g catalyst successively in 100mL pressure autoclave type reactor, 3mL reactant benzene, reaction temperature is 80 DEG C, and reaction pressure is 4MPa, and the reaction time is 0.5h.Catalytic reaction result is as shown in table 1.
Table 1:
TOF (h in table 1
-1), represent that catalyst is within the unit interval, the mole of the reactant that unit metal ruthenium avtive spot transforms is the important indicator of catalytic efficiency.
Embodiment 2 ~ 5
The preparation of catalyst: prepare carried metal ruthenium catalyst according to the method identical with embodiment 1, then by changing the addition of ruthenic chloride solution in step (1), thus the load capacity of regulation and control catalyst, all the other steps, all with embodiment 1, obtain catalyst B ~ E.The condition of catalyst preparing cyclohexane by hydrogenating benzene is with embodiment 1.Catalytic reaction the results are shown in Table 1.
Embodiment 6 ~ 9
The preparation of catalyst: prepare carried metal ruthenium catalyst according to the method identical with embodiment 1, then change dipping temperature in step (3), all the other steps, all with embodiment 1, obtain catalyst F ~ I.The condition of catalyst preparing cyclohexane by hydrogenating benzene is with embodiment 1.Catalytic reaction the results are shown in Table 1.
Embodiment 10 ~ 13
The preparation of catalyst: prepare carried metal ruthenium catalyst according to the method identical with embodiment 1, then change Chinese arborvitae twig extract concentration in step (3), all the other steps, all with embodiment 1, obtain catalyst J ~ M.The condition of catalyst preparing cyclohexane by hydrogenating benzene is with embodiment 1.Catalytic reaction the results are shown in Table 1.
Embodiment 14 ~ 17
The preparation of catalyst: prepare carried metal ruthenium catalyst according to the method identical with embodiment 1, then change sintering temperature in step (4), all the other steps, all with embodiment 1, obtain catalyst n ~ Q.The condition of catalyst preparing cyclohexane by hydrogenating benzene is with embodiment 1.Catalytic reaction the results are shown in Table 1.
Embodiment 18
Step (1): accurately measure 2.372mL ruthenic chloride solution (48.2mM) is solvent with deionized water, is mixed with the ruthenium presoma settled solution of 50mL.
Step (2): active carbon (AC) carrier of precise 0.6g, joins in above-mentioned settled solution, at 60 DEG C, stirs 1h, allows ruthenium metal ion in the abundant adsorptive liquid of carbon carrier.
Step (3): get 1g Chinese Arborvitae Twig and Leaf in conical flask, add 100mL deionized water, puts into heat collecting type heated at constant temperature agitator (30 DEG C, 200rpm) and floods 4h, and filter after dipping, gained filtrate is Chinese arborvitae twig extract.At 60 DEG C, the carrier of mixing 30mL Chinese arborvitae twig extract and adsorbing metal ions, is reduced to ruthenium nano-particle by Ru (III), recovery time is 5h, filters, and washs 3 times by 50mL deionized water, at 60 DEG C, vacuum drying 12h, obtains catalyst precarsor.
Step (4): by catalyst precarsor calcination activation 3h under electron tubes type high temperature furnace nitrogen atmosphere, sintering temperature is 500 DEG C, namely obtains carbon supported ruthenium catalyst R, and ruthenium load capacity is 2wt%, and Electronic Speculum transmission plot as shown in Figure 2.
Carbon supported ruthenium catalyst catalysis maleic anhydride hydrogenation: add 0.05g catalyst successively in 100mL pressure autoclave type reactor, 5ml mass concentration is the maleic anhydride tetrahydrofuran solution of 18wt%, reaction temperature is 150 DEG C, and reaction pressure is 6MPa, and the reaction time is 0.5h.Catalytic reaction result is as shown in table 2.
Table 2:
Embodiment 19 ~ 22
Carried metal ruthenium catalyst is prepared according to the method identical with embodiment 18.Change the reaction temperature of catalysis maleic anhydride hydrogenation, catalytic reaction the results are shown in Table 2.
Embodiment 23 ~ 26
Carried metal ruthenium catalyst is prepared according to the method identical with embodiment 18.Change the reaction pressure of catalysis maleic anhydride hydrogenation, catalytic reaction the results are shown in Table 2.
Embodiment 27 ~ 30
Carried metal ruthenium catalyst is prepared according to the method identical with embodiment 18.Change the solvent kind of catalysis maleic anhydride hydrogenation, catalytic reaction the results are shown in Table 2.
Embodiment 31 ~ 32
With comparing of existing method Kaolinite Preparation of Catalyst.Buy the standby carbon supported ruthenium catalyst (Ru/C catalyst) obtained of commercial chemical legal system in Aladdin Reagent Company, ruthenium load capacity is 5wt%.Change embodiment 1 and catalyst type in embodiment 18 hydrogenation reaction, catalytic reaction the results are shown in Table 3.
Table 3
As shown in Table 3, and purchase compared with available 5% carbon supported ruthenium catalyst, 2% carbon supported ruthenium catalyst catalysis benzene and the maleic acid anhydride reactant that preparation method of the present invention (plant reduction method) is obtained, the conversion ratio of reactant is higher.
