CN101168132A - Process for preparing high dispersion supported type transition metal phosphide catalyst - Google Patents
Process for preparing high dispersion supported type transition metal phosphide catalyst Download PDFInfo
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- CN101168132A CN101168132A CNA2006101340203A CN200610134020A CN101168132A CN 101168132 A CN101168132 A CN 101168132A CN A2006101340203 A CNA2006101340203 A CN A2006101340203A CN 200610134020 A CN200610134020 A CN 200610134020A CN 101168132 A CN101168132 A CN 101168132A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention relates to a catalyst of supported metal phosphide, in particular to a process for preparing the catalyst of high dispersive supported metal phosphide. The catalyst is composed of two parts of active components and a carrier which can be represented by AP/Z or B2P/Z, wherein the A of the active components is Mo or W, the B of the active components is Ni or Co, and the Z of the carrier is Al2O3 or SiO2. The operation steps of the catalyst are that transient metal salt and mammonium dihydrogen phosphate are dissolved in deionized water according to the stoichiometric ratio of targeted phosphide, and simultaneously moderate hydroxy acid as chelating agent is added to get the impregnating solution for preparing supported transition metal phosphide. The porous carrier is immersed in the impregnating solution, and is rested, the procedure gains temperature and returns after the impregnating solution is dried, roasted and under the atmosphere of hydrogen gas, and finally the supported transition metal phosphide is made. The supported transition metal phosphide prepared by the preparation method has the advantages of high dispersion, simple and convenient operation, low cost, no pollution, good repeatability and easiness of large scale preparation.
Description
Technical field
The present invention relates to loaded metal phosphorizing mixture catalyst, specifically a kind of preparation method of high dispersion supported type transition metal phosphide catalyst.
Background technology
Phosphide has class precious metal catalyst characteristic, is a kind of new catalytic material after transition metal carbide, nitride, successfully is applied to the deep hydrodesulfurizationof of oil product, and the hydrodenitrogeneration reaction has alternative existing C o (Ni) MoS/Al
2O
3Commercial potentiality (Joumal of Catalysis, 216 (2003), 343) with catalyst.On the other hand, such novel substance can also be widely applied in a lot of other hydrogen-involved reactions, as hydrogenation reaction, and the reduction of NO and electrochemical reducting reaction etc.
In these catalytic reactions, people adopt mostly is loaded transition metal phosphide catalyst (Joumal of Catalysis, 218 (2003), 78).Loaded phosphide mainly is to adopt will to be impregnated with phosphatic carrier method of direct reduction and to prepare.But the phosphide of preparing so is not very even in the distribution of carrier surface.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of high dispersion supported type transition metal phosphide catalyst, the present invention can improve the degree of scatter of active material at carrier surface greatly, thereby prepares the supported type transition metal phosphide of high dispersive.
For achieving the above object, the technical solution used in the present invention is:
A kind of preparation method of high dispersion supported type transition metal phosphide catalyst, catalyst comprises active component and carrier two parts, can be with AP/Z or B
2P/Z represents; Wherein, active component A is Mo or W, and B is Ni or Co, promptly comprises carrier and active component, and described active part is phosphatization molybdenum, tungsten phosphide, phosphatization cobalt or nickel phosphide; Carrier Z is Al
2O
3Or SiO
2In the weight (vehicle weight+active component weight) of phosphide, the load capacity of sample is 5-30wt%.It can be operated as follows,
1) preparation of target phosphide presoma:
According to the molecular formula of target phosphide,, accurately take by weighing the soluble transition metal salt and the diammonium hydrogen phosphate of target phosphide stoichiometric proportion according to the difference of supported carrier amount; In deionized water fully after the dissolving, the full water absorption of closing of the volumetric usage of its deionized water and carrier is suitable with the two, adding chelating agent carboxylic acid, and wherein the mol ratio of metal consumption is 1-3 in chelating agent and the phosphide, the maceration extract that obtains clarifying; Add an amount of carrier to this maceration extract, flooded 3-12 hour, descended dry 10-14 hour,, promptly get target phosphide presoma at last in 400-600 ℃ of following roasting 5-10 of moving air atmosphere hour at 100-160 ℃; According to the mass percent meter, the load capacity of phosphide is 5-30wt% on the carrier;
2) preparation of target phosphide:
Adopt the temperature programmed reduction method, with the presoma that makes 600～850 ℃ of following reductase 12s hour under hydrogen atmosphere, and at room temperature with 1% O
2/ N
2(V/V) passivating gas passivation promptly obtains the supported type transition metal phosphide catalyst of high dispersive.
