CN100479918C - Method for preparing metal phosphide hydrogenation refining catalyst by using hydrogen plasma reduction method - Google Patents
Method for preparing metal phosphide hydrogenation refining catalyst by using hydrogen plasma reduction method Download PDFInfo
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- CN100479918C CN100479918C CNB2007100100828A CN200710010082A CN100479918C CN 100479918 C CN100479918 C CN 100479918C CN B2007100100828 A CNB2007100100828 A CN B2007100100828A CN 200710010082 A CN200710010082 A CN 200710010082A CN 100479918 C CN100479918 C CN 100479918C
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- metal phosphide
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- hydrogenation refining
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Abstract
The invention discloses a solid catalyst in the oil distill hydrogenating course, which comprises the following steps: adopting metal oxide and phosphate salt to make oxide primer; placing the primer in the plasma reactor; aerating hydrogen at 10-600h-1; loading 10-20kV to generate plasma; reducing for 10-180 min; obtaining deep solid as phosphate catalyst.
Description
Technical field
The invention belongs to coal processing, PETROLEUM PROCESSING and petrochemical technology field, relate to employed solid catalyst in fraction oil of petroleum (gasoline, kerosene and the diesel oil etc.) hydrofining technology.
Technical background
Along with the sustained and rapid development of China's economy and the swift and violent increase of automobile pollution, the oil consumption amount of China increases in recent years fast.A large amount of SOx that sulphur in the fraction oil of petroleum and nitrogen element produce after burning and NOx can major polluting atmosphere environments, not only can damage popular healthyly, and can cause disaster such as acid rain, destroy ecological environment.In order to subdue the pollution of sulfur-containing compound and nitrogen-containing compound from the source, countries in the world have all been formulated the standard of fuel of increasingly stringent in recent years.At present, import volume has surpassed the yield of China's oil in the China's oil refining raw material, and the oil of import mostly is sulfur-bearing and sour crude, thereby China's oil refining enterprise is faced with more stern challenge.
Sulfur-containing organic compound in the fuel oil and nitrogen-containing compound remove on same catalyst simultaneously by hydrofining technology, and traditional Hydrobon catalyst is load type Co-Mo, Ni-Mo or Nj-W sulfide.Six during the last ten years, though sulfide catalyst through updating, its activity still can't satisfy the requirement of the environmental regulation of increasingly stringent.Therefore, people are when continuing to manage to improve sulfide catalyst, also seeking new active phase, as transition metal nitride, carbide and phosphide.Wherein, though very high its activity stability of nitride and carbide catalyst initial activity is very poor, and the active not anti-sulphur mutually of this two class.
People such as Robinson reported that Ni2P was higher than industrial Ni-Mo/Al2O3 sulfide catalyst to the hydrodenitrogeneration reactivity of quinoline in 1996.Transition metal (as Ni, Mo and W) phosphide not only has very high activity, and has good activity stability.Have multiplely though prepare the method for metal phosphide, phosphide hydrogenation refining catalyst generally adopts the method preparation of hydrogen reducing transition metal oxide and phosphorous oxides.Because transition metal phosphide is met water can be oxidized, and have water to generate in the product of hydrogenating reduction, the preparation of phosphide must be adopted high hydrogen flow rate and low heating rate.Thereby the preparation required time of transition metal phosphide is long, and consumes a large amount of hydrogen.
Summary of the invention
The purpose of this invention is to provide a kind of new transition metal phosphide preparation method, prepared metal phosphide is a kind of oil plant hydrofining reaction catalyst, can effectively remove sulfur-containing compound and nitrogen-containing compound in the fraction oil of petroleum, thereby deep desulfuration and denitrogenation are realized in economical and efficient ground, produce clean fuel.
Technical scheme of the present invention is to adopt hydrogen plasma method reducing metal and phosphorous oxides precursor preparation metal phosphide, and reaction can obtain the metal phosphide crystal of structural integrity more than 30 minutes, thus energy savings and hydrogen resource.
Employed metal is meant a kind of transition metal among Ni, Mo, W, Co, Fe, Ti and the Mn or the combination of several metals.The method of being invented both can prepare the carrier-borne transition metal phosphide, also can prepare non-loading type (claiming the body phase again) transition metal phosphide.
Effect of the present invention and benefit are that prepared transition metal phosphide catalyst has very high catalytic reaction activity to condensed ring sulfur-containing compound in the petroleum distillate and nitrogen-containing compound under the typical commercial application condition, but the deep desulfuration and the denitrogenation of fraction oil of petroleum are realized in economical and efficient ground, thereby the production clean fuel oil, enterprise has wide application prospect in petroleum refining.
The specific embodiment
Below be described in detail the specific embodiment of the present invention.