Claims (10)
1. a plant reduction preparation method for carbon supported ruthenium catalyst, comprises the following steps:
(1) ruthenium precursor water solution and carbon carrier mix and blend, obtains the carbon carrier solution adsorbing ruthenium ion;
(2) there is reduction reaction after the carbon carrier solution mixing of Chinese arborvitae twig extract and absorption ruthenium ion, treatedly obtain catalyst precarsor;
(3) catalyst precarsor obtains carbon supported ruthenium catalyst through roasting.
2. the plant reduction preparation method of carbon supported ruthenium catalyst as claimed in claim 1, it is characterized in that, the ruthenium presoma described in step (1) is at least one in ruthenic chloride, nitric acid ruthenium and acetic acid ruthenium; In ruthenium precursor water solution, the concentration of ruthenium presoma is 0.25 ~ 5mmol/L.
3. the plant reduction preparation method of carbon supported ruthenium catalyst as claimed in claim 1, it is characterized in that, the mol ratio of ruthenium presoma and carbon carrier is 1:50 ~ 250.
4. the plant reduction preparation method of carbon supported ruthenium catalyst as claimed in claim 1, is characterized in that, in step (1), the temperature of ruthenium precursor water solution and carbon carrier mixing is 30 ~ 90 DEG C.
5. the plant reduction preparation method of carbon supported ruthenium catalyst as claimed in claim 1, it is characterized in that, step (2) Chinese arborvitae twig extract concentration is 5 ~ 60g/L.
6. the plant reduction preparation method of carbon supported ruthenium catalyst as claimed in claim 1, is characterized in that, in step (2), Chinese arborvitae twig extract is 1:1 ~ 3 with the volume ratio of the carbon carrier solution of absorption ruthenium ion.
7. the plant reduction preparation method of carbon supported ruthenium catalyst as claimed in claim 1, it is characterized in that, step (2) reduction reaction temperature is 30 ~ 90 DEG C.
8. the plant reduction preparation method of carbon supported ruthenium catalyst as claimed in claim 1, it is characterized in that, step (3) sintering temperature is 100 ~ 600 DEG C.
9. the carbon supported ruthenium catalyst that the plant reduction preparation method as described in as arbitrary in claim 1 ~ 8 is obtained, it is characterized in that, in carbon supported ruthenium catalyst, ruthenium load capacity is 0.01 ~ 5wt%.
10. the application of carbon supported ruthenium catalyst as claimed in claim 9 in aromatic ring structure or the reaction of carbon-carbon double bond saturated hydrogenation.
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Cited By (6)
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| CN108993497A (en) * | 2018-08-14 | 2018-12-14 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of nano ruthenium carbon catalyst and the preparation method and application thereof |
| CN109317141A (en) * | 2018-11-14 | 2019-02-12 | 泉州师范学院 | A kind of preparation method of the Pt base catalyst for benzene catalysis oxidation |
| CN110732325A (en) * | 2019-09-11 | 2020-01-31 | 浙江工业大学 | ruthenium-carbon catalyst, and preparation method and application thereof |
| CN110860287A (en) * | 2019-11-07 | 2020-03-06 | 湖北工业大学 | Preparation method of graphene/copper nanocrystalline composite catalytic material |
| CN113083297A (en) * | 2021-04-08 | 2021-07-09 | 中国矿业大学 | Preparation method of high-activity and extremely-low-load ruthenium catalyst Ru @ ZIF-8 and application of catalyst Ru @ ZIF-8 in aspect of catalytic hydrogenation |
| CN115770569A (en) * | 2022-11-21 | 2023-03-10 | 西安航天动力研究所 | Preparation method of ruthenium catalyst |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108993497A (en) * | 2018-08-14 | 2018-12-14 | 中国科学院兰州化学物理研究所苏州研究院 | A kind of nano ruthenium carbon catalyst and the preparation method and application thereof |
| CN108993497B (en) * | 2018-08-14 | 2021-05-28 | 中国科学院兰州化学物理研究所苏州研究院 | Nano ruthenium-carbon catalyst and preparation method and application thereof |
| CN109317141A (en) * | 2018-11-14 | 2019-02-12 | 泉州师范学院 | A kind of preparation method of the Pt base catalyst for benzene catalysis oxidation |
| CN110732325A (en) * | 2019-09-11 | 2020-01-31 | 浙江工业大学 | ruthenium-carbon catalyst, and preparation method and application thereof |
| CN110732325B (en) * | 2019-09-11 | 2022-10-11 | 浙江工业大学 | Ruthenium-carbon catalyst and preparation method and application thereof |
| CN110860287A (en) * | 2019-11-07 | 2020-03-06 | 湖北工业大学 | Preparation method of graphene/copper nanocrystalline composite catalytic material |
| CN110860287B (en) * | 2019-11-07 | 2022-08-19 | 湖北工业大学 | Preparation method of graphene/copper nanocrystalline composite catalytic material |
| CN113083297A (en) * | 2021-04-08 | 2021-07-09 | 中国矿业大学 | Preparation method of high-activity and extremely-low-load ruthenium catalyst Ru @ ZIF-8 and application of catalyst Ru @ ZIF-8 in aspect of catalytic hydrogenation |
| CN113083297B (en) * | 2021-04-08 | 2022-01-21 | 中国矿业大学 | Preparation method of high-activity and extremely-low-load ruthenium catalyst Ru @ ZIF-8 and application of catalyst Ru @ ZIF-8 in aspect of catalytic hydrogenation |
| CN115770569A (en) * | 2022-11-21 | 2023-03-10 | 西安航天动力研究所 | Preparation method of ruthenium catalyst |
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Application publication date: 20150729 |