CN101850249B - Structured ruthenium catalyst and preparation method thereof - Google Patents
Structured ruthenium catalyst and preparation method thereof Download PDFInfo
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- CN101850249B CN101850249B CN2009100485637A CN200910048563A CN101850249B CN 101850249 B CN101850249 B CN 101850249B CN 2009100485637 A CN2009100485637 A CN 2009100485637A CN 200910048563 A CN200910048563 A CN 200910048563A CN 101850249 B CN101850249 B CN 101850249B
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Abstract
The invention provides a structured ruthenium catalyst taking integral carbon nanofibers as carriers and a preparation method thereof. The catalyst of the invention takes structured carbon nanofibers as catalyst carriers and loads ruthenium catalyst. The preparation method of the structured ruthenium catalyst comprises the steps that: structured carbon nanofiber carriers are equivalently or excessively dipped in ruthenium compound solution, the carriers are aged at room temperature and are dried, and finally the carriers are reduced to obtain the ruthenium catalyst loaded on structured carbon nanofibers. The structured ruthenium catalyst can be used for continuous production and industrial kettle reactor liquid-phase catalytic reaction and can be combined with the research and the design of reactors, the separation and treatment troubles do not exits in the industrial application, and the process can be easily amplified and can be technically managed. Moreover, the structured ruthenium catalyst has good catalytic activity and selectivity in sorbierite hydrogenolysis.
Description
Technical field
The present invention relates to catalyst field, being specifically related to a kind of is ordered structure ruthenium (Ru) Catalysts and its preparation method of carrier with the monolithic devices carbon nano-fiber.
Background technology
The development and application of novel catalyst carrier material is the key areas of heterogeneous catalytic reaction research.In recent years, carbon nano-fiber (carbon nanofiber is called for short CNF) as a kind of novel carbonaceous material, becomes one of research focus of catalytic field.CNF is applied to catalytic field as catalyst carrier, compare with traditional carbonaceous carriers such as active carbon, have many advantages, controlled as micro-structural, interfacial effect is strong, middle hole characteristic, heat endurance and mechanical strength are high, therefore can produce active influence to activity of such catalysts, selectivity, life-span etc. as catalyst carrier.
On the other hand, reactive metal being carried on the ordered structure carrier making catalyst structureization, is the environmental protection of chemical industry and the requirement of sustainable development.For the chemical field that has numerous heterogeneous catalytic reactions to exist, structural catalyst/reactor is owing to have the characteristics and the performance of catalyst and reactor concurrently, can improve the selectivity of activity of such catalysts and specialities, improve the efficient and the utilization rate of catalyst, become hot research in recent years.
Usually the fibre diameter of carbon nano-fiber is generally less than 200nm, and length is that μ m～mm does not wait.Therefore macroscopical form of carbon nano-fiber is trickle powder, and the size of powder particle depends on the preparation method and the growth conditions of carbon nano-fiber.When it was applied to adopt the continuous process of fixed bed reactors, fine catalyst was very easily taken away by liquid stream at a high speed, the clog downstream pipeline, or cause catalyst loss, also exist the resistance of fine catalyst bed big simultaneously, unfavorable factors such as energy consumption height.On the other hand, when it is applied to the liquid-phase catalysis process of industrial tank reactor, have catalyst and reactant liquor separation difficulty equally, catalyst recovery is utilized problems such as difficulty, is unfavorable for commercial Application and amplification process.Therefore, with the material that the further processing and preparing of powder nanometer carbon fiber becomes to have certain macro-size and certain geometrical shape, become the prerequisite of its industrial applications.
