CN105214684B - The preparation method of the hydrogen-supplemented fuel desulphurization catalyst of bar-shaped recessed soil matrix synergistic sorption - Google Patents
The preparation method of the hydrogen-supplemented fuel desulphurization catalyst of bar-shaped recessed soil matrix synergistic sorption Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of the hydrogen-supplemented fuel desulphurization catalyst of bar-shaped recessed soil matrix synergistic sorption, the method with bar-shaped attapulgite as carrier, respectively by soaking absorption, reduction activation and Ni-P carried metal nickel, palladium and ruthenium（Or cerium or europium or neodymium）, obtain MFP base composite catalysts.Catalyst prepared by the inventive method is using MFP excellent absorption property fast selective absorption and enrichment sulfurous organic compound, adsorbent surface is cleaned by the mutual concerted catalysis hydrodesulfurization of the various metals for loading again, lasting efficient absorption is ensured, hydrogen is not consumed excessively while catalytic desulfurhydrogenation effect is effectively played, processing cost is reduced, a new field has been started in the also development and application to recessed soil.
Description
Technical field
The invention belongs to chemical plating and technical field of material, concretely relate to a kind of bar-shaped recessed soil matrix collaboration and inhale
The preparation method of attached hydrogen-supplemented fuel desulphurization catalyst.
Background technology
Conventional fuel oil desulfurization mainly uses hydrodesulfurization (HDS), and HDS generally uses metal or sulphur（Nitrogen）Changing metal is
Catalyst, can thoroughly remove sulfurous organic compound, eliminate secondary pollution.In addition, multiple fuel desulfurization is there have been developed at present
Technique, including absorption, extraction, biological and oxidation sweetening etc..Wherein, absorption desulfurization is because operating condition is gentle, energy consumption is low, desulfurization
Speed is fast, do not change the advantages of fuel qualities and ultralow desulfurization and gain great popularity.Fuel desulfuration adsorbent is main with inorganic material
Based on material, including metal oxygen (sulphur, halogen) compound, zeolite molecular sieve, mesopore silicon oxide, activated carbon, mesoporous carbon, black alkene etc..
Concave-convex clay rod（Hereinafter referred to as recessed soil）It is also a kind of the aqueous of layer chain structure with good adsorption properties
Rich zeopan clay mineral.The microstructure feature of recessed native powder has been recognized, it be by length be 0.1~1 μ
The m orders of magnitude, width（Diameter）Constituted for the rod of the 15-20nm orders of magnitude is brilliant；But the place of production its microstructure of difference also has certain
Difference, is mainly manifested in the brilliant draw ratio aspect of rod different.
Under normal conditions, recessed soil is but difficult with scattered independent rhabdolith state presence as a kind of powder body material,
But the crystal aggregates of formation certain forms, these rod crystalline substance beam referred to as crystalline substance beams assembled by rod crystalline substance close parallel.Therefore
In actual applications, it is necessary to purification is carried out to attapulgite with rod crystalline substance cleavage treatment.
The content of the invention
It is an object of the invention to：A kind of preparation of the hydrogen-supplemented fuel desulphurization catalyst of bar-shaped recessed soil matrix synergistic sorption is provided
Method, the bar-shaped recessed soil matrix composite catalyst obtained using the method not only increases the economic value added of recessed soil, also provides
A kind of new way of fuel desulfuration.
Technical solution of the invention is：With bar-shaped recessed soil（Hereinafter referred to as MFP）It is carrier, by soaking absorption, going back
Original activation, Ni-P obtain MFP base composite catalysts；Its preparation method comprises the following steps：First, recessed native original soil is adopted
Acidification is carried out with hydrochloric acid solution and obtains bar-shaped attapulgite MFP；Then, bar-shaped attapulgite MFP uses different oxidation solutions
Immersion absorption is carried out, and activation process is carried out with corresponding reducing solution；Finally, will repeatedly soak at absorption and repeatedly reduction activation
MFP after reason carries out Ni-P again, obtains MFP base composite catalysts.
Wherein, the preparation method of the MFP base composite catalysts includes step in detail below：
（1）Acidifying purification：By recessed native original soil with mass volume ratio 1:60 are added to immersion, machine in the hydrochloric acid of mass concentration 5~30%
Tool stirs 6h, and centrifugation, deionized water cleaning obtains bar-shaped attapulgite MFP；
（2）Once immersion absorption and reduction activation：By bar-shaped attapulgite MFP with mass volume ratio 1:80 are added to quality
Concentration be 0.30% palladium chloride solution in soak absorption, room temperature, mechanical agitation 3h, centrifugation, deionized water cleaning；Then
With mass volume ratio 1:100 are added to reduction activation in the stannous chloride solution of 30g/L, room temperature, mechanical agitation 3h, centrifugation,
Deionized water is cleaned；
（3）Secondary immersion absorption and reduction activation：Will be by step（2）MFP after single treatment is with mass volume ratio 1:
Absorption, room temperature, mechanical agitation 2h, centrifugation, deionized water cleaning are soaked in 80 nickel chloride solutions for adding 40g/L；Then
With mass volume ratio 1:100 are added to reduction activation in the sodium borohydride solution of 20g/L, room temperature, mechanical agitation 2h, centrifugation,
Deionized water is cleaned；
(4) repeatedly immersion absorption and reduction activation：Circulating repeat step（2）, step（3）Each 2 times；
（5）Ni-P：Will be by step（4）Repeatedly the MFP of immersion absorption and reduction activation treatment is with quality volume
Than 1:500 are added in chemically composited plating liquor, the mechanical agitation 60min in 40~70.0 DEG C of water-baths, after plating terminates, centrifugation
Separate, deionized water cleaning, MFP base composite catalysts are obtained after 90 DEG C of vacuum drying 1h（Ni-M-Pd / MFP）；Wherein change
Learn composite plating bath formula be：The g/L of nickel chloride 10.0~50, hydrazine hydrate 15~60.0 ml/L, 10~40g/ of sodium citrate
L, HEDP (1- hydroxyls-ethylidene -1,1- di 2 ethylhexyl phosphonic acids) 20~60 ml/L, SPS（Sodium polydithio-dipropyl sulfonate）0.1~1mg/
L, MCl3 2.0~10 g/L, M are the one kind in Ru, Ce, Eu, Nd, pH 8.0~11.0, remaining water.
The present invention has advantages below：
1st, bar-shaped attapulgite MFP is respectively by repeatedly immersion absorption, reduction activation and chemically composited plating back loading
Metallic nickel, palladium and ruthenium（Or cerium or europium or neodymium）, they are mutually cooperateed with, and effectively play the effect of catalytic desulfurhydrogenation.
2nd, bar-shaped attapulgite MFP excellent adsorptivity fast selective absorption and enrichment sulfurous