CN103285901A - Preparation method of porous carbon-loaded metal oxide catalyst - Google Patents
Preparation method of porous carbon-loaded metal oxide catalyst Download PDFInfo
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- CN103285901A CN103285901A CN2013101687628A CN201310168762A CN103285901A CN 103285901 A CN103285901 A CN 103285901A CN 2013101687628 A CN2013101687628 A CN 2013101687628A CN 201310168762 A CN201310168762 A CN 201310168762A CN 103285901 A CN103285901 A CN 103285901A
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- metal oxide
- porous carbon
- oxidation
- catalyst
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Abstract
The invention relates to a preparation method of a porous carbon-loaded metal oxide catalyst, and particularly relates to a composite catalyst preparation method for enhancing the desulfurization capacity of catalysts by using the synergistic effect of the strong adsorption of porous carbon and the good catalytic oxidation desulfurization capacity of metal oxides. The method is a porous carbon-loaded metal oxide catalyst preparation process implemented through combining porous carbon, H2O2 and metal oxides mainly in a sol-gel method-carbonization mode, wherein the porous carbon adsorbs H2O2 in a water phase, the H2O2 has a catalytic action and can catalyze the adsorption of the porous carbon, and the metal oxides can slowly and permanently release HO.
Description
Technical field
The present invention relates to a kind of preparation method of porous charcoal metal oxide supporting catalyst, the synergy of the catalytic oxidation desulfurization ability that particularly a kind of strong adsorptivity of utilizing porous charcoal and metal oxide are good, promote the method for the desulphurizing ability of catalyst.
Background technology
In recent decades, the development of auto industry is very swift and violent, for very large contribution has been made in human civilization and social progress.But the consumption of vehicle fuel oil also increases greatly, and the air pollution that motor vehicle exhaust emission causes also is on the rise.The burning of sulfide in petrol has caused very large harm to environment and human health, caused the public's common concern, in recent years, countries in the world have all proposed new requirement to quality of gasoline, therefore, the sulfur method of seeking a kind of high-efficiency and economic has become the focus that the various countries scholar falls over each other research.
At present, in the face of the huge challenge of Clean Fuel Production, China has developed the new technology of various production clean fuels, especially produces low-sulfur, super low-sulfur oil and diesel oil technology.The sulfur method of fuel oil development at present mainly contains hydro desulfurization, absorption method, acid-alkali refining method, extraction, complexometry, oxidizing process and biological desulfurization method etc.With the hydrodesulfurization technology, compare, oxidation sweetening and adsorption desulfurize technology are without HTHP and use expensive hydrogen, do not reduce octane number, reaction condition is gentle, simple to operate, cost of investment is low, is the gasoline desulfur technology that has very much prospects for commercial application.Yet also there is many difficulties in the application of these technology at present, wherein just comprise that the catalytic activity of gasoline oxidation desulphurization catalyst is lower, poor to the removal effect of organic thiophenic sulfur compound in gasoline.Although a lot of to the report of the thiophene derivants such as catalytic oxidative desulfurization BT, DBT, DMDBT in the world, less to the report of thiophene, and effect is not ideal enough.
Summary of the invention
Technical problem to be solved by this invention is a kind of novel metal oxide-loaded preparation method of catalyst-porous carbon, and the method is mainly the mode by sol-gal process-charing, will have H in the absorption water
2o
2porous carbon, and there is catalytic action, H that can the absorption of catalysis porous carbon
2o
2, slow lasting release HO
.metal oxide in conjunction with and the preparation a kind of porous charcoal metal oxide supporting catalyst.The method technique is simple, and cost is low, can produce in enormous quantities.
One of the object of the invention is to provide a kind of new method for preparing the porous charcoal metal oxide supporting catalyst.
Two of the object of the invention is to provide a kind of porous charcoal metal oxide supporting catalyst.
Three of the object of the invention is to provide the application of this porous charcoal metal oxide supporting catalyst.
