CN103861625A - Preparation method of supported Ni2P catalyst - Google Patents
Preparation method of supported Ni2P catalyst Download PDFInfo
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- CN103861625A CN103861625A CN201410070762.9A CN201410070762A CN103861625A CN 103861625 A CN103861625 A CN 103861625A CN 201410070762 A CN201410070762 A CN 201410070762A CN 103861625 A CN103861625 A CN 103861625A
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- silicon dioxide
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Abstract
The invention discloses a preparation method of supported Ni2P catalyst. The preparation method of the supported Ni2P catalyst comprises the following steps: preparing a silicon dioxide, MCM-41, SBA-15, aluminium oxide, titanium oxide, HY molecular sieve or HZSM-5 molecular sieve supported nickel oxide precursor by adopting an impregnation way; reducing the supported nickel oxide precursor into a supported Ni precursor in a fixed bed reactor, then introducing hydrogen, introducing a triphenylphosphine or tri-n-octylphosphine solution into the fixed bed reactor at a certain temperature, and phosphating for a period of time at constant temperature, thus obtaining the supported Ni2P catalyst in situ. Compared with a general method for preparing the supported Ni2P catalyst by adopting a supported nickel phosphate temperature programmed reduction method, the preparation method of the supported Ni2P catalyst is simple and practicable, generation of aluminium phosphate owning to reaction between phosphorus species and aluminium oxide in a carrier can be avoided, and the phosphorus species can be effectively utilized.
Description
Technical field
The present invention relates to a kind of load Ni
2the preparation method of P catalyst, belongs to catalysis technical field.
Background technology
Since the nineties in last century; much research shows that transition metal phosphide has shown unique catalytic perfomance (Journal of Catalysis in hydrodesulfurization, hydrodenitrogeneration, hydrogenation-dechlorination, hydrogenation deoxidation and some hydrogenation reactions; 2003,216:343; Catalysis Letters, 2012,142:1413; Applied Catalysis B:Environmental, 2014,144:870), more and more receive in recent years the concern of Chinese scholars and industrial quarters.In reported Ni, Co, Fe, Mo and W phosphide catalyst, Ni
2p catalyst has preferably catalytic performance.
Ni
2the preparation method of P catalyst has multiple, comprises phosphate temperature-programmed reduction method, hydrogen phosphide reducing process, phosphite and hypophosphites reducing process, phosphorus solvothermal method and metal and simple substance high-temperature solid phase reaction method etc.Phosphorus solvothermal method and metal and simple substance high-temperature solid phase reaction method can not be for the preparation of support type Ni
2p catalyst.Although processing load Ni, hydrogen phosphide can prepare load Ni
2p catalyst, but hydrogen phosphide is hypertoxicity gas, has safety problem in actual application.Load nickel phosphate presoma temperature-programmed reduction method is preparation load Ni
2the common method of P catalyst.But, because P-O key thermodynamic stability in nickel phosphate is higher, must at comparatively harsh reaction condition, (temperature be usually above 600
oC, heating rate 1
oC/ min and higher H
2air speed) descend reduction just can make Ni
2p, not only energy consumption is high for the method, preparation time is long, and because higher reduction temperature is unsuitable for preparing load Ni at stainless steel fixed bed reactors situ
2p.Under normal circumstances, first in quartz tube reactor, the reduction of load nickel phosphate presoma is made to load Ni
2p catalyst, Ni
2p catalyst is transferred in stainless steel reactor after passivation, then by passivation Ni
2after P catalyst reduces again for hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation and hydrogenation reaction.Therefore, this process is comparatively loaded down with trivial details, very inconvenience in actual application.Though adopt the reducing process can be at lower temperature (300 ~ 550 taking load nickelous hypophosphite or phosphorous acid nickel as presoma
oC) prepare load Ni
2p, remains in catalyst but can generate impurity thing phase and have compared with polyphosphate simultaneously; When adopting Al
2o
3and Si-Al molecular sieve etc. is during containing alumina supporter, hypophosphites and phosphite can be had an effect and form AlPO with carrier
4, be preparation Ni
2p needs the more phosphorus species of load and affects catalyst performance.In addition, taking tri octyl phosphine or triphenylphosphine etc. as phosphorus source, 250 ~ 370
oit can be single Ni of dispersion by metal Ni nano particle phosphatization that C adopts liquid phase method
2p particle, then adopts infusion process to be loaded on carrier; Although the method can be prepared load Ni
2p, this process is more loaded down with trivial details, and Ni
2p and carrier are in use easily reunited a little less than interacting.Based on current load Ni
2the existing limitation of P preparation method, the invention provides under a kind of temperate condition and prepares load Ni at fixed bed reactors situ
2the technology of P catalyst.
