CN102029169B - Method for preparing loaded transitional metal phosphide catalyst - Google Patents
Method for preparing loaded transitional metal phosphide catalyst Download PDFInfo
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- CN102029169B CN102029169B CN200910187728.9A CN200910187728A CN102029169B CN 102029169 B CN102029169 B CN 102029169B CN 200910187728 A CN200910187728 A CN 200910187728A CN 102029169 B CN102029169 B CN 102029169B
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Abstract
The invention relates to a method for preparing a loaded transitional metal phosphide catalyst. Red phosphorus is taken as a phosphorus source, chlorides, nitrates and acetates of one or more of metallic elements in a VIB family and/or a VIII family are taken as metal precursors, and wave-absorbing materials such as activated carbon, carbon nanotubes, carbon fibers, carbon molecular sieves, mesoporous carbon, silicon carbide and the like are taken as carriers, the loaded transitional metal phosphide catalyst is efficiently and rapidly synthesized by a microwave heating method in an argon or hydrogen flow atmosphere. The catalyst prepared by the method has high activity and selectivity in a catalytic reaction.
Description
Technical field
The present invention relates to transition metal phosphide, a kind of method of preparing efficiently, fast loaded transitional metal phosphide catalyst specifically, its metal phosphide with low cost, that take in group vib and/or VIII family is active component.
Background technology
Transition metal phosphide is the very important catalysis material of a class.As catalyst, in many hydrogen-involved reactions, shown good catalytic activity, as: selective hydrogenation reaction, HDS, HDN and hydrazine decomposition reaction.But the method that current routine is prepared carrier-borne transition metal phosphide is by reducing metal phosphate, to obtain phosphide under hydrogen atmosphere.The method need to be longer recovery time (more than 8 hours), process is complicated, reduction temperature is high, energy consumption is high.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of efficient, quick, energy-conservation loaded transitional metal phosphide catalyst.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of preparation method of loaded transitional metal phosphide catalyst, take red phosphorus as phosphorus source, one or more metallic elements of take in group vib and/or VIII family are metal component, take absorbing material as carrier, under microwave heating condition, prepare transition metal phosphide catalyst.
Be specially:
According to carrying metal active component 1.15 * 10 on every gram of carrier
-2-4.6 * 10
-5mol meter, is supported on the soluble-salt of metal active constituent on carrier by infusion process, then with red phosphorus mixed grinding, and P elements and intermetallic mol ratio>=1 in red phosphorus;
Under argon gas or hydrogen atmosphere, utilize heating using microwave 2-30min; Under last normal temperature, take mol ratio as 90-99: the N of 1-10
2/ O
2atmosphere passivation obtains finished product for 3-5 hour; In finished product, the mol ratio of metal and phosphorus is 3: 1-1: 2.
The soluble-salt of described metal active constituent is chloride, nitrate or acetate, by equi-volume impregnating, supports on carrier; The carrier of described loaded catalyst is material with carbon element or the carborundum with absorbing property, and described material with carbon element is one or more in active carbon, CNT, carbon fiber, carbon molecular sieve, mesoporous carbon;
Described metal component is preferably one or more in Fe, Co, Ni, Mo, W metallic element.
In metal and red phosphorus, the mol ratio of P elements is generally 1: 1-1: 5, be preferably 1: 2-1: 3.
Under microwave power 10-900W condition, in every gram of carrier, catalyst utilizes the common 4-10min of heating using microwave under the atmosphere that flows.
Tool of the present invention has the following advantages:
1. efficiently, synthesize fast loaded transitional metal phosphide catalyst.Preparation overall process is simple, and utilizes heating using microwave can within a few minutes, synthesize fast transition metal phosphide
2. with low cost.Raw material of the present invention is cheap transition metal chloride, nitrate, acetate and red phosphorus, with low cost.
3. save the energy.Adopt heating using microwave to be rapidly heated, selectively heating, homogeneous heating, power output is low, in heating process, bed temperature is no more than 250 ℃, and except a small amount of loss almost without other energy consumptions.