Invention is achieved by the following technical programs:
At first, invention provides a kind of preparation method of porous charcoal metal oxide supporting catalyst, comprises the following steps:
S1. the preparation of collosol and gel: prepare poly-vinyl alcohol solution, toward source metal in poly-vinyl alcohol solution, obtain gel sample;
S2. cooled gel sample in S1 is carried out to pre-oxidation;
S3. charing is processed: further the sample after pre-oxidation is carried out under inert gas shielding to high-temperature process, obtain product.
Preferably, the metal of described source metal is manganese, vanadium, nickel, cobalt or tungsten.
More preferably, described source metal is manganese nitrate, ammonium metavanadate, nickel nitrate, cobalt chloride or sodium tungstate.
Preferably, in S1, the mass ratio of source metal and polyvinyl alcohol is 0.5:1 ~ 2:1.Described source metal and ZnCl
2mol ratio be 1:1～1:3.
Preferably, when preparing poly-vinyl alcohol solution, be to take water as solvent, being prepared into mass fraction 10 ~ 20%(please supplement) poly-vinyl alcohol solution.
The oxidizing condition of described S2 preoxidation process is 100 ℃ ~ 200 ℃ of oxidizing temperatures, oxidization time 1 ~ 9 hour.
The described high-temperature process of S3, be the heating rate with 2～5 ℃/min, from room temperature, starts to be warming up to 550 ℃ ~ 750 ℃, keeps 15 min ~ 120 min.
Preferably, the product after the S3 high-temperature process is cooling after, also, through further washing and dry, obtain finished product.Preferably, be cooled to 150 ℃ or following.
The present invention discloses and has protected simultaneously the porous charcoal metal oxide supporting catalyst prepared by said method.
Except this, the present invention also discloses and has protected the application of above-mentioned porous charcoal metal oxide supporting catalyst aspect catalytic oxidation desulfurization.
Specifically, the substrate of institute's catalysis can be thiophene.
Catalysis process is: described catalyst is dropped in thiophene, add H
2o
2and CH
3cOOH, carry out catalytic oxidation desulfurization under the condition that is 40～70 ℃ in reaction temperature.
Described thiophene can thiophene (200-500 ppm)-and the form of normal heptane simulation oil product exists.
Described thiophene (200-500 ppm)-normal heptane simulation oil product and the H added
2o
2and CH
3cOOH, calculate according to volume parts, is respectively 50 parts, 2～3 parts, 2 ~ 5 parts.
Pass between the amount of the catalyst added and the amount of thiophene is: in every 50mL thiophene, the consumption of catalyst is 0.05～0.2g.Preferably the concentration of thiophene is 100 ppm.
In particular, for probing into the catalytic effect of catalyst, a certain amount of catalyst is put in 50 mL thiophene (200-500 ppm)-normal heptane simulation oil product, Gu utilization water--oily three-phase system, in reaction temperature, be 40～70 ℃, H
2o
2consumption is 2～3 mL, CH
3the COOH consumption is the catalytic oxidation desulfurization under 2～5 mL conditions.The oxidation sweetening rate can reach 80 ~ 97.5%.
As a kind of specific embodiment, can prepare by the following method described catalyst:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, and adding mass fraction is 10 ~ 20% polyvinyl alcohol (PVA), constantly stirs, and adds 10g ZnCl after it is dissolved fully
2and the source metal of different quality, make a series of sample;
Source metal in the preparation process of described collosol and gel is manganese nitrate or ammonium metavanadate;
In the preparation process of described collosol and gel, the mass ratio of source metal and polyvinyl alcohol is 0.5:1 ~ 2:1.
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, put into baking oven and carry out pre-oxidation;
Pre-oxidation condition in described preoxidation process is respectively (100 ℃, 2 h), (120 ℃, 2 h), (140 ℃, 1 h), (160 ℃, 1 h), (180 ℃, 1 h), (200 ℃, constant temperature spends the night).
3) charing
The pre-oxidation products obtained therefrom is placed in respectively the high temperature carbonization stove under nitrogen protection (flow velocity 400 mL/min), heating rate with 5 ℃/min keeps certain hour from room temperature directly starts to be raised to uniform temperature, takes out sample when temperature is down to below 150 ℃ in the retort stove;
In described carbonization process the rising temperature on be limited to 550 ℃ ~ 750 ℃, the retention time is 15 min ~ 120 min.