Carrier is the aluminium oxide or the silica of porous; Carboxylic acid is citric acid, malic acid or tartaric acid; Transition metal is molybdenum, tungsten, nickel or cobalt.
Described employing temperature programmed reduction technology is specially, and under hydrogen atmosphere, predecessor is raised to 350 ℃ at 0.5-2 hour from room temperature, and the speed with 1-8 ℃/min is raised to 600-850 ℃ again, and keeps 1-3 hour under this temperature, is cooled to room temperature then.
For preventing that phosphide from contacting with air violent oxidation reaction taking place, before the catalyst sample ingress of air for preparing, uses the O of volume ratio 1% earlier
2/ N
2Passivating gas passivation 1-3 hour.
The present invention has following advantage:
1. active material is at the degree of scatter height of carrier surface.The present invention utilizes carboxylic acid, and as chelating agent, they can generate stable chelate with metal ion as citric acid, malic acid, tartaric acid.Chelate on the carrier could decompose under higher temperature, simultaneously because in dry run, carboxylic acid has very strong gel-formation power, so active specy is not easy on the surface of carrier to take place to arrange again, has reduced the reunion of active material.With adopt not hydroxyl-containing acid, compare with the loaded phosphide that common maceration extract is prepared, the active sites number significantly increases on the transition metal phosphide of preparing with the present invention, decentralization also obviously improves.
2. the present invention has attempted the presoma of loaded phosphide is modified first, can improve the degree of scatter of active material greatly at carrier surface, thereby prepare the supported type transition metal phosphide catalyst of high dispersive, it is easy and simple to handle, cost is low, pollution-free, good reproducibility, be easy to the advantage of mass preparation.
Description of drawings
Fig. 1 is embodiment 1 (a) and the activity of comparative example 1 (b) in 30 ℃ of following hydrazine decomposition reactions.
The specific embodiment
Below by example the present invention is further described.Be noted that these embodiment only are in order to demonstrate the invention, in office where face does not constitute limitation of the scope of the invention.
Embodiment 1MoP/Al
2O
3
Measure the pore volume (mlg of used carrier in advance
-1), according to the consumption of carrier, determine the content of water in the maceration extract.The Al that uses in the present embodiment
2O
3Pore volume be 1.1mlg
-1(molybdenum: ammonium molybdate 0.364g phosphorus=1: 1) and diammonium hydrogen phosphate 0.276g also are dissolved in the 3.3ml water, after treating to dissolve fully, citric acid are joined above-mentioned solution, obtain maceration extract to take by weighing target phosphide (MoP) stoichiometric proportion.The consumption of citric acid and metal molybdenum are 2: 1 (mol ratio).Take by weighing 3.0g Al
2O
3Be dipped in the maceration extract, leave standstill 6 hours after, 120 ℃ of dryings 12 hours, at last under moving air atmosphere, 500 ℃ of calcinings 5 hours obtained presoma.Under hydrogen atmosphere, predecessor was raised to 350 ℃ at 0.5 hour from room temperature, the speed with 5 ℃/min is raised to 850 ℃ again, and keeps 2 hours under this temperature, is cooled to room temperature then.For preventing that phosphide from contacting with air violent oxidation reaction takes place, before the sample ingress of air, earlier with 1% O
2/ N
2(V/V) the passivating gas passivation is 2 hours.Can obtain 8wt%MoP/Al
2O
3, the decentralization of MoP on carrier is as shown in table 1.