Summary of the invention
The object of the invention is to provide a kind of load Ni
2the preparation method of P catalyst, the method process condition gentleness, prepared Ni
2the reactions such as the desulfurization of P catalyst hydrogenation, hydrodenitrogeneration, hydrogenation-dechlorination, hydrogenation deoxidation and hydrogenation have the advantages that efficiency is high.
The present invention is realized by the following technical programs, a kind of load Ni
2the preparation method of P catalyst, is characterized in that comprising the following steps:
1), in the nickel nitrate aqueous solution that is 1.4 ~ 38% by silica, MCM-41, SBA-15, aluminium oxide, titanium oxide, HY molecular sieve or HZSM-5 molecular sieve carrier incipient impregnation in mass concentration, after drying, in air atmosphere, within 4 hours, prepare load nickel oxide precursor through 120 DEG C of dry 12 hours, 500 DEG C roastings;
2) load nickel oxide precursor step 1) being made adds in fixed bed reactors, at H for 450 DEG C of temperature
2after reductase 12 hour, make load Ni presoma, wherein the mass content of Ni is 1 ~ 30%; Then continue to pass into H
2, and taking solution quality air speed as 2 ~ 40 h
-1with control under the condition that P/Ni mol ratio is 0.5 ~ 2, at 250 ~ 450 DEG C of temperature, be that the tri octyl phosphine benzole soln reaction in-situ that 1 ~ 20% triphenylphosphine dodecane solution or the mass concentration tri octyl phosphine dodecane solution that is 1 ~ 20% or the mass concentration triphenylphosphine benzole soln that is 1 ~ 20% or mass concentration are 1 ~ 20% obtains load Ni to passing into mass concentration in fixed bed reactors
2p catalyst.
Feature of the present invention is to prepare load Ni in fixed bed reactors situ under temperate condition
2p catalyst.Compared with conventional load nickel phosphate temperature-programmed reduction method, operation is simple for the method, can also avoid phosphorus species to react with the aluminium oxide in carrier and generate aluminum phosphate, can effectively utilize phosphorus species.Prepared Ni
2p catalyst can be used for the reactions such as hydrodesulfurization, hydrodenitrogeneration, hydrogenation-dechlorination, hydrogenation deoxidation and hydrogenation.
Detailed description of the invention:
Embodiment 1
By 4.36 grams of Ni (NO
3)
26H
2o is dissolved in that in 9.0 ml deionized water, to be made into mass concentration be 20.4% nickel nitrate aqueous solution, 5 grams of silica supports incipient impregnations, in this solution, are obtained to silicon dioxide carried nickel oxide sample for 4 hours 120 DEG C of dry 12 hours, 500 DEG C roastings after drying in air atmosphere.Get 1 gram of silicon dioxide carried nickel oxide sample and be placed in stainless steel fixed bed reactors, 450
oit is 15% silicon dioxide carried Ni presoma that C obtains Ni mass content with hydrogen reducing 2 h.Then, cool the temperature to 400
oc is 8h passing into hydrogen and solution quality air speed
-1and to control P/Ni mol ratio be under 0.75 condition, with micro-feed pump be that 3% triphenylphosphine dodecane solution carries out phosphatization processing to silicon dioxide carried Ni to passing into mass concentration in reactor.After processing finishes, prepared sample is down to room temperature, uses 0.5%O
2/ N
2after passivation 4 h, test for XRD.XRD test result shows, in prepared catalyst, nickel phosphide thing is Ni mutually
2p.
