CN101524648A - Loaded type catalyst for preparing elemental phosphorus and preparation method thereof - Google Patents
Loaded type catalyst for preparing elemental phosphorus and preparation method thereof Download PDFInfo
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- CN101524648A CN101524648A CN200910067758A CN200910067758A CN101524648A CN 101524648 A CN101524648 A CN 101524648A CN 200910067758 A CN200910067758 A CN 200910067758A CN 200910067758 A CN200910067758 A CN 200910067758A CN 101524648 A CN101524648 A CN 101524648A
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Abstract
The invention discloses a loaded type catalyst for catalyzing and decomposing phosphine to prepare elemental phosphorus, which takes a carbon nano tube as carrier and forms Co-P/CNTs amorphous alloy together with Co and P. A method for preparing the loaded type catalyst comprises: water-soluble cobalt salt, sodium citrate, sodium hypophosphite and ammonium sulphate are dissolved in de-ionized water and then added with the carbon nano tube which is purified and functionalized, and is steeped by the cobalt salt; the pH of the reaction liquid is adjusted to be about 9 by using ammonia water; under the condition of 80-90 DEG C, the reaction liquid is added with potassium borohydride for initiation and then fully stirred, so that black precipitate is produced in the reaction; after being separated, the precipitate is respectively washed by the de-ionized water and absolute ethyl alcohol, and then put into the absolute ethyl alcohol to be saved. The invention has the advantages that the carbon nano tube (CNTs) is adopted as the carrier to prepare the Co-P/CNTs amorphous alloy which is taken as catalyst for pyrolyzing the phosphine, decomposition temperature is low, and the catalytic activity and the thermal stability are good.
Description
Technical field
The present invention relates to catalyst and technology of preparing thereof, particularly a kind ofly be used to prepare elemental phosphorous loaded catalyst and preparation method thereof.
Background technology
High purity phosphorus is the prerequisite of meticulous phosphorous chemical industry, and the electron level phosphorus that exploitation has high added value has good economic worth and social benefit.To prepare high purity phosphorus be the most frequently used method to decomposing phosphine under catalytic condition, currently used catalyst, shortcomings such as ubiquity complex process, conversion ratio is low, energy consumption is high, poor stability.
Amorphous alloy enjoys catalysis worker's favor as a kind of new catalytic material, if amorphous alloy is prepared the carrier of the catalyst of high purity phosphorus as decomposing phosphine, it will be a kind of desirable selection, but amorphous alloy is in a kind of metastable condition, gathers easily and easy crystallization and its catalytic activity is reduced at high temperature.
Summary of the invention
The objective of the invention is at above-mentioned existing problems, provide a kind of high strength, high rigidity, acid and alkali-resistance, heat endurance height, specific surface big, to hydrogen have extremely strong absorption and desorption ability and energy consumption low be used for decomposing phosphine and preparing elemental phosphorous loaded catalyst.
Technical scheme of the present invention:
A kind of being used to prepares elemental phosphorous loaded catalyst, is carrier with the CNT, and with the CoP/CNTs amorphous alloy that Co, P constitute, the mass percent of its each component is that Co 41.3～37.5%, P 4.7～6.8%, CNTs are surplus.
The described preparation method who is used to prepare elemental phosphorous loaded catalyst comprises the steps:
1) carbon nanotube carrier is carried out the load of purifying preliminary treatment, surface-functionalized modification and tube wall surface trace amorphous state CoB;
2) solubility cobalt salt and natrium citricum are dissolved in the deionized water, add ammonium sulfate, sodium hypophosphite and above-mentioned CNT then;
3) be that pH is 8～10 with ammoniacal liquor conditioned reaction liquid under 80 ℃～90 ℃ water-baths in temperature, reaction generates black powder shape sediment;
4) sediment is separated the back and reach neutral with deionized water washing sediment to supernatant, place absolute ethyl alcohol to preserve with absolute ethanol washing and with sediment at last, this sediment is the Co-P/CNTs amorphous alloy.