4) sample post processing
By pure water supersound washing 4h for sample, suction filtration, be placed in 120 ℃ of baking oven inner dryings and obtain testing required product.
Using thiophene as catalytic substrate, then a certain amount of catalyst is put in 50 mL thiophene (200-500 ppm)-normal heptane simulation oil product, in reaction temperature, be 50
oc, H
2o
2consumption is 2～3 mL, CH
3the COOH consumption is that the catalytic oxidation desulfurization rate under 2～5 mL conditions can reach 80 ~ 97.5%.
As a kind of preferred scheme wherein, the source metal that the present invention adopts is manganese nitrate or ammonium metavanadate.To take manganese nitrate or ammonium metavanadate and polyvinyl alcohol as presoma, a kind of composite catalyst prepared by sol-gel process.
Compared with prior art, the present invention has following originality characteristics and beneficial effect:
Polyvinyl alcohol in the preparation process of collosol and gel of the present invention (PVA) is carbon source, ZnCl
2for pore-foaming agent, NaCl is presoma prepared by dispersion stabilizer;
Solid-phase catalyst prepared by the present invention, under the catalytic action of metal oxide, can must discharge HO slowly lastingly
., by CH
3cOOH is oxidized to CH
3cOOOH, CH
3cOOOH enters oxidation of thiophene in the simulation oil product that thiophene-normal heptane forms;
The catalyst that porous charcoal prepared by the present invention is metal oxide-loaded, be the synergy of utilizing the strong adsorptivity of porous charcoal and the good catalytic oxidation desulfurization ability of metal oxide, promotes the desulphurizing ability of catalyst.
The specific embodiment
In order further to explain technical solution of the present invention, invention further provides following specific embodiment, but following examples can not be as the restriction of invention protection domain.
Embodiment 1:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, add 5g polyvinyl alcohol (PVA), constantly stir, add 10g ZnCl after it is dissolved fully
2and 18.3g manganese nitrate (source metal and ZnCl
2mol ratio be 1:1);
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, put into pre-oxidation 2 h under 100 ℃ of conditions of baking oven;
3) charing
By 2) in the pre-oxidation products obtained therefrom be placed in the high temperature carbonization stove under nitrogen protection (flow velocity 400 mL/min), heating rate with 5 ℃/min keeps 120min from room temperature directly starts to be raised to 550 ℃, takes out sample when temperature is down to below 150 ℃ in retort;
4) sample post processing
By pure water supersound washing 4h for sample, suction filtration, be placed in 120 ℃ of baking oven inner dryings and obtain testing required product;
Using thiophene as catalytic substrate, then the 0.1g catalyst is put in 50 mL thiophene (200ppm)-normal heptane simulation oil product, in reaction temperature, be 70
oc, H
2o
2consumption is 3 mL, CH
3the COOH consumption is that the catalytic oxidation desulfurization rate under the 2mL condition can reach 88.2%.
Embodiment 2:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, add 8 g polyvinyl alcohol (PVA), constantly stir, add 10g ZnCl after it is dissolved fully
2and 2.86g ammonium metavanadate (source metal and ZnCl
2mol ratio be 1:3);
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, put into pre-oxidation constant temperature under 200 ℃ of conditions of baking oven and spend the night;
3) charing
By 2) in the pre-oxidation products obtained therefrom be placed in the high temperature carbonization stove under nitrogen protection (flow velocity 400 mL/min), heating rate with 2 ℃/min keeps 90min from room temperature directly starts to be raised to 750 ℃, takes out sample when temperature is down to below 150 ℃ in the retort stove;
4) sample post processing
By pure water supersound washing 4 h for sample, suction filtration, be placed in 120 ℃ of baking oven inner dryings and obtain testing required product.
The catalyst 1g prepared under this condition is put in 50 mL thiophene (500 ppm)-normal heptane simulation oil product, Gu utilization water--oily three-phase system, in reaction temperature, be 40
oc, H
2o
2consumption is 2mL, CH
3the COOH consumption is that the catalytic oxidation desulfurization rate under 5 mL conditions can reach 95.7%.