Shown in being calculated as follows of decentralization:
Active figure place * 100% of the surface-active figure place that decentralization=probe molecule CO is measured/support in theory
Embodiment 2 WP/SiO
2
The preparation method is with embodiment 1.The SiO that uses in the present embodiment
2Pore volume be 1.5mlg
-1(tungsten: ammonium metatungstate phosphorus=1: 1) is 0.567g, and diammonium hydrogen phosphate 0.275g is dissolved in the 4.5ml water, after treating to dissolve fully, malic acid is joined above-mentioned solution, obtains maceration extract to take by weighing target phosphide (WP) stoichiometric proportion.The consumption of malic acid and metal molybdenum are 1: 1 (mol ratio).Take by weighing 3.0g SiO
2In maceration extract.After leaving standstill 10 hours, 140 ℃ of dryings 10 hours, at last under moving air atmosphere, 450 ℃ of calcinings 5 hours obtained presoma.Under hydrogen atmosphere, predecessor was raised to 350 ℃ at 0.5 hour from room temperature, the speed with 5 ℃/min is raised to 750 ℃ again, and keeps 2 hours under this temperature, is cooled to room temperature then.For preventing that phosphide from contacting with air violent oxidation reaction taking place, before the sample ingress of air, uses O earlier
2/ N
2(1%V/V) passivation is 2 hours.Can obtain 13wt%WP/SiO
2, the decentralization of WP on carrier is as shown in table 1.
Embodiment 3 Ni
2P/SiO
2
Take by weighing target phosphide (Ni
2P) (nickel: nickel nitrate 3.15g phosphorus=2: 1) mixes with diammonium hydrogen phosphate 0.74g and is dissolved in the 4.5ml water stoichiometric proportion, has green precipitate to generate; Then with tartrate anion according to joining above-mentioned solution with the ratio (mol ratio, 3: 1) of metal, treat that tartaric acid dissolves fully after, the maceration extract that obtains clarifying.Take by weighing 3.0g SiO
2Put into maceration extract, leave standstill 10 hours after, 140 ℃ of dryings 10 hours, at last under moving air atmosphere, 450 ℃ of calcinings 5 hours obtained presoma.Under hydrogen atmosphere, predecessor was raised to 350 ℃ at 0.5 hour from room temperature, the speed with 5 ℃/min is raised to 600 ℃ again, and keeps 2 hours under this temperature, is cooled to room temperature then.For preventing that phosphide from contacting with air violent oxidation reaction taking place, before the sample ingress of air, uses O
2/ N
2(1%V/V) passivation is 2 hours.Can obtain 18wt%Ni
2P/SiO
2, Ni
2The decentralization of P on carrier is as shown in table 1.
Embodiment 4 Co
2P/SiO
2
Get cobalt nitrate 3.90g and mix with diammonium hydrogen phosphate 1.01g and be dissolved in the 4.5ml water, have the aubergine precipitation to generate; Then with tartrate anion according to joining above-mentioned solution with the ratio (mol ratio, 2: 1) of metal, treat that tartaric acid dissolves fully after, the maceration extract that obtains clarifying.Take by weighing 3.0g SiO
2Put into maceration extract, leave standstill 10 hours after, 120 ℃ of dryings 10 hours, at last under moving air atmosphere, 450 ℃ of calcinings 5 hours obtained presoma.Under hydrogen atmosphere, predecessor was raised to 350 ℃ at 0.5 hour from room temperature, the speed with 5 ℃/min is raised to 600 ℃ again, and keeps 2 hours under this temperature, is cooled to room temperature then.For preventing that phosphide from contacting with air violent oxidation reaction taking place, before the sample ingress of air, uses O
2/ N
2(1%V/V) passivation is 2 hours, can obtain 25wt%Co
2P/SiO
2, Co
2The decentralization of P on carrier is as shown in table 1.
Comparative example 1
Prepared 8wt%MoP/Al with the phosphatic method of direct reduction
2O
3To contain molybdenum, with the mol ratio of phosphorus be that 1 ammonium molybdate and diammonium hydrogen phosphate are dissolved in appropriate amount of deionized water and obtain maceration extract.Then, alumina support is joined in the maceration extract, obtain predecessor after drying, the roasting.Employing with the method for the identical temperature programmed reduction of embodiment 1 with the predecessor that makes at 850 ℃ of reductase 12s hour, and passivation at room temperature.The decentralization numerical value of the phosphide in this compound and the embodiment of the invention is listed in table 1.