Described carbon nanotube carrier is carried out the purifying preliminary treatment and is comprised: 1) CNT be impregnated in the NaOH and 0.018mol/L lauryl sodium sulfate mixed solution of 2mol/L, ultrasonic dispersion is after 60 minutes, in temperature is to add hot reflux under 100 ℃ 2 hours, wash to neutrality, 60 ℃ of oven dry down; 2) above-mentioned CNT be impregnated in again in red fuming nitric acid (RFNA) and the concentrated sulfuric acid mixed liquor, the concentration of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid is respectively 68% and 98%, and its volume ratio is 1: 1, and ultrasonic dispersion is after 60 minutes, in temperature is to add hot reflux under 120 ℃ 6 hours, and it is dry to neutral back to spend deionised water.
Described carbon nanotube carrier is carried out surface-functionalized being modified to: 1) the pretreated CNT of stating be impregnated in the ammoniacal liquor that weight percent concentration is 25%-28%, ultrasonic processing is after 15 minutes, in temperature is to add hot reflux under 100 ℃ 2 hours, spends deionised water then to neutral, dry; 2) above-mentioned CNT be impregnated in the citric acid solution of 0.25mol/L again, ultrasonic processing was to add hot reflux under 80 ℃ 2 hours in temperature after 20 minutes, and it is dry to neutral back to spend deionised water.
The load that described carbon nanotube carrier is carried out tube wall surface trace amorphous state CoB is: 1) CNT behind the functional modification is placed the 0.40mol/L cobalt salt solution, ultrasonic dispersion was flooded 5 hours after 20 minutes; 2) under electromagnetic agitation, add the solution of potassium borohydride of 0.30～0.50mL 0.50mol/L, make load trace amorphous state Co-B nucleus on the CNT, be convenient to the deposition of Co-P alloy.
Described solubility cobalt salt is cobaltous sulfate, cobalt chloride or cobalt nitrate, Co in the reactant liquor
2+The concentration of ion is 0.20～0.30mol/L.
The concentration of described natrium citricum in reactant liquor is 0.30～0.50mol/L.
The concentration of described ammonium sulfate in reactant liquor is 0.60～0.80mol/L.
The concentration of described sodium hypophosphite in reactant liquor is 1.20～3.50mol/L.
The weight percent concentration of described conditioned reaction liquid pH value and the used ammoniacal liquor of washing precipitate is 25%～28%.
Advantage of the present invention is: CNT (CNTs) has high intensity and hardness, anti-strong acid, highly basic, has good heat endurance, and it is little to have a caliber, major diameter when specific surface big, hydrogen is had characteristics such as extremely strong absorption and desorption ability, be desirable nanometer amorphous catalyst carrier, be that carrier can significantly improve activity of such catalysts and selectivity with it, CNT is the Co-P/CNTs amorphous alloy catalyst of preparing carriers, to PH
3Decomposition have good catalytic performance.Adopt the CoP/CNTs amorphous alloy as hydrogen phosphide thermal decomposition catalyst, can make the actual heat decomposition temperature of hydrogen phosphide low, conversion ratio is high and have good catalytic activity and heat endurance.
The specific embodiment
Embodiment 1
The cobaltous sulfate of 0.048mol and the natrium citricum of 0.070mol are dissolved in the deionized water, add the sodium hypophosphite of 0.384mol, the ammonium sulfate of 0.136mol and the CNTS that 1.0g handled then, with deionized water reactant liquor is diluted to 200mL again, in reactant liquor, Co
2+The concentration of ion, natrium citricum, sodium hypophosphite and ammonium sulfate is respectively 0.24mol/L, 0.35mol/L, 1.92mol/L and 0.68mol/L; Being 25% ammoniacal liquor with concentration reactant liquor pH is adjusted to about 9.0, is under 90 ℃ the condition in temperature, fully stirs, and generates the black powder sediment; Reach neutral with spending deionised water to supernatant after the sediment separation, place absolute ethyl alcohol to preserve with absolute ethanol washing 2 times and with sediment at last, this sediment is fresh Co-P/CNTS amorphous alloy.Show that after testing the mass percent of Co, P is Co in this product
38.9P
5.8/ CNTS, specific area is 76.43m
2/ g.
