CN101734633B - Preparation method of nickel phosphide - Google Patents
Preparation method of nickel phosphide Download PDFInfo
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- CN101734633B CN101734633B CN2008102346850A CN200810234685A CN101734633B CN 101734633 B CN101734633 B CN 101734633B CN 2008102346850 A CN2008102346850 A CN 2008102346850A CN 200810234685 A CN200810234685 A CN 200810234685A CN 101734633 B CN101734633 B CN 101734633B
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- nickel phosphide
- phosphide
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- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- -1 phosphorous acid ions Chemical class 0.000 claims abstract description 6
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 229910052759 nickel Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 230000004913 activation Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 8
- 238000002161 passivation Methods 0.000 claims description 8
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000005201 scrubbing Methods 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims 1
- 239000002283 diesel fuel Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract 1
- 239000012071 phase Substances 0.000 abstract 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- 239000000446 fuel Substances 0.000 description 11
- 229910052723 transition metal Inorganic materials 0.000 description 11
- 239000005864 Sulphur Substances 0.000 description 10
- 238000006477 desulfuration reaction Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 150000003624 transition metals Chemical class 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 230000023556 desulfurization Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 3
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- HDUHSISAGHHYRW-UHFFFAOYSA-N [N].N1=CC=CC2=CC=CC=C21 Chemical compound [N].N1=CC=CC2=CC=CC=C21 HDUHSISAGHHYRW-UHFFFAOYSA-N 0.000 description 2
- NQFKCCCPJFIMCA-UHFFFAOYSA-N [S].C1=CC=C2C3=CC=CC=C3SC2=C1 Chemical compound [S].C1=CC=C2C3=CC=CC=C3SC2=C1 NQFKCCCPJFIMCA-UHFFFAOYSA-N 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910001463 metal phosphate Inorganic materials 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
On the premise of deep hydrodesulfurization, the main problem in diesel fuel's hydrotreatment is to rid the refractory sulfide and hydrogenate polycyclic aromatic hydrocarbon. Loaded nickel phosphide catalyst demonstrates higher hydrodesulfurization activity and better activity stability. However, the traditional nickel phosphide catalyst is prepared by temperature programming of nickel phosphide, so that dispersion degree of active components is low. In the invention, through solid-phase reaction between phosphorous acid ions and nickel ions, bulk phase and loaded nickel phosphide catalyst with higher active component dispersion degree and fine catalytic activity are obtained at low temperature. The invention is applicable to diesel oil hydroprocessing.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the catalyst of phosphatizing nickel of diesel oil hydrogenation processing.
Background technology
Transport fuel oil mainly comprises gasoline, diesel oil and aviation kerosene three major types, and they account for the major part of petroleum products.Over the past decade, countries in the world have proposed increasingly high requirement to the exhaust emissions of the vehicles, mainly are the dischargings that reduces obnoxious flavour and greenhouse gases in the tail gas.Existing European IV standard of fuel (EU 2005) requires sulphur content in gasoline and the diesel oil all less than 50ppmw; To then require sulphur content to be lower than 10ppmw (process engineering journal in the European V standard of fuel (EU 2009) that on January 1st, 2009 came into force; 2007 the 7th volumes, the 176-185 page or leaf).Existing motor spirit standard of China (GB 19730-1999) and diesel oil standard (GB/T 19147-2003) all require the sulphur content of oil fuel to be lower than 500ppmw, and Hesperian standard such as this and America and Europe has bigger gap.On the one hand, the oil fuel of countries in the world consumption is more and more, China particularly, and annual consumption increases very fast.On the other hand, the proportion of crude oil is increasing, and sulphur content is increasingly high.Such situation makes the processing tasks that cleans of oil fuel become more and more arduous.Oil fuel is being carried out under the prerequisite of deep desulfuration, traditional oil fuel hydrotreatment is faced with bigger difficulty.Only traditional technology is improved or is optimized and can not meet day by day harsh oil fuel standard, and exploration can better desulfurization, denitrification catalyst has been urgent task.In recent years; When transition metal sulfide catalyst is updated; The research of the Hydrobon catalyst of other types has obtained bigger progress; Like metal phosphide, carbide, nitride and boride etc., they have shown higher hydrogenating desulfurization, denitrification activity, and the development of handling catalyzer for novel hydrogenation has brought hope.