Comparative example 2
Prepared 13wt%WP/SiO with the phosphatic method of direct reduction
2With tungsten and phosphorus mol ratio is that 1 ammonium metatungstate and diammonium hydrogen phosphate are dissolved in appropriate amount of deionized water.Then, silica support is joined in the above maceration extract, obtain predecessor after drying, the roasting.Employing with the method for the identical temperature programmed reduction of embodiment 2 with the predecessor that makes at 750 ℃ of reductase 12s hour, after waiting to drop to room temperature, with O
2/ N
2(1%V/V) passivation is 2 hours.The decentralization numerical value of the phosphide in this phosphide and the embodiment of the invention is listed in table 1.
Comparative example 3
Prepared 18wt%Ni with the phosphatic method of direct reduction
2P/SiO
2Method is as follows: with the mol ratio of nickel and phosphorus is that 2 nickel nitrate and diammonium hydrogen phosphate are dissolved in appropriate amount of deionized water.Add nitric acid simultaneously with dissolution precipitation, obtain clarifying maceration extract.Then, silica support is joined in the above maceration extract, obtain predecessor after drying, the roasting.Employing with the method for the identical temperature programmed reduction of embodiment 3 with the predecessor that makes at 600 ℃ of reductase 12s hour, and at room temperature with O
2/ N
2(1%V/V) passivation is 2 hours.The decentralization numerical value of the phosphide in this phosphide and the embodiment of the invention is listed in table 1.
Comparative example 4
Prepared 25wt%Co with the phosphatic method of direct reduction
2P/SiO
2Method is as follows: with the mol ratio of cobalt and phosphorus is that 2 cobalt nitrate and diammonium hydrogen phosphate are dissolved in appropriate amount of deionized water, adds nitric acid simultaneously with dissolution precipitation, obtains clarifying maceration extract.Then, silica support is joined in the above maceration extract, obtain predecessor after drying, the roasting.Employing with the method for the identical temperature programmed reduction of embodiment 4 with the predecessor that makes at 600 ℃ of reductase 12s hour, and at room temperature with O
2/ N
2(1%V/V) passivation is 2 hours.The decentralization numerical value of the phosphide in this phosphide and the embodiment of the invention is listed in table 1.
MoP, WP, the Ni of the preparation of table 1 distinct methods
2P, Co
2The decentralization of P
Application examples
Evaluating catalyst
Evaluating catalyst of the present invention carries out in microreactor.Experimentation is as follows: the 0.04gMoP catalyst be loaded on U type quartz reactor fixed bed after 0.1g quartz sand evenly mixes.Catalyst feeds hydrogen before reaction, with 10 ℃ of min
-1Speed be warmed up to 650 ℃, and keep 30 minutes to remove surface passivation layer, obtain the MoP catalyst of fresh attitude.The temperature of question response device is reduced to room temperature, with the temperature to 30 of water-bath conditioned reaction device ℃, then feeds the hydrazine unstripped gas.The hydrazine raw material is to bring beds by Bubbling method into by argon gas under 30 ℃, and flow is 85ml min
-1, hydrazine content is about 3% (hydrazine/argon gas v/v).Reaction raw materials and product adopt 13X molecular sieve column separation of nitrogen and hydrogen by the online detection of Agilent 6890 chromatograms (TCD detector), and the Chromosorb103 post separates ammonia and hydrazine, carries out full product analysis.The conversion ratio of hydrazine is calculated by following formula:
Reaction result sees Table 1.
The phosphide that adopts this example preparation and the phosphide of embodiment preparation are under 30 ℃, and the activity in the hydrazine decomposition as shown in Figure 1.The phosphide catalyst that adopts the example method to prepare has than the better hydrazine degrading activity of comparative example.