Embodiment 2
Change that the sodium hypophosphite addition is 0.240mol among the embodiment 1, the concentration in reactant liquor is 1.20mol/L, all the other steps and condition are with embodiment 1.Products therefrom shows after testing, and the mass percent of its Co, P is: Co
41.3P
4.7/ CNTS, specific area is 72.32m
2/ g.
Embodiment 3
Change that the sodium hypophosphite addition is 0.624mol among the embodiment 1, the concentration in reactant liquor is 3.12mol/L, all the other steps and condition are with embodiment 1.Products therefrom shows after testing, and the mass percent of its Co, P consists of: Co
37.5P
6.8/ CNTS, specific area is 79.52m
2/ g.
The catalyst that above-mentioned three embodiment are made carries out the phosphine and preparing elemental phosphorous reaction experiment of catalytic decomposition, employing U type quartz ampoule also heats up in heating furnace, technological parameter is: catalyst amount 0.10～0.15g, hydrogen phosphide flow 5mL/min, nitrogen flow 85mL/min, 340 ℃～520 ℃ of reaction temperatures, reaction time 60min, experimental result sees Table 1, table 2.
Table 1: the phosphine decomposes rate (%) of heterogeneity catalyst
Experimental result shows: adopt the Co-P/CNTs amorphous alloy as hydrogen phosphide thermal decomposition catalyst, decomposition temperature is low, conversion ratio is high and have good catalytic activity and heat endurance, and is respond well.
Claims (10)
1. one kind is used to prepare elemental phosphorous loaded catalyst, it is characterized in that: be carrier with the CNT, with the CoP/CNTs amorphous alloy that Co, P constitute, the mass percent of its each component is that Co 41.3～37.5%, P 4.7～6.8%, CNTs are surplus.
2. the preparation method who is used to prepare elemental phosphorous loaded catalyst according to claim 1 is characterized in that comprising the steps:
1) carbon nanotube carrier is carried out the load of purifying preliminary treatment, surface-functionalized modification and tube wall surface trace amorphous state CoB;
2) solubility cobalt salt and natrium citricum are dissolved in the deionized water, add ammonium sulfate, sodium hypophosphite and above-mentioned CNT then;
3) be that pH is 8～10 with ammoniacal liquor conditioned reaction liquid under 80 ℃～90 ℃ water-baths in temperature, reaction generates black powder shape sediment;
4) sediment is separated the back and reach neutral with deionized water washing sediment to supernatant, place absolute ethyl alcohol to preserve with absolute ethanol washing and with sediment at last, this sediment is the Co-P/CNTs amorphous alloy.
3. the preparation method who is used to prepare elemental phosphorous loaded catalyst according to claim 2, it is characterized in that: described carbon nanotube carrier is carried out the purifying preliminary treatment and is comprised: 1) CNT be impregnated in the NaOH and 0.018mol/L lauryl sodium sulfate mixed solution of 2mol/L, ultrasonic dispersion is after 60 minutes, in temperature is to add hot reflux under 100 ℃ 2 hours, wash to neutrality, 60 ℃ of oven dry down; 2) above-mentioned CNT be impregnated in again in red fuming nitric acid (RFNA) and the concentrated sulfuric acid mixed liquor, the concentration of the red fuming nitric acid (RFNA) and the concentrated sulfuric acid is respectively 68% and 98%, and its volume ratio is 1: 1, and ultrasonic dispersion is after 60 minutes, in temperature is to add hot reflux under 120 ℃ 6 hours, and it is dry to neutral back to spend deionised water.