Embodiment 2
Catalyst preparation process is with embodiment 1, and difference is by 0.248 gram of Ni (NO
3)
26H
2o is dissolved in that in 10.6 ml distilled waters, to be made into mass concentration be 1.4% nickel nitrate aqueous solution, by 5 grams of silica supports incipient impregnations in this solution.In prepared silicon dioxide carried Ni sample, Ni mass content is 1%, and this sample prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 3
Catalyst preparation process is with embodiment 1, and difference is by 10.59 grams of Ni (NO
3)
26H
2o is dissolved in that in 6.8 ml distilled waters, to be made into mass concentration be 38% nickel nitrate aqueous solution, by 5 grams of silica supports incipient impregnations in this solution.In prepared silicon dioxide carried Ni sample, Ni mass content is 30%, and this sample prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 4
Catalyst preparation process is with embodiment 1, and difference is to be 2 h in triphenylphosphine dodecane solution quality air speed
-1condition under silicon dioxide carried Ni sample is carried out to phosphatization processing, after phosphatization, prepare silicon dioxide carried Ni
2p.
Embodiment 5
Catalyst preparation process is with embodiment 1, and difference is to be 30 h in triphenylphosphine dodecane solution quality air speed
-1condition under silicon dioxide carried Ni sample is carried out to phosphatization processing, after phosphatization, prepare silicon dioxide carried Ni
2p.
Embodiment 6
Catalyst preparation process is with embodiment 1, and difference is to be 40 h in triphenylphosphine dodecane solution quality air speed
-1condition under silicon dioxide carried Ni sample is carried out to phosphatization processing, after phosphatization, prepare silicon dioxide carried Ni
2p.
Embodiment 7
Catalyst preparation process, with embodiment 1, is carried out phosphatization processing to silicon dioxide carried Ni sample under the condition that difference is is 0.5 in control P/Ni mol ratio, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 8
Catalyst preparation process, with embodiment 1, is carried out phosphatization processing to silicon dioxide carried Ni sample under the condition that difference is is 1 in control P/Ni mol ratio, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 9
Catalyst preparation process, with embodiment 1, is carried out phosphatization processing to silicon dioxide carried Ni sample under the condition that difference is is 2 in control P/Ni mol ratio, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 10
Catalyst preparation process is with embodiment 1, and difference is that the triphenylphosphine dodecane solution that silicon dioxide carried Ni sample mass concentration is 1% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 11
Catalyst preparation process is with embodiment 1, and difference is that the triphenylphosphine dodecane solution that silicon dioxide carried Ni sample mass concentration is 10% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 12
Catalyst preparation process is with embodiment 1, and difference is that the triphenylphosphine dodecane solution that silicon dioxide carried Ni sample mass concentration is 20% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 13
Catalyst preparation process is with embodiment 1, and difference is that the triphenylphosphine benzole soln that silicon dioxide carried Ni sample mass concentration is 1% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 14
Catalyst preparation process is with embodiment 1, and difference is that the triphenylphosphine benzole soln that silicon dioxide carried Ni sample mass concentration is 5% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 15
Catalyst preparation process is with embodiment 1, and difference is that the triphenylphosphine benzole soln that silicon dioxide carried Ni sample mass concentration is 10% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 16