The present inventor discloses a kind of nano carbon fiber/graphite felt compound catalytic material and preparation method thereof in publication number is the Chinese invention patent of CN1736585, obtained to have the ordered structure carbon nano-fiber composite than bigger serface.Simultaneously in publication number is the Chinese invention patent of CN101070250, disclose Integrated nano carbon-fiber composite porous materila and preparation method, obtained the regular carbon nano-fiber that the carbon nano-fiber by growth in situ on graphite fibre felt matrix, carbon coating and the carbon coating constitutes.In the above-mentioned invention, by distinct methods formed in situ carbon nano-fiber on the graphite felt matrix, the ordered structure carbon nano-fiber that obtains has bigger specific area, can reach 100～300m
2/ g, because its duct is to be twined to pile up by fiber to form, and micropore is few, its specific area almost all is an external surface area, thereby it effectively utilizes area very big as catalyst carrier simultaneously.But have not yet to see the report of the ruthenium catalyst that utilizes the load of described ordered structure carbon nano-fiber.
Summary of the invention
Primary and foremost purpose of the present invention is the carbon nano-fiber of ordered structure is further developed, and is the structured ruthenium catalyst of carrier with the monolithic devices carbon nano-fiber thereby provide a kind of.
It is the preparation method of the structured ruthenium catalyst of carrier that second purpose of the present invention is to provide with the monolithic devices carbon nano-fiber.
Structured ruthenium catalyst of the present invention is a catalyst carrier with the ordered structure carbon nano-fiber, and load ruthenium catalyst.
According to catalyst of the present invention, be benchmark with ordered structure carbon nano-fiber quality, the load capacity of described metal Ru is 1～5%.
The preparation method of structured ruthenium catalyst of the present invention may further comprise the steps:
The ordered structure nano-carbon fibre carrier is with containing ruthenium compound solution equivalent impregnation or excessive dipping, at room temperature aging, oven dry then, reduction at last obtains to be carried on the ruthenium catalyst on the ordered structure carbon nano-fiber.
Preparation in accordance with the present invention, described reduction is meant at H
2In/Ar the atmosphere, under 200～300 ℃ condition, reduced 5～10 hours.
Preparation in accordance with the present invention, the described ruthenium compound that contains is a ruthenium trichloride.
Preparation in accordance with the present invention also comprises the pretreated step that the ordered structure nano-carbon fibre carrier is soaked, washs, dries with dilute acid soln.
Preparation in accordance with the present invention also comprises pretreated ordered structure nano-carbon fibre carrier is used 30% H again
2O
2Solution carries out the step of surface oxidation treatment.
Preparation in accordance with the present invention also comprises pretreated ordered structure nano-carbon fibre carrier is used HNO again
3Solution carries out the step of surface oxidation treatment.
Of the present invention is that the structured ruthenium catalyst of carrier has the following advantages with the monolithic devices carbon nano-fiber:
(1) bigger specific area can contact reactant fast with active site, can improve activity of such catalysts and selectivity;
(2) can be applied to produce continuously and the reaction of industrial tank reactor liquid-phase catalysis, can be when commercial Application the research and the design of catalyst and reactor be organically combined;
(3) do not have the separation and the handling problem of catalyst, the process that makes is amplified and technical management easily;
(4) be used for carrying out hydrogenolysis on sorbierite as new catalyst and prepare ethylene glycol and propane diols, can obtain sorbierite conversion ratio and ethylene glycol preferably preferably, the propane diols yield;
(5) can in suitability for industrialized production, be used on a large scale.
Description of drawings
Fig. 1 is the photo of ordered structure nano-carbon fibre carrier and supported ruthenium catalyst thereof, and wherein A is the ordered structure carbon nano-fiber of embodiment 1, and B～D is followed successively by the structured ruthenium catalyst of embodiment 2,3,4.
Fig. 2 is the scanning electron microscope diagram sheet of the structured ruthenium catalyst of embodiment 3.
The specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.Should be understood that following examples only are used to the present invention is described but not are used to limit scope of the present invention.
Ordered structure carbon nano-fiber of the present invention is meant and adopts chemical vapour deposition technique at the resulting compound catalyze material with globality of graphite felt matrix surface growth in situ carbon nano-fiber, can be carried according to actual needs to cut and be obtained certain shape and size, its size may diminish to several millimeters, also can arrive tens of centimetres greatly.Can be by patent CN1736585, the disclosed method of CN101070250 is synthetic.