4. the preparation method who is used to prepare elemental phosphorous loaded catalyst according to claim 2, it is characterized in that: described carbon nanotube carrier is carried out surface-functionalized being modified to: 1) the pretreated CNT of stating be impregnated in the ammoniacal liquor that weight percent concentration is 25%-28%, ultrasonic processing is after 15 minutes, in temperature is to add hot reflux under 100 ℃ 2 hours, spends deionised water then to neutral, dry; 2) above-mentioned CNT be impregnated in the citric acid solution of 0.25mol/L again, ultrasonic processing was to add hot reflux under 80 ℃ 2 hours in temperature after 20 minutes, and it is dry to neutral back to spend deionised water.
5. the preparation method who is used to prepare elemental phosphorous loaded catalyst according to claim 2, it is characterized in that: the load that described carbon nanotube carrier is carried out tube wall surface trace amorphous state CoB is: 1) CNT behind the functional modification is placed the 0.40mol/L cobalt salt solution, ultrasonic dispersion was flooded 5 hours after 20 minutes; 2) under electromagnetic agitation, add the solution of potassium borohydride of 0.30～0.50mL 0.50mol/L, make load trace amorphous state Co-B nucleus on the CNT, be convenient to the deposition of Co-P alloy.
6. the preparation method who is used to prepare elemental phosphorous loaded catalyst according to claim 2 is characterized in that: described solubility cobalt salt is cobaltous sulfate, cobalt chloride or cobalt nitrate, Co in the reactant liquor
2+The concentration of ion is 0.20～0.30mol/L.
7. the preparation method who is used to prepare elemental phosphorous loaded catalyst according to claim 2 is characterized in that: the concentration of described natrium citricum in reactant liquor is 0.30～0.50mol/L.
8. the preparation method who is used to prepare elemental phosphorous loaded catalyst according to claim 2 is characterized in that: the concentration of described ammonium sulfate in reactant liquor is 0.60～0.80mol/L.
9. the preparation method who is used to prepare elemental phosphorous loaded catalyst according to claim 2 is characterized in that: the concentration of described sodium hypophosphite in reactant liquor is 120～3.50mol/L.
10. the preparation method who is used to prepare elemental phosphorous loaded catalyst according to claim 2 is characterized in that: the weight percent concentration of described conditioned reaction liquid pH value and the used ammoniacal liquor of washing precipitate is 25%～28%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102935371A (en) * | 2012-11-16 | 2013-02-20 | 南开大学 | Catalyst for preparing yellow phosphorus through catalytic decomposition of phosphine gas and preparation method thereof |
| CN110302787A (en) * | 2018-03-20 | 2019-10-08 | 南开大学 | The New Nickel plating spinel catalyst and preparation method thereof decomposed for hydrogen phosphide |
| CN110975899A (en) * | 2019-11-15 | 2020-04-10 | 北京科技大学 | Preparation method of cobalt phosphide nanosheet composite material with carbon particle intercalation |
-
2009
- 2009-01-21 CN CN200910067758A patent/CN101524648A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102935371A (en) * | 2012-11-16 | 2013-02-20 | 南开大学 | Catalyst for preparing yellow phosphorus through catalytic decomposition of phosphine gas and preparation method thereof |
| CN110302787A (en) * | 2018-03-20 | 2019-10-08 | 南开大学 | The New Nickel plating spinel catalyst and preparation method thereof decomposed for hydrogen phosphide |
| CN110302787B (en) * | 2018-03-20 | 2022-09-27 | 南开大学 | Nickel plating spinel catalyst for phosphine decomposition and preparation method thereof |
| CN110975899A (en) * | 2019-11-15 | 2020-04-10 | 北京科技大学 | Preparation method of cobalt phosphide nanosheet composite material with carbon particle intercalation |
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Open date: 20090909 |