The transition metal phosphide that is used for the oil fuel hydrotreatment mainly comprises unit or the binary metal phosphide of Ni, W, Co, Mo, Fe etc.; They have very high hydrogenating desulfurization, denitrification activity; Satisfactory stability property and anti-sulphur ability; Be expected to become the hydrorefined commercial catalysts of oil fuel of future generation (J.Catal.2002 the 210th volume, 207-217 page or leaf).The temperature programmed reduction(TPR) (J.Catal.2002 the 208th volume, 321-331 page or leaf) or the metal that generally adopt metal phosphate as the transition metal phosphide of the use of catalyzer are at PH
3In direct phosphatization (J.Catal.2006 the 237th volume, 118-130 page or leaf).Phosphide catalyst has used SiO
2With gac etc. as carrier, shown good diesel oil hydrogenation handling property.Research shows (J.Catal.2002 the 210th volume, 207-217 page or leaf), SiO
2The catalytic activity of the metal phosphide that supports is by Fe
2P＜CoP＜MoP＜WP＜Ni
2P increases progressively, wherein Ni
2P/SiO
2Hydrogenating desulfurization and denitrification activity all be higher than commercial catalysts Ni-Mo/Al
2O
3(J.Catal.2006 the 237th volume such as Yang; The 118-130 page or leaf) thinks; The phosphide of transition metal has higher anti-sulphur ability than carbide and nitride; Under hydrodesulfurizationconditions conditions, although catalyst surface has the sulphur atom occupy-place, the kernel of the phosphide of transition metal (kernel) can be kept perfectly.
Oyama etc. (J.Catal.2002 the 210th volume, 207-217 page or leaf) have stressed transformation frequency (TOF) when comparing the hydrogenation activity of metal phosphide and commercial catalysts, their result shows that metal phosphide has higher TOF.But the dispersity of metal phosphide is often lower, and the CO adsorptive capacity on the unit mass catalyzer only is equivalent to O on the commercial catalysts
21/3 of adsorptive capacity.So preparation high dispersive, highly active loaded metal phosphide will be the striving directions of development oil fuel Hydrobon catalyst of new generation.
Chinese patent CN 200410006271 discloses a kind of preparation method of transition metal phosphide.This patent is dissolved mixing, load, drying and roasting by a certain percentage through metal-salt and Secondary ammonium phosphate, under hydrogen atmosphere temperature programmed reduction(TPR) and under oxygen-containing atmosphere passivation make phosphide catalyst, staple is Ni
2P.The phosphide catalyst that this method prepares shows the higher dibenzothiophene and the hydrodesulfurization activity of verivate thereof.
Chinese patent CN 200410096933 discloses the preparation method of other a kind of transition metal phosphide.This patent is with NiSO
46H
2O and NaH
2PO
2Be dissolved in the deionized water, add oil phase, tensio-active agent, clarify at stirring at room to solution, be warming up to 140-160 ℃ of reaction again and be not less than 8 hours, the staple of prepared catalyzer is Ni
12P
5, be nano level hollow ball.
Although transition metal phosphide has important application prospects as catalyzer, study seldom (Chem.Eur.J.2004 the 10th volume, 3364-3371 page or leaf) to the preparation method of transition metal phosphide.The compound method of the transition metal phosphide of having reported comprises solvent-thermal method, the reduction of transition metal phosphate, and through phosphuret-(t)ed hydrogen reducing metal or oxide compound, the reaction of the decomposition of metal precursor and organometallic reagent and phosphuret-(t)ed hydrogen.In this patent, body phase and the Ni that supports
2P is through the low-temperature decomposition preparation in nitrogen of ortho phosphorous acid nickel, the Ni that makes
2The P catalyzer has shown higher desulfurization, denitrification activity and certain condensed-nuclei aromatics hydrogenation ability.
Summary of the invention
The commercial catalysts of domestic diesel hydrogenation for removal sulphur, like FH-98, the general requirement temperature of reaction is greater than 340 ℃.And general aromatic hydrocarbon hydrogenation catalyst is the precious metal of anti-sulphur not.External refinery carries out deep desulfuration to diesel oil earlier, on noble metal catalyst, makes aromatic hydrogenation saturated then.Though solved the sulfur poisoning problem of hydrogenation catalyst like this, diesel oil has been carried out twice hydrotreatment, improved investment and energy consumption.Therefore, the difunctional diesel oil hydrogenation catalyzer that possesses desulfurization and aromatic hydrogenation activity has just become important goal in research.It is thus clear that the main task that diesel oil is handled is that to remove the hydrogenation of lower many rings sulfocompound of reactive behavior and condensed-nuclei aromatics saturated.