Embodiment 3:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, add 10g polyvinyl alcohol (PVA), constantly stir, add 10g ZnCl after it is dissolved fully
2and 21.33g nickel nitrate (source metal and ZnCl
2mol ratio be 1:1), make sample.
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, put into pre-oxidation constant temperature 1h under 160 ℃ of conditions of baking oven;
3) charing
By 2) in the pre-oxidation products obtained therefrom be placed in the high temperature carbonization stove under nitrogen protection (flow velocity 400 mL/min), heating rate with 4 ℃/min keeps 15min from room temperature directly starts to be raised to 600 ℃, takes out sample when temperature is down to below 150 ℃ in the retort stove;
4) sample post processing
By pure water supersound washing 4 h for sample, suction filtration, be placed in 120 ℃ of baking oven inner dryings and obtain testing required product.
The catalyst 0.3g prepared under this condition is put in 50 mL thiophene (300 ppm)-normal heptane simulation oil product, Gu utilization water--oily three-phase system, in reaction temperature, be 60
oc, H
2o
2consumption is 3 mL, CH
3the COOH consumption is that the catalytic oxidation desulfurization rate under the 4mL condition can reach 90.7%.
Embodiment 4:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, add 10g polyvinyl alcohol (PVA), constantly stir, add 10g ZnCl after it is dissolved fully
2and 8.73g cobalt chloride (source metal and ZnCl
2mol ratio be 1:2), make sample.
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, put into pre-oxidation constant temperature 1h under 180 ℃ of conditions of baking oven;
3) charing
By 2) in the pre-oxidation products obtained therefrom be placed in the high temperature carbonization stove under nitrogen protection (flow velocity 400 mL/min), heating rate with 4 ℃/min keeps 20min from room temperature directly starts to be raised to 650 ℃, takes out sample when temperature is down to below 150 ℃ in the retort stove;
4) sample post processing
By pure water supersound washing 4 h for sample, suction filtration, be placed in 120 ℃ of baking oven inner dryings and obtain testing required product.
The catalyst prepared under this condition is put in 50 mL thiophene (200-500 ppm)-normal heptane simulation oil product, Gu utilization water--oily three-phase system, in reaction temperature, be 50
oc, H
2o
2consumption is 3 mL, CH
3the COOH consumption is that the catalytic oxidation desulfurization rate under the 4mL condition can reach 93.3%.
Embodiment 5:
1) preparation of collosol and gel
50 mL ultra-pure waters are heated to boiling, add 6g polyvinyl alcohol (PVA), constantly stir, add 10g ZnCl after it is dissolved fully
2and 8.07g sodium tungstate (source metal and ZnCl
2mol ratio be 1:3), make sample.
2) pre-oxidation
By 1) in cooled gel sample proceed to culture dish, put into pre-oxidation constant temperature 9h under 100 ℃ of conditions of baking oven;
3) charing
By 2) in the pre-oxidation products obtained therefrom be placed in the high temperature carbonization stove under nitrogen protection (flow velocity 400 mL/min), heating rate with 3 ℃/min keeps 30min from room temperature directly starts to be raised to 700 ℃, takes out sample when temperature is down to below 150 ℃ in the retort stove;
4) sample post processing
By pure water supersound washing 4 h for sample, suction filtration, be placed in 120 ℃ of baking oven inner dryings and obtain testing required product.
The catalyst 0.4g prepared under this condition is put in 50 mL thiophene (400 ppm)-normal heptane simulation oil product, Gu utilization water--oily three-phase system, in reaction temperature, be 50
oc, H
2o
2consumption is 3 mL, CH
3the COOH consumption is that the catalytic oxidation desulfurization rate under the 4mL condition can reach 82.8%.