Claims (6)
1. the preparation method of a high dispersion supported type transition metal phosphide catalyst, it is characterized in that: catalyst comprises active component and carrier two parts, can be with AP/Z or B
2P/Z represents; Wherein, active component A is Mo or W, and B is Ni or Co; Carrier Z is Al
2O
3Or SiO
2It can be operated as follows,
1) preparation of target phosphide presoma:
According to the molecular formula of target phosphide,, accurately take by weighing the soluble transition metal salt and the diammonium hydrogen phosphate of target phosphide stoichiometric proportion according to the difference of supported carrier amount; In deionized water fully after the dissolving, the full water absorption of closing of the volumetric usage of its deionized water and carrier is suitable with the two, adding chelating agent carboxylic acid, and wherein the mol ratio of metal consumption is 1-3 in chelating agent and the phosphide, the maceration extract that obtains clarifying; Add carrier to this maceration extract, flooded 3-12 hour, descended dry 10-14 hour,, promptly get target phosphide presoma at last in 400-600 ℃ of following roasting 5-10 of moving air atmosphere hour at 100-160 ℃; According to the mass percent meter, the load capacity of phosphide is 5-30wt% on the carrier;
2) preparation of target phosphide:
Adopt the temperature programmed reduction method, with the presoma that makes 600-850 ℃ of following reductase 12 hour under hydrogen atmosphere, and at room temperature with 1% O
2/ N
2(V/V) passivating gas passivation promptly obtains the supported type transition metal phosphide catalyst of high dispersive.
2. according to the described preparation method of claim 1, it is characterized in that: carrier is the aluminium oxide or the silica of porous.
3. according to the described preparation method of claim 1, it is characterized in that: described carboxylic acid is citric acid, malic acid or tartaric acid.
4. according to the described preparation method of claim 1, it is characterized in that: described transition metal is molybdenum, tungsten, nickel or cobalt.
5. according to the described preparation method of claim 1, it is characterized in that: described employing temperature programmed reduction is specially, under hydrogen atmosphere, predecessor was raised to 350 ℃ at 0.5-2 hour from room temperature, speed with 1-8 ℃/min is raised to 600-850 ℃ again, and under this temperature, kept 1-3 hour, be cooled to room temperature then.
6. according to the described preparation method of claim 1, it is characterized in that: for preventing that phosphide from contacting with air violent oxidation reaction takes place, before the catalyst sample ingress of air for preparing, use the O of volume ratio 1% earlier
2/ N
2Passivating gas passivation 1-3 hour.
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| CN111822021A (en) * | 2019-04-18 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of bulk phase hydrofining catalyst |
| CN111822020A (en) * | 2019-04-18 | 2020-10-27 | 中国石油化工股份有限公司 | Rare earth-containing hydrofining catalyst and preparation method thereof |
| CN111822039B (en) * | 2019-04-18 | 2023-05-05 | 中国石油化工股份有限公司 | Preparation method of rare earth-containing hydrocracking catalyst |
| CN111822039A (en) * | 2019-04-18 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of rare earth-containing hydrocracking catalyst |
| CN111822020B (en) * | 2019-04-18 | 2023-04-14 | 中国石油化工股份有限公司 | Rare earth-containing hydrofining catalyst and preparation method thereof |
| CN111822021B (en) * | 2019-04-18 | 2022-10-11 | 中国石油化工股份有限公司 | Preparation method of bulk phase hydrofining catalyst |
| CN111822022A (en) * | 2019-04-18 | 2020-10-27 | 中国石油化工股份有限公司 | Preparation method of phosphorus-containing hydrocracking catalyst |
| CN112973660B (en) * | 2019-12-14 | 2022-04-22 | 中国科学院大连化学物理研究所 | High-dispersion non-noble metal catalyst and preparation method and application thereof |
| CN112973660A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | High-dispersion non-noble metal catalyst and preparation method and application thereof |
| CN114073986A (en) * | 2020-08-19 | 2022-02-22 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method and preparation method thereof |
| CN114073986B (en) * | 2020-08-19 | 2024-03-29 | 中国石油化工股份有限公司 | Catalyst for synthesizing vinyl acetate by ethylene method and preparation method thereof |
| CN114763620A (en) * | 2022-04-15 | 2022-07-19 | 天津科技大学 | Preparation method of transition metal phosphorus sulfide electrolyzed water hydrogen evolution catalyst |
| CN114763620B (en) * | 2022-04-15 | 2023-12-05 | 天津科技大学 | Preparation method of transition metal phosphorus sulfide electrolytic water hydrogen evolution catalyst |
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