4. catalytic performance is high.The present invention, in the selection of catalyst carrier, has adopted the carrier that has better wave-sucking performance, specifically comprises active carbon, CNT, carbon fiber, carbon molecular sieve, mesoporous carbon, and the absorbing material such as carbofrax material; Wave-sucking performance by carrier heats, its homogeneous heating, and preparation temperature is low, has improved the decentralization of catalyst particle, thereby has improved its catalytic performance.
Accompanying drawing explanation
Heating using microwave Ni processed under Fig. 1 argon gas atmosphere
2xRD collection of illustrative plates (a) Ni/P=1/2 (b) Ni/P=1/3 (c) Ni/P=1/5 (Ni of P/AC different Ni/P
2p (◆), Ni
5p
4(*), NiCl
2(●), NiP
2(▽));
Heating using microwave Ni processed under Fig. 2 hydrogen atmosphere
2xRD collection of illustrative plates (a) Ni/P=1/2 (b) Ni/P=1/3 (c) the Ni/P=1/5 ((Ni of P/AC different Ni/P
2p (◆), Ni
5p
4(*), NiCl
2(●), NiP
2(▽));
Heating using microwave CoP/AC processed and FeP/AC collection of illustrative plates (a) CoP/AC (b) FeP/AC ((o) CoP/AC, (◆) FeP/AC) under Fig. 3 hydrogen atmosphere;
Fig. 4 hydrogenation process schematic diagram.
The specific embodiment
Embodiment 1
The preparation of catalyst: the wet point wet impregnations such as loaded transitional metal phosphide catalyst employing involved in the present invention are supported on metal active constituent on carrier.Here take nickel phosphide/active carbon as example, the preparation of catalyst of the present invention is done to general description.
0.559g six water nickel chlorides are dissolved in 1ml distilled water and are stirred, and the settled solution obtaining adds and in 1g active carbon, carries out incipient impregnation, then at 120 ℃, dries 12 hours, and the sample obtaining and 0.183g red phosphorus mixed grinding are even, obtain predecessor.
The presoma obtaining is packed in vertical catalyst preparation feedback pipe, carry out heating using microwave in mobile argon gas or hydrogen atmosphere, microwave power is 50W.In heating process, occur white cigarette (white phosphorus distillation) in pipe, infrared detecting set shows that in course of reaction, reaction bed temperature is no more than 250 ℃.After white cigarette disappears, after 10～60 seconds, stop heating, heating overall process only needs 5～7 minutes.Then pass into mol ratio and be the N of 99: 1
2/ O
2carry out passivation 3 hours, obtain catalyst.
Embodiment 2
Preparation result: preparation process is with embodiment 1, when microwave heating process carries out under argon gas atmosphere, mol ratio (the Ni/P=1/2 of different nickel and phosphorus, 1/3,1/5) catalyst obtaining, the result that application XRD characterizes is as Fig. 1, and from Fig. 1 XRD result, figure can find out, under the condition of heating using microwave, react after 5-7 minute, can successfully prepare the phosphide catalyst with typical nickel phosphide crystal phase structure.Concrete outcome shows, when Ni/P=1/2, only have and seldom measure nickel chloride not by red phosphorus phosphatization, and work as phosphorus ratio, is increased to Ni/P=1/3, and 1/5 o'clock, metal, completely by phosphatization, generated nickel phosphide.
Preparation process is with embodiment 1, when microwave heating process carries out under hydrogen atmosphere, mol ratio (the Ni/P=1/2 of different nickel and phosphorus, 1/3,1/5) catalyst obtaining, the result that application XRD characterizes, as Fig. 2, can be found out from Fig. 2 result, when Ni/P=1/2, nickel chloride transforms generate product nickel phosphide completely.These results suggest that, under hydrogen atmosphere, be more conducive to the carrying out of building-up process.
Embodiment 3
Utilize method described in embodiment 1, under hydrogen atmosphere, prepare CoP/AC, the result that FeP/AC catalyst application XRD characterizes is as Fig. 3: as can be seen from the results, cobalt chloride and iron chloride all transform completely and generate product phosphide.Illustrate that the method is applicable to prepare the load type metal phosphide of different metal (group vib and/or VIII family) too.