Claims (10)
1. the preparation method of a porous charcoal metal oxide supporting catalyst, is characterized in that, comprises the following steps:
S1. the preparation of collosol and gel: prepare poly-vinyl alcohol solution, in poly-vinyl alcohol solution, add ZnCl
2and source metal, obtain gel sample;
S2. cooled gel sample in S1 is carried out to pre-oxidation;
S3. charing is processed: further the sample after pre-oxidation is carried out under inert gas shielding to high-temperature process, obtain product.
2. preparation method as claimed in claim 1, the metal that it is characterized in that described source metal is manganese, vanadium, nickel, cobalt or tungsten.
3. preparation method as claimed in claim 2, is characterized in that described source metal is manganese nitrate, ammonium metavanadate, nickel nitrate, cobalt chloride or sodium tungstate.
4. preparation method as claimed in claim 1, is characterized in that in S1, and the mass fraction of poly-vinyl alcohol solution is 10 ~ 20%, and the mass ratio of source metal and polyvinyl alcohol is 0.5:1 ~ 2:1; Described source metal and ZnCl
2mol ratio be 1:1～1:3.
5. preparation method as claimed in claim 1, is characterized in that, the oxidizing condition of described S2 preoxidation process is 100 ℃ ~ 200 ℃ of oxidizing temperatures, oxidization time 1 ~ 9 hour.
6. preparation method as claimed in claim 1, is characterized in that the described high-temperature process of S3, is the heating rate with 2-5 ℃/min, from room temperature, starts to be warming up to 550 ℃ ~ 750 ℃, keeps 15 min ~ 120 min.
7. preparation method as claimed in claim 1, after it is characterized in that product after the S3 high-temperature process is cooling, also, through further washing and dry, obtain finished product, described cooling be to be cooled to 150 ℃ or following.
8. the porous charcoal metal oxide supporting catalyst that the method for claim 1 prepares.
9. the application of porous charcoal metal oxide supporting catalyst as claimed in claim 8 aspect catalytic oxidation desulfurization.
10. application as claimed in claim 9, is characterized in that catalytic substrate is thiophene, and catalysis process is: described catalyst is dropped in thiophene, add H
2o
2and CH
3cOOH, carry out catalytic oxidation desulfurization under the condition that is 40～70 ℃ in reaction temperature.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925284A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of preparation method of high efficiency, low cost desulfurization catalyst of flue gas |
| CN113648987A (en) * | 2021-09-08 | 2021-11-16 | 东北大学 | Preparation method of porous carbon and carbon supported catalyst |
| CN115382538A (en) * | 2022-09-17 | 2022-11-25 | 湖州师范学院 | Novel metal-based carbon catalyst for hydrogen production by catalytic degradation of organic wastewater and preparation method thereof |
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| CN101376114A (en) * | 2008-10-09 | 2009-03-04 | 大连理工大学 | Method for preparing metal or metallic oxide/carbon composite material |
| US7572427B2 (en) * | 2001-07-03 | 2009-08-11 | Facultes Universitaires Notre-Dame De La Paix | Catalyst supports and carbon nanotubes produced thereon |
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2013
- 2013-05-09 CN CN201310168762.8A patent/CN103285901B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7572427B2 (en) * | 2001-07-03 | 2009-08-11 | Facultes Universitaires Notre-Dame De La Paix | Catalyst supports and carbon nanotubes produced thereon |
| CN101376114A (en) * | 2008-10-09 | 2009-03-04 | 大连理工大学 | Method for preparing metal or metallic oxide/carbon composite material |
Non-Patent Citations (1)
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| 余国贤等: "活性炭及甲酸催化过氧化氢氧化噻吩脱硫研究", 《燃料化学学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925284A (en) * | 2015-12-29 | 2017-07-07 | 天津市英派克石化工程有限公司 | A kind of preparation method of high efficiency, low cost desulfurization catalyst of flue gas |
| CN113648987A (en) * | 2021-09-08 | 2021-11-16 | 东北大学 | Preparation method of porous carbon and carbon supported catalyst |
| CN115382538A (en) * | 2022-09-17 | 2022-11-25 | 湖州师范学院 | Novel metal-based carbon catalyst for hydrogen production by catalytic degradation of organic wastewater and preparation method thereof |
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