In following examples, ruthenium compound solution adopts equivalent impregnation method or excessive infusion process (" the catalyst engineering introduction " of Wang Shangdi, Sun Junquan work, Chemical Industry Press, 2001) to load on the ordered structure carbon nano-fiber.
Among the present invention:
Initial concentration * 100% of sorbierite conversion ratio (%)=(initial concentration of sorbierite-reaction finishes the concentration of back sorbierite)/sorbierite.
Amount of substance * 1/3 * 100% of the sorbierite of the amount of substance of ethylene glycol in glycol selectivity (%)=product/participation reaction.
Amount of substance * 1/2 * 100% of the sorbierite of the amount of substance of propane diols in propane diols selectivity (%)=product/participation reaction.
Embodiment 1, the ordered structure nano-carbon fibre carrier preparation
With definite shape and the size original graphite felt under air atmosphere, about 6 hours of about 500 ℃ of roastings.The nickel nitrate solid is configured to maceration extract in the water-soluble or absolute ethyl alcohol.By the equivalent impregnation method nickel nitrate is loaded to through on the graphite felt of roasting, dry at ambient temperature aging 12 hours then, again in air 120 ℃ the oven dry 8 hours, in 150 ℃ of roastings 3 hours or directly use hydrogen reducing, the load capacity (weight) of nickel metal is 0.1～3% to dried sample on the graphite felt of Huo Deing at last in air.
The graphite felt of above-mentioned nickel-loaded is placed vertical quartz glass pipe reactor, at H
2In/Ar (volume ratio 1: the 3) gaseous mixture, 600 ℃ were reduced 3 hours, and heating rate is 5 ℃/min.Switch to C then
2H
6And H
2Gaseous mixture (volume ratio 1: 1), kept 8 hours, obtain the ordered structure carbon nano-fiber, shown in Figure 1A, its size is far longer than conventional powder finely grained catalyst, and shape, size can be to set arbitrarily on demand.
Embodiment 2, structured ruthenium catalyst preparation
With ruthenium content 37% RuCl
3Slaine is dissolved in deionized water or the absolute ethyl alcohol and is configured to maceration extract, by the equivalent impregnation method with RuCl
3Uniform load is to the ordered structure carbon nano-fiber of embodiment 1 gained, and dry at ambient temperature aging 24 hours of impregnated sample was dried 12 hours under 120 ℃ of conditions in baking oven again.At H
2300 ℃ reduction 5 hours in/Ar (volume ratio 1: the 4) atmosphere, obtain the Ru load capacity and be 3.0% be the structured ruthenium catalyst of carrier with the carbon nano-fiber, shown in Figure 1B.
Embodiment 3, structured ruthenium catalyst preparation
3.1, the preliminary treatment of ordered structure nano-carbon fibre carrier
With the ordered structure Nano carbon fibers 2M of the Wesy dilute hydrochloric acid solution washing by soaking of embodiment 1 preparation 6～24 hours, the purpose of washing is to wash the required catalyst metals nickel of growing nano carbon fiber off, then with deionized water rinsing till the neutrality, sample after the soaking flushing was 120 ℃ of oven dry 6～18 hours, and said process repeats 3～5 times.
3.2, ordered structure Ru Preparation of catalysts
With ruthenium content 37% RuCl
3Slaine is dissolved in deionized water or the absolute ethyl alcohol and is configured to maceration extract, by the equivalent impregnation method with RuCl
3Uniform load is to the pretreated ordered structure carbon nano-fiber of step 3.1 gained, and dry at ambient temperature aging 24 hours of impregnated sample was dried 12 o'clock under 110 ℃ of conditions in baking oven again.At H
2300 ℃ reduction 8 hours in/Ar (volume ratio 1: the 4) atmosphere, the load capacity that obtains Ru be 5.0% be the structured ruthenium catalyst of carrier with the carbon nano-fiber, shown in Fig. 1 C, its scanning electron microscope diagram sheet is as shown in Figure 2.