Transition metal phosphide catalyst has shown higher desulfurization, denitrification activity, particularly supports Ni
2The specific activity of P catalyzer even be higher than traditional sulfide catalyst.But the preparation method of traditional phosphide catalyst is phosphatic temperature programmed reduction(TPR), and temperature of reaction is high, and the active site dispersity is low.When being used for the diesel oil hydrogenation processing, has the not high shortcoming of yield of unit mass catalyzer.This patent has been avoided the high temperature reduction step in the catalyst preparation process, utilizes the automatic oxidation reduction reaction of hypophosphite, under lower temperature of reaction, has prepared the catalyst of phosphatizing nickel with greater activity through solid state reaction.
Technical scheme of the present invention is following:
A kind of preparation method of nickel phosphide, key step is: ortho phosphorous acid nickel and ammonium hypophosphite are dissolved in the deionized water, mix, evaporate to dryness gets the yellow-green colour solid.Get above-mentioned solid and place in the tube furnace, the atmosphere that flows, temperature programming is stablized 2～8h to temperature of reaction, reduces to room temperature, switches to that to contain oxygen be 0.2～2% the inertia atmosphere that flows, and passivation 2～8h takes out.Sample ammonia scrubbing after the passivation arrives neutrality with deionized water wash then to colourless, and 373K is dried 12h, gets nickel phosphide.The nickel phosphide that makes carries out activation treatment before using.
The mixing solutions equivalent impregnation of ortho phosphorous acid nickel and ammonium hypophosphite to carrier, is dried in the shade,, make the catalyst of phosphatizing nickel of load through above-mentioned roasting, washing and activation step.
The ratio of the ortho phosphorous acid radical ion that is adopted in the above-mentioned nickel phosphide preparation and the amount of substance of nickel ion is 2～5.
It is in hydrogen, nitrogen, helium and the argon gas one or more that above-mentioned nickel phosphide reacts used mobile atmosphere.
The temperature rise rate of above-mentioned nickel phosphide reaction is 1～5K/min, and temperature of reaction is 373～673K, and the reaction times is 2～8h.
The used rare gas element of above-mentioned nickel phosphide passivation is one or more in hydrogen, nitrogen, helium and the argon gas.
Above-mentioned nickel phosphide activation method: in hydrogen atmosphere, be warmed up to 623～773K, activation 2～5h, pressure 0～5MPa, air speed 1000～4000h with 1～5K/min
-1(V/V).
Above-mentioned catalyst-supporting support is MCM-41, SBA-15, SiO
2, TiO
2, ZrO
2, gac (AC), mesoporous carbon (MC), Al
2O
3In a kind of.
The loading of above-mentioned supported catalyst Ni is 1～4mmol Ni/g carrier.
Above-mentioned catalyst of phosphatizing nickel is used for the method that diesel oil hydrogenation is handled, and it is characterized in that: catalyst of phosphatizing nickel of the present invention is loaded in the reactor drum, and catalyzer is earlier at H
2Temperature of reaction is reduced in middle activation then, feeds model diesel oil.Model diesel oil is the positive nonane solution of octane (interior mark) of the naphthane and 0.5% (wt.) of the dibenzothiophene sulphur that contains 3000ppmw, 200ppmw quinoline nitrogen, 5% (wt).Reaction pressure 2.0～4.0MPa, air speed 1～4h
-1, hydrogen-oil ratio 500～2000 (v/v).Sulphur, nitrogen content and hydrocarbon behind reaction 24h in the sampling analysis product are formed.
Description of drawings
Fig. 1 is the XRD spectrum of embodiment 1 and embodiment 3 gained samples.