Embodiment 4
Catalyst 1,3-butadiene is selected Hydrogenation Experiment: the nickel phosphide/active carbon (mol ratio of nickel phosphorus is 1: 3, and wherein nickel phosphide is 15wt%) of take is here example, the general 1,3-butadiene selective hydrogenation reaction experiment of describing the catalyst in the present invention.
0.05g catalyst mixes with 0.2g quartz sand that (quartz sand plays peptizaiton, itself is to catalytic process inertia) after be loaded on logical hydrogen in quartz reactor, at 400 ℃, carry out prereduction 2 hours, until temperature be down to after 30 ℃, pass into about 2% (v/v) 1,3-butadiene/nitrogen, flow velocity is 15ml/min., and flow is 15ml/min H
2, reaction pressure is normal pressure, adopts electric furnace to regulate reaction temperature, reaction end gas carries out full product analysis by gas-chromatography.
1,3-butadiene at low temperatures (300 ℃ of <) hydrogenation products comprises: half hydrogenation products 1-butylene, and suitable, Trans-2-butene, and full hydrogenation products butane.Hydrogenation process is as Fig. 4;
Embodiment 5
Catalyst is synthetic Ni under argon gas atmosphere
2p/AC (400 ℃ of prereduction), synthetic Ni under hydrogen atmosphere
2p/AC (400 ℃ of prereduction) experimental result is respectively in Table 1,2.Reaction condition is with embodiment 4.
Table 1 synthetic Ni under argon gas atmosphere
2p/AC (400 ℃ of prereduction) 1,3-butadiene is selected hydrogenation result
Table 2 synthetic Ni under hydrogen atmosphere
2p/AC (400 ℃ of prereduction) 1,3-butadiene is selected hydrogenation result
From Table 1 and Table 2, the Ni preparing under argon gas or hydrogen atmosphere
2p/AC catalyst, when 200 ℃ and 160 ℃, reaction conversion ratio approaches 100 ℃ respectively, and all keeps half very high hydrogenation selectivity.
Comparative example 1
Conventional method is prepared Ni
2p/AC, that is: under hydrogen atmosphere, temperature programmed reduction charcoal carries nickel phosphate, and its process is as follows:
0.684g nickel nitrate and cobalt nitrate are mixed to be dissolved in 2.5ml distilled water and stir, adding with the mol ratio of nickel is the phosphoric acid one hydrogen ammonia of metering in 1: 1 again, the precipitation obtaining is dissolved with a small amount of (1-2 drips) red fuming nitric acid (RFNA), the settled solution obtaining adds and in 1g active carbon, carries out incipient impregnation, then at 120 ℃, dry 12 hours, under 500 ℃ of nitrogen atmospheres, roasting is 4 hours, obtains presoma.
Again the presoma obtaining carried out to temperature programmed reduction from normal temperature to 580 ℃ and maintains 1 hour with the speed of 1 ℃/min in hydrogen atmosphere, being down to normal temperature; Then pass into mol ratio and be the N of 99: 1
2/ O
2carry out passivation 3 hours, obtain catalyst.
Compare with preparation method of the present invention, in the present invention, preparation method has the advantages such as preparation process is simple, reaction is efficient fast, low energy consumption.
Comparative example 2
Involved preferred catalysts in the present invention, synthetic Ni under hydrogen atmosphere
2p/AC, the Ni preparing with the method for traditional program heating reduction nickel phosphate
2p/AC compares, and experimental result is in Table 3,4, and reaction condition is with embodiment 4.
Table 3 synthetic Ni under hydrogen atmosphere
2p/AC (Ni/P=1/3) 1,3-butadiene is selected hydrogenation result
Ni prepared by the method for table 4 traditional program heating reduction nickel phosphate
2p/AC 1,3-butadiene is selected hydrogenation result
Experimental result can be found out in Table 3,4 result, involved preferred catalysts, synthetic Ni under hydrogen atmosphere
2ni prepared by the method for P/AC (Ni/P=1/3) and traditional program heating reduction nickel phosphate
2p/AC compares, quite active, 160 ℃ of left and right, substantially approaches 100% conversion.But the Ni preparing by method involved in the present invention
2p/AC catalyst, the Ni that its half hydrogenation selectivity will be prepared apparently higher than conventional method
2p/AC catalyst, has shown the superiority (be catalyst prepared by the present invention has shown in catalytic reaction good active and selective) of its catalytic performance.