Embodiment 4, structured ruthenium catalyst preparation
4.1, the preliminary treatment of ordered structure nano-carbon fibre carrier
According to the described method of step 3.1 ordered structure Nano carbon fibers Wesy watery hydrochloric acid is carried out preliminary treatment.
4.2, the surface oxidation treatment of ordered structure nano-carbon fibre carrier
The ordered structure carbon nano-fiber that step 4.1 is pretreated places beaker, pours a certain amount of 30% H into
2O
2Solution, 40～150 ℃ of surface oxidation treatment 1～24 hour, used H
2O
2The amount of solution is every gram carrier 20～50mL.
4.3, ordered structure Ru Preparation of catalysts
With ruthenium content 37% RuCl
3Slaine is dissolved in deionized water or the absolute ethyl alcohol and is configured to maceration extract, by the equivalent impregnation method with RuCl
3On the ordered structure carbon nano-fiber that uniform load is crossed to step 4.2 gained surface oxidation treatment, dry at ambient temperature aging 12 hours of impregnated sample, oven dry 24 hours under 110 ℃ of conditions in baking oven again.At H
2300 ℃ reduction 10 hours in/Ar (volume ratio 1: the 4) atmosphere, the load capacity that obtains Ru be 1.0% be the structured ruthenium catalyst of carrier with the carbon nano-fiber, shown in Fig. 1 D.
Embodiment 5, structured ruthenium catalyst preparation
5.1, the preliminary treatment of ordered structure nano-carbon fibre carrier
According to the described method of step 3.1 ordered structure Nano carbon fibers Wesy watery hydrochloric acid is carried out preliminary treatment.
5.2, the surface oxidation treatment of ordered structure nano-carbon fibre carrier
The ordered structure carbon nano-fiber that step 5.1 is pretreated places beaker, pours 4～14mol/L HNO into
3Solution, 40 ℃ of surface oxidation treatment 24 hours, used HNO
3The amount of solution is every gram carrier 20～50mL.
5.3, ordered structure carbon nano-fiber load Ru Preparation of catalysts
With ruthenium content 37% RuCl
3Slaine is dissolved in deionized water or the absolute ethyl alcohol and is configured to maceration extract, by the equivalent impregnation method with RuCl
3On the ordered structure carbon nano-fiber that uniform load is crossed to step 5.2 gained surface oxidation treatment, dry at ambient temperature aging 24 hours of impregnated sample, oven dry 48 hours under 80 ℃ of conditions in baking oven again.At H
2200 ℃ reduction 10 hours in/Ar (volume ratio 1: the 4) atmosphere, the load capacity that obtains Ru be 3.0% be the structured ruthenium catalyst of carrier with the carbon nano-fiber.
Embodiment 6, structured ruthenium catalyst is used for the sorbierite hydrogenolysis
In the stainless steel autoclave of 500mL, add calcium oxide 10 grams, sorbierite 66 grams are configured to the solution that gross mass is 330g with deionized water.The various ordered structure Ru catalyst of the reduction that embodiment 2～5 is prepared are cut into the form of the blade of reactor, are fixed on the shaft, and the quality of catalyst is got 1.5g.Sorbierite hydrogenolysis temperature is 220 ℃, and the hydrogen dividing potential drop is 8.0MPa, and stir speed (S.S.) is made as 600 rev/mins, and the reaction time is 6 hours, and question response finishes back cooling sampling, and institute's sample thief adopts efficient liquid phase chromatographic analysis, and the result is as shown in table 1.
Table 1
As shown in Table 1, of the present invention is that the structured ruthenium catalyst of carrier can be used for carrying out hydrogenolysis on sorbierite with the carbon nano-fiber, load capacity is that 1～5% structured ruthenium catalyst all can obtain sorbierite conversion ratio and ethylene glycol, propane diols yield preferably preferably, can be applied industrial.Under Ru load capacity and the identical condition of reaction condition, use catalyst to react through watery hydrochloric acid preliminary treatment and surface oxidation treatment, have lower sorbierite hydrogenolysis activity (conversion ratio), but it shows higher ethylene glycol and propane diols selectivity.