Catalyst preparation process is with embodiment 1, and difference is that the triphenylphosphine benzole soln that silicon dioxide carried Ni sample mass concentration is 20% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 17
Catalyst preparation process is with embodiment 1, and difference is that the tri octyl phosphine dodecane solution that silicon dioxide carried Ni sample mass concentration is 1% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 18
Catalyst preparation process is with embodiment 1, and difference is that the tri octyl phosphine dodecane solution that silicon dioxide carried Ni sample mass concentration is 5% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 19
Catalyst preparation process is with embodiment 1, and difference is that the tri octyl phosphine dodecane solution that silicon dioxide carried Ni sample mass concentration is 10% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 20
Catalyst preparation process is with embodiment 1, and difference is that the tri octyl phosphine dodecane solution that silicon dioxide carried Ni sample mass concentration is 20% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 21
Catalyst preparation process is with embodiment 1, and difference is that the tri octyl phosphine benzole soln that silicon dioxide carried Ni sample mass concentration is 1% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 22
Catalyst preparation process is with embodiment 1, and difference is that the tri octyl phosphine benzole soln that silicon dioxide carried Ni sample mass concentration is 5% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 23
Catalyst preparation process is with embodiment 1, and difference is that the tri octyl phosphine benzole soln that silicon dioxide carried Ni sample mass concentration is 10% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 24
Catalyst preparation process is with embodiment 1, and difference is that the tri octyl phosphine benzole soln that silicon dioxide carried Ni sample mass concentration is 20% carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 25
Catalyst preparation process is with embodiment 1, and difference is that silicon dioxide carried Ni sample is 250
oc carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 26
Catalyst preparation process is with embodiment 1, and difference is that silicon dioxide carried Ni sample is 300
oc carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 27
Catalyst preparation process is with embodiment 1, and difference is that silicon dioxide carried Ni sample is 450
oc carries out phosphatization processing, prepares silicon dioxide carried Ni after phosphatization
2p.
Embodiment 28
Catalyst preparation process is with embodiment 1, and difference is that carrier adopts MCM-41 mesopore molecular sieve, and prepared sample is MCM-41 load Ni
2p.
Embodiment 29
Catalyst preparation process is with embodiment 1, and difference is that carrier adopts SBA-15 mesopore molecular sieve, and prepared sample is SBA-15 load Ni
2p.
Embodiment 30
Catalyst preparation process is with embodiment 1, and difference is that carrier adopts titanium oxide, and prepared sample is titania oxide supported Ni
2p.
Embodiment 31
Catalyst preparation process is with embodiment 1, and difference is that carrier adopts gama-alumina, and prepared sample is gama-alumina load Ni
2p.
Embodiment 32
Catalyst preparation process is with embodiment 1, and difference is that carrier adopts HY molecular sieve, and prepared sample is HY load Ni
2p.
Embodiment 33
Catalyst preparation process is with embodiment 1, and difference is that carrier adopts HZSM-5 molecular sieve, and prepared sample is HZSM-5 load Ni
2p.
Claims (1)
1. a load Ni
2the preparation method of P catalyst, is characterized in that comprising the following steps:
1), in the nickel nitrate aqueous solution that is 1.4 ~ 38% by silica, MCM-41, SBA-15, aluminium oxide, titanium oxide, HY molecular sieve or HZSM-5 molecular sieve carrier incipient impregnation in mass concentration, after drying, in air atmosphere, within 4 hours, prepare load nickel oxide precursor through 120 DEG C of dry 12 hours, 500 DEG C roastings;