The preparation of catalyst precarsor
Preparing silica supported molybdenum sulphur phosphorus catalyst precursor with co-impregnation is example, MoO
3Load capacity be 40% (quality).Take by weighing 3.65 gram ammonium molybdate ((NH
4)
6Mo
7O
24.4H
2O) and 2.729 the gram diammonium hydrogen phosphates ((NH4)
2HPO
4), adding 10 ml deionized water, dipping solution is made in dissolving.Take by weighing 3 gram porous silicas, add dipping solution, room temperature dipping 12 hours.Slurry was in 120 ℃ of oven dry 12 hours, and roasting 5h in 500 ℃ of air obtains oxide precursor then.
Preparation of Catalyst
Oxide precursor is made 0.3～0.5 mm granules through compressing tablet, takes by weighing pack into the nonequilibrium plasma reactor of 8 millimeters of internal diameters of 0.8 gram.Plasma reactor die opening 3mm, discharge voltage 10kV, frequency 11kHz.Feed hydrogen, flow is 150ml/min.Reduction is 60 minutes under spontaneous temperature and normal pressure, obtains dark MoP catalyst.
Evaluating catalyst
Hydrodesulfurization reaction activity rating with catalyst is an example.After bed temperature is reduced to reaction temperature (360 ℃), Hydrogen Vapor Pressure is increased to 4.0MPa, in reactor, carry the decahydronaphthalene solution that contains the 0.8wt% dibenzothiophenes with high-pressure metering pump then, be used for product analysis through gas-liquid separator separates fluid body at reactor exit.Other reaction conditions: liquid air speed (WHSV) is 21h
-1, H
2/ solid-liquid ratio is 1600Nm
3/ m
3Raw material and product are represented with the conversion ratio of dibenzothiophenes with Agilent 6890 gas chromatographic analysis, hydrodesulfurization reaction activity.
The conversion ratio of dibenzothiophenes illustrates that greater than 99% this catalyst has very high hydrodesulfurization reaction activity under this reaction condition, is a kind of desirable Hydrobon catalyst.
Claims (1)
1. the method for a preparing metal phosphide hydrogenation refining catalyst by using hydrogen plasma reduction mehtod is characterized in that adopting hydrogen plasma method reducing metal and phosphorous oxides precursor preparation metal phosphide; Employed metal is meant a kind of transition metal among Ni, Mo, W, Co, Fe, Ti and the Mn or the combination of several metals.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100100828A CN100479918C (en) | 2007-01-09 | 2007-01-09 | Method for preparing metal phosphide hydrogenation refining catalyst by using hydrogen plasma reduction method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100100828A CN100479918C (en) | 2007-01-09 | 2007-01-09 | Method for preparing metal phosphide hydrogenation refining catalyst by using hydrogen plasma reduction method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101011664A CN101011664A (en) | 2007-08-08 |
| CN100479918C true CN100479918C (en) | 2009-04-22 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100100828A Expired - Fee Related CN100479918C (en) | 2007-01-09 | 2007-01-09 | Method for preparing metal phosphide hydrogenation refining catalyst by using hydrogen plasma reduction method |
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Cited By (1)
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|---|---|---|---|---|
| CN103240076A (en) * | 2013-05-12 | 2013-08-14 | 大连理工大学 | Method for preparing supported molybdenum-oxide-based and tungsten-oxide-based oxidation desulfurization catalysts |
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| US8575059B1 (en) | 2007-10-15 | 2013-11-05 | SDCmaterials, Inc. | Method and system for forming plug and play metal compound catalysts |
| US9119309B1 (en) | 2009-12-15 | 2015-08-25 | SDCmaterials, Inc. | In situ oxide removal, dispersal and drying |
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| US9586179B2 (en) | 2013-07-25 | 2017-03-07 | SDCmaterials, Inc. | Washcoats and coated substrates for catalytic converters and methods of making and using same |
| CN103495427B (en) * | 2013-10-17 | 2015-11-18 | 大连理工大学 | Low temperature plasma is utilized to prepare the method for load type metal sulfide catalyst |
| CA2926133A1 (en) | 2013-10-22 | 2015-04-30 | SDCmaterials, Inc. | Catalyst design for heavy-duty diesel combustion engines |
| US9517448B2 (en) | 2013-10-22 | 2016-12-13 | SDCmaterials, Inc. | Compositions of lean NOx trap (LNT) systems and methods of making and using same |
| EP3119500A4 (en) | 2014-03-21 | 2017-12-13 | SDC Materials, Inc. | Compositions for passive nox adsorption (pna) systems |
| CN108855161A (en) * | 2018-07-19 | 2018-11-23 | 淮北师范大学 | A kind of preparation method of transition metal phosphide |
| CN110747536B (en) * | 2019-02-28 | 2022-04-05 | 安徽科技学院 | Preparation method of nanofiber with wide visible light absorption range |
-
2007
- 2007-01-09 CN CNB2007100100828A patent/CN100479918C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103240076A (en) * | 2013-05-12 | 2013-08-14 | 大连理工大学 | Method for preparing supported molybdenum-oxide-based and tungsten-oxide-based oxidation desulfurization catalysts |
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