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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- Prior art keywords
- catalyst
- metal phosphide
- hydrogen plasma
- hydrogenation refining
- preparing metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 12
- 239000001257 hydrogen Substances 0.000 title claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 title claims description 14
- 239000002184 metal Substances 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 9
- 238000007670 refining Methods 0.000 title claims description 6
- 230000009467 reduction Effects 0.000 title claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 10
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract 1
- 150000004706 metal oxides Chemical class 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- -1 nitrogen-containing compound Chemical class 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910019614 (NH4)6 Mo7 O24.4H2 O Inorganic materials 0.000 description 1
- AALFFVYDSNTLLQ-UHFFFAOYSA-N [S].[P].[Mo] Chemical compound [S].[P].[Mo] AALFFVYDSNTLLQ-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000007562 laser obscuration time method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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 |
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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 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100479918C (en) |
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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| WO2008140786A1 (en) | 2007-05-11 | 2008-11-20 | Sdc Materials, Inc. | Method and apparatus for making uniform and ultrasmall nanoparticles |
| US8575059B1 (en) | 2007-10-15 | 2013-11-05 | SDCmaterials, Inc. | Method and system for forming plug and play metal compound catalysts |
| US9039916B1 (en) | 2009-12-15 | 2015-05-26 | SDCmaterials, Inc. | In situ oxide removal, dispersal and drying for copper copper-oxide |
| US8652992B2 (en) * | 2009-12-15 | 2014-02-18 | SDCmaterials, Inc. | Pinning and affixing nano-active material |
| US9126191B2 (en) | 2009-12-15 | 2015-09-08 | SDCmaterials, Inc. | Advanced catalysts for automotive applications |
| US8669202B2 (en) | 2011-02-23 | 2014-03-11 | SDCmaterials, Inc. | Wet chemical and plasma methods of forming stable PtPd catalysts |
| JP2014524352A (en) | 2011-08-19 | 2014-09-22 | エスディーシーマテリアルズ， インコーポレイテッド | Coated substrate for use in catalysis and catalytic converters and method for coating a substrate with a washcoat composition |
| US9156025B2 (en) | 2012-11-21 | 2015-10-13 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| US9511352B2 (en) | 2012-11-21 | 2016-12-06 | SDCmaterials, Inc. | Three-way catalytic converter using nanoparticles |
| WO2015013545A1 (en) | 2013-07-25 | 2015-01-29 | SDCmaterials, Inc. | Washcoats and coated substrates for catalytic converters |
| 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 |
| JP2016536120A (en) | 2013-10-22 | 2016-11-24 | エスディーシーマテリアルズ， インコーポレイテッド | Catalyst design for heavy duty diesel combustion engines |
| CA2926135A1 (en) | 2013-10-22 | 2015-04-30 | SDCmaterials, Inc. | Compositions of lean nox trap |
| WO2015143225A1 (en) | 2014-03-21 | 2015-09-24 | SDCmaterials, 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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| CN101011664A (en) | 2007-08-08 |
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Granted publication date: 20090422 Termination date: 20140109 |