2) load nickel oxide precursor step 1) being made adds in fixed bed reactors, at H for 450 DEG C of temperature
2after reductase 12 hour, make load Ni presoma, wherein the mass content of Ni is 1 ~ 30%; Then continue to pass into H
2, and taking solution quality air speed as 2 ~ 40 h
-1with control under the condition that P/Ni mol ratio is 0.5 ~ 2, at 250 ~ 450 DEG C of temperature, be that the tri octyl phosphine benzole soln reaction in-situ that 1 ~ 20% triphenylphosphine dodecane solution or the mass concentration tri octyl phosphine dodecane solution that is 1 ~ 20% or the mass concentration triphenylphosphine benzole soln that is 1 ~ 20% or mass concentration are 1 ~ 20% obtains load Ni to passing into mass concentration in fixed bed reactors
2p catalyst.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841465A (en) * | 2015-05-08 | 2015-08-19 | 中国石油大学(华东) | Load type nickel phosphide catalyst and pre-phosphating preparation method thereof |
| CN104971749A (en) * | 2015-06-18 | 2015-10-14 | 大连理工大学 | Ni2P/Al2O3 catalyst and preparation method therefor |
| CN105879898A (en) * | 2016-02-06 | 2016-08-24 | 温州大学 | Ni2P/zeolite catalyst and preparation and application thereof |
| CN107088432A (en) * | 2017-04-12 | 2017-08-25 | 南京师范大学 | A kind of two-dimentional Ru doping Ni2P plate-like nano flakes and its preparation method and application |
| CN108273532A (en) * | 2018-01-14 | 2018-07-13 | 常州大学 | A kind of catalyst of phosphatizing nickel of high activity and its preparation method and application |
| CN109967101A (en) * | 2019-05-08 | 2019-07-05 | 西安近代化学研究所 | A kind of selection hydrogenation-dechlorination preparation chlorotrifluoroethylene catalyst |
| CN110813352A (en) * | 2019-10-31 | 2020-02-21 | 润泰化学（泰兴）有限公司 | Ni2Preparation method of P/NC catalyst, Ni2P/NC catalyst and application thereof |
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| CN102836739A (en) * | 2012-08-25 | 2012-12-26 | 东北石油大学 | Method for preparing supported oil product hydrodesulphurization catalyst with solvothermal method at normal pressure |
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| KYE-SUNG CHO ET AL.: "A new synthesis of highly active Ni2P/Al2O3 catalyst by liquid phase phosphidation for deep hydrodesulfurization", 《CATALYSIS COMMUNICATIONS》 * |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104841465A (en) * | 2015-05-08 | 2015-08-19 | 中国石油大学(华东) | Load type nickel phosphide catalyst and pre-phosphating preparation method thereof |
| CN104971749A (en) * | 2015-06-18 | 2015-10-14 | 大连理工大学 | Ni2P/Al2O3 catalyst and preparation method therefor |
| CN105879898A (en) * | 2016-02-06 | 2016-08-24 | 温州大学 | Ni2P/zeolite catalyst and preparation and application thereof |
| CN105879898B (en) * | 2016-02-06 | 2019-01-15 | 温州大学 | A kind of Ni2P/ zeolite catalyst and its preparation and application |
| CN107088432A (en) * | 2017-04-12 | 2017-08-25 | 南京师范大学 | A kind of two-dimentional Ru doping Ni2P plate-like nano flakes and its preparation method and application |
| CN107088432B (en) * | 2017-04-12 | 2019-09-06 | 南京师范大学 | A kind of two dimension Ru doping Ni2P plate-like nano flake and its preparation method and application |
| CN108273532A (en) * | 2018-01-14 | 2018-07-13 | 常州大学 | A kind of catalyst of phosphatizing nickel of high activity and its preparation method and application |
| CN109967101A (en) * | 2019-05-08 | 2019-07-05 | 西安近代化学研究所 | A kind of selection hydrogenation-dechlorination preparation chlorotrifluoroethylene catalyst |
| CN109967101B (en) * | 2019-05-08 | 2021-12-21 | 西安近代化学研究所 | Catalyst for preparing chlorotrifluoroethylene by selective hydrogenation dechlorination |
| CN110813352A (en) * | 2019-10-31 | 2020-02-21 | 润泰化学（泰兴）有限公司 | Ni2Preparation method of P/NC catalyst, Ni2P/NC catalyst and application thereof |
| CN110813352B (en) * | 2019-10-31 | 2022-05-03 | 润泰化学（泰兴）有限公司 | Ni2Preparation method of P/NC catalyst, Ni2P/NC catalyst and application thereof |
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Application publication date: 20140618 |