Claims (9)
1. the preparation method of a loaded transitional metal phosphide catalyst, it is characterized in that: take red phosphorus as phosphorus source, one or more metallic elements of take in group vib and/or VIII family are metal component, take absorbing material as carrier, under microwave heating condition, prepare transition metal phosphide catalyst;
According to carrying metal active component 1.15 * 10 on every gram of carrier
-2-4.6 * 10
-5mol meter, is supported on the soluble-salt of metal active constituent on carrier by infusion process, then with red phosphorus mixed grinding, and P elements and intermetallic mol ratio>=1 in red phosphorus;
Under argon gas or hydrogen atmosphere, utilize heating using microwave 2-30min; Under last normal temperature, take mol ratio as 90-99: the N of 1-10
2/ O
2atmosphere passivation obtains finished product for 3-5 hour; In finished product, the mol ratio of metal and phosphorus is 3: 1-1: 2.
2. according to the preparation method of loaded transitional metal phosphide catalyst claimed in claim 1, it is characterized in that: the soluble-salt of described metal active constituent is chloride, nitrate or acetate, by equi-volume impregnating, supports on carrier.
3. according to preparation method claimed in claim 1, it is characterized in that: the carrier of described loaded catalyst is the material with carbon element with absorbing property.
4. according to preparation method claimed in claim 1, it is characterized in that: the carrier of described loaded catalyst is carborundum.
5. according to preparation method claimed in claim 3, it is characterized in that: described material with carbon element is one or more in active carbon, CNT, carbon fiber, carbon molecular sieve, mesoporous carbon.
6. according to preparation method claimed in claim 1, it is characterized in that: described metal component is one or more in Fe, Co, Ni, Mo, W metallic element.
7. according to preparation method claimed in claim 1, it is characterized in that: in metal and red phosphorus, the mol ratio of P elements is 1: 1-1: 5.
8. according to preparation method claimed in claim 7, it is characterized in that: in metal and red phosphorus, the mol ratio of P elements is 1: 2-1: 3.
9. according to preparation method claimed in claim 1, it is characterized in that: catalyst utilizes heating using microwave 4-10min, microwave power 10-900W under the atmosphere that flows.
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| CN103084192B (en) * | 2011-10-28 | 2015-05-27 | 中国科学院大连化学物理研究所 | Cobalt phosphide catalyst for preparing 3-pentanone and propanal from hydrogen, carbon monoxide and ethylene |
| WO2014040372A1 (en) | 2012-09-13 | 2014-03-20 | The Chinese University Of Hong Kong | Cop2 loaded red phosphorus, preparation and use of the same |
| CA2887657C (en) * | 2012-10-15 | 2020-08-11 | Stc.Unm | Non-pgm catalyst for orr based on pyrolyzed poly-complexes |
| US9012349B1 (en) | 2013-11-01 | 2015-04-21 | Ut-Battelle Llc | Method of synthesizing bulk transition metal carbide, nitride and phosphide catalysts |
| CN103657704A (en) * | 2013-11-15 | 2014-03-26 | 中国科学院过程工程研究所 | Catalyst for preparing tetrahydronaphthalene by naphthalene via selective hydrogenation as well as preparation method and application thereof |
| CN104056631B (en) * | 2014-06-10 | 2017-02-08 | 青岛东方循环能源有限公司 | Method for activating Ni/AC catalyst in microwave heating way |
| CN109772385B (en) * | 2019-02-25 | 2021-08-17 | 浙江工业大学 | Carbon self-supported metal phosphide catalyst and preparation method and application thereof |
| CN109821561A (en) * | 2019-03-22 | 2019-05-31 | 黑龙江大学 | A kind of preparation method of self-supporting phosphatization ferro-cobalt nanosphere elctro-catalyst |
| CN112909271A (en) * | 2021-01-25 | 2021-06-04 | 华南理工大学 | Integral transition metal phosphide electrocatalyst with sea urchin-shaped morphology and preparation method and application thereof |
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| US20030052011A1 (en) * | 2000-11-08 | 2003-03-20 | Zhuping Chen | Plasma electroplating |
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