In sum, of the present invention is that the structured ruthenium catalyst of carrier has bigger specific area with the monolithic devices carbon nano-fiber, and reactant can be contacted fast with active site, can improve activity of such catalysts and selectivity; There are not the separation and the handling problem of catalyst, can be used on a large scale in follow-up commercial Application and amplification process.
Claims (9)
1. structured ruthenium catalyst, it is characterized in that, described catalyst is a catalyst carrier with the ordered structure carbon nano-fiber, and load metal Ru catalyst, wherein, described ordered structure carbon nano-fiber is meant and adopts chemical vapour deposition technique at the resulting compound catalyze material with globality of graphite felt matrix surface growth in situ carbon nano-fiber.
2. catalyst as claimed in claim 1 is characterized in that, is benchmark with ordered structure carbon nano-fiber quality, and the load capacity of described metal Ru is 1～5%.
3. the preparation method of a structured ruthenium catalyst as claimed in claim 1 or 2 is characterized in that, may further comprise the steps:
The ordered structure nano-carbon fibre carrier is with containing ruthenium compound solution equivalent impregnation or excessive dipping, at room temperature aging, oven dry then, reduction at last obtains to be carried on the ruthenium catalyst on the ordered structure carbon nano-fiber.
4. method as claimed in claim 3 is characterized in that described reduction is meant at H
2In/Ar the atmosphere, under 200～300 ℃ condition, reduced 5～10 hours.
5. method as claimed in claim 3 is characterized in that, the described ruthenium compound that contains is a ruthenium trichloride.
6. method as claimed in claim 3 is characterized in that, also comprises the ordered structure nano-carbon fibre carrier is soaked with dilute acid soln, the pretreated step of washing, oven dry.
7. method as claimed in claim 6 is characterized in that, also comprises pretreated ordered structure nano-carbon fibre carrier is used 30%H again
2O
2Solution carries out the step of surface oxidation treatment.
8. method as claimed in claim 6 is characterized in that, also comprises pretreated ordered structure nano-carbon fibre carrier is used HNO again
3Solution carries out the step of surface oxidation treatment.
9. ordered structure nail Application of Catalyst as claimed in claim 1 or 2 is characterized in that, is used for carrying out hydrogenolysis on sorbierite and produces ethylene glycol and propane diols.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1736585A (en) * | 2005-07-18 | 2006-02-22 | 华东理工大学 | Nano carbon fiber/graphite felt compound catalytic material and preparation process thereof |
| JP2006281201A (en) * | 2005-03-10 | 2006-10-19 | Japan Science & Technology Agency | Method for preparing metal nanoparticles and structural body of carbon nanofiber |
| CN101293799A (en) * | 2008-05-20 | 2008-10-29 | 大连理工大学 | Method for preparing aldehyde or ketone compounds with catalytic oxidation of alcohol compounds |
| CN101347731A (en) * | 2008-09-03 | 2009-01-21 | 华东理工大学 | Platelet-carbon nanofibers supported ruthenium catalyst and preparation method and use thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006281201A (en) * | 2005-03-10 | 2006-10-19 | Japan Science & Technology Agency | Method for preparing metal nanoparticles and structural body of carbon nanofiber |
| CN1736585A (en) * | 2005-07-18 | 2006-02-22 | 华东理工大学 | Nano carbon fiber/graphite felt compound catalytic material and preparation process thereof |
| CN101293799A (en) * | 2008-05-20 | 2008-10-29 | 大连理工大学 | Method for preparing aldehyde or ketone compounds with catalytic oxidation of alcohol compounds |
| CN101347731A (en) * | 2008-09-03 | 2009-01-21 | 华东理工大学 | Platelet-carbon nanofibers supported ruthenium catalyst and preparation method and use thereof |
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| JP特开2006281201A 2006.10.19 |
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