Embodiment
Embodiment with following is described further the present invention:
Embodiment 1
Press H
2PO
2 -: Ni
2+Than being 3 ortho phosphorous acid nickel and ammonium hypophosphite to be dissolved in the deionized water, stir the 333K water bath method.Get above-mentioned presoma 5.0g, place in the tube furnace, logical N
2, arrive temperature of reaction with the speed temperature programming of 2K/min, stablize 3h, reduce to room temperature with containing O
21% nitrogen passivation was taken out after 3 hours.Wherein, N
2Flow is 100ml/min, and temperature is 473K eventually.Sample after the roasting is extremely colourless with ammonia scrubbing earlier, arrives neutrality with deionized water wash then, oven dry.The specific surface area of prepared sample (called after NP3) is 14m
2/ g, the XRD spectrum is seen Fig. 1.
Embodiment 2
1.78g ortho phosphorous acid nickel and 0.50g ammonium hypophosphite are dissolved in the 6.6g deionized water, add 6.0g gac (AC, textural property is seen table 1, equivalent impregnation point 1.1ml/g), stir, dry in the shade.Get impregnated sample 5.0g roasting in 473K nitrogen, washing and oven dry, method is with embodiment 1.The catalyzer called after NPAC that makes.Carrier and catalyst-loaded structural property see Table 1.
The textural property of table 1 catalyzer and carrier.
Embodiment 3
5.94g ortho phosphorous acid nickel and 1.66g ammonium hypophosphite are dissolved in the 14.0g deionized water, add 5.0g mesoporous carbon (textural property is seen table 1, equivalent impregnation point 2.8ml/g), stir, dry in the shade.Get impregnated sample 5.0g roasting in 473K nitrogen, washing and oven dry, method is with embodiment 1.The catalyzer called after NPMC that makes.Carrier and catalyst-loaded structural property see Table 1, and the XRD spectrum is seen Fig. 1.
Embodiment 4
The body phase catalyst of phosphatizing nickel 2.3g that embodiment 1 is prepared is loaded in the reactor drum, and catalyzer is at H
2Middle activation 3h, activation pressure 3.1MPa, activation temperature 673K, air speed 2000h
-1(V/V).Reduce to temperature of reaction after catalyst activation finishes, feed model diesel oil.Model diesel oil is the positive nonane solution of octane (interior mark) of the naphthane and 0.5% (wt.) of the dibenzothiophene sulphur that contains 3000ppmw, 200ppmw quinoline nitrogen, 5% (wt).Reaction pressure 3.1MPa, air speed 2h
-1, hydrogen-oil ratio 1500 (v/v).Sulphur, nitrogen content and hydrocarbon behind reaction 24h in the sampling analysis product are formed.Evaluation result is seen table 2, table 3.
Table 2 supports Ni
2The hydrodenitrogenationactivity activity of the hydrogenating desulfurization of DBT and quinoline on the P catalyzer.
The Ni that table 3 naphthane is supporting
2Transformation efficiency on the P catalyzer and selectivity.
Embodiment 5
The catalyst of phosphatizing nickel 2.3g that supports that embodiment 2 is prepared is loaded in the reactor drum, and evaluation method is with embodiment 4, and evaluation result is seen table 2, table 3.
Embodiment 6
The catalyst of phosphatizing nickel 2.3g that supports that embodiment 3 is prepared is loaded in the reactor drum, and evaluation method is with embodiment 4, and evaluation result is seen table 2, table 3.
Claims (5)
1. the preparation method of a nickel phosphide, key step is:
(a) ortho phosphorous acid nickel and ammonium hypophosphite are dissolved in the deionized water, mix, wherein, the ratio of the amount of substance of ortho phosphorous acid radical ion and nickel ion is 2～5, and evaporate to dryness gets the yellow-green colour solid;
(b) getting above-mentioned solid and place the tube furnace internal reaction, react used mobile atmosphere and be in hydrogen, nitrogen, helium and the argon gas one or more, is 1～5K/min with temperature rise rate; Temperature programming is to 373-673K; Stablize 2～8h, reduce to room temperature, switch to that to contain oxygen be 0.2～2% the inertia atmosphere that flows; Passivation 2～8h takes out;
(c) the sample ammonia scrubbing after the passivation arrives neutrality with deionized water wash then to colourless, and 373K is dried 12h, gets nickel phosphide;
(d) nickel phosphide that makes carries out activation treatment before using.
2. according to the described preparation method of claim 1, it is characterized in that step (a) can also be with the mixing solutions equivalent impregnation of ortho phosphorous acid nickel and ammonium hypophosphite to carrier, used carrier is MCM-41, SBA-15, SiO
2, TiO
2, ZrO
2, gac (AC), mesoporous carbon (MC) and Al
2O
3In a kind of, dry in the shade behind the dipping, again by the described method roasting of step (b)-(d), washing and the activation of claim 1, make the catalyst of phosphatizing nickel of load.
3. according to the described preparation method of claim 1, it is characterized in that the used mobile atmosphere of inertia of passivation is one or more in hydrogen, nitrogen, helium and the argon gas.
4. according to the described preparation method of claim 1, being characterized as of its activation method: in hydrogen atmosphere, be warmed up to 623～773K, activation 2～5h, pressure 0～5MPa, air speed 1000～4000h with 1～5K/min
-1(V/V).
5. according to the described preparation method of claim 2, it is characterized in that the loading of Ni is 1～4mmol Ni/g carrier.
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|---|---|---|---|
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102373078B (en) * | 2010-08-12 | 2014-02-26 | 中国石油天然气股份有限公司 | Deep hydrodesulfurization method for diesel oil |
| CN101979141B (en) * | 2010-09-15 | 2012-08-22 | 天津大学 | Modified nickel phosphide catalyst and method for hydrogenating and dechlorinating chlorobenzene compounds in presence of same |
| CN102151578B (en) * | 2011-01-21 | 2012-12-19 | 李伟 | Nickel phosphide catalyst for producing vinyl chloride by acetylene hydrochlorination method and preparation method thereof |
| CN102994141A (en) * | 2011-09-15 | 2013-03-27 | 中国石油天然气股份有限公司 | Inferior aviation kerosene hydrotreating method |
| CN102836739B (en) * | 2012-08-25 | 2014-12-17 | 东北石油大学 | Method for preparing supported oil product hydrodesulphurization catalyst with solvothermal method at normal pressure |
| CN105312071A (en) * | 2014-07-28 | 2016-02-10 | 南京大学 | Method for preparing composite oxide supported Ni2P catalyst |
| CN104445116A (en) * | 2014-11-19 | 2015-03-25 | 中国科学院长春应用化学研究所 | Preparation method of transition metal phosphide with good morphology |
| US10406509B2 (en) | 2015-04-23 | 2019-09-10 | Western Washington University | Nanoscale nickel phosphide catalysts for hydrotreatment |
| CN105536860B (en) * | 2015-12-29 | 2018-04-27 | 海南大学 | Ni2The preparation of P/Zr-MCM-41 catalyst and the application of catalysis biological oil and fat preparation bio-fuel |
| CN107876072B (en) * | 2017-11-10 | 2020-02-11 | 中国石油大学(北京) | Hydrogenation catalyst, preparation method and application thereof |
| CN109046438B (en) * | 2018-08-21 | 2021-06-29 | 海南大学 | Double-activity Ni2P/Zr-SBA-15 catalyst and preparation method and application thereof |
| CN109402663B (en) * | 2018-09-04 | 2021-09-07 | 青岛科技大学 | Preparation of FePx with 3D mesoporous structure and application of FePx in hydrogen production by electrolyzing water |
| CN109876835A (en) * | 2019-03-28 | 2019-06-14 | 济南大学 | A kind of preparation and the reduction application of electro-catalysis nitrogen of nano-sheet Fe2O3 doping nickel phosphide |
| CN110627031A (en) * | 2019-09-25 | 2019-12-31 | 常熟理工学院 | Preparation method of molybdenum-doped cobalt phosphide-carbon coral sheet composite material |
| CN110707321A (en) * | 2019-10-23 | 2020-01-17 | 合肥国轩高科动力能源有限公司 | Copper-coated hollow nickel phosphide material and preparation method and application thereof |
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| CN1660695A (en) * | 2004-02-26 | 2005-08-31 | 中国科学院大连化学物理研究所 | Method for preparing phosphide of transition metal |
| CN1958159A (en) * | 2006-10-19 | 2007-05-09 | 安徽师范大学 | Catalyst of phosphatizing nickel, and preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1660695A (en) * | 2004-02-26 | 2005-08-31 | 中国科学院大连化学物理研究所 | Method for preparing phosphide of transition metal |
| CN1958159A (en) * | 2006-10-19 | 2007-05-09 | 安徽师范大学 | Catalyst of phosphatizing nickel, and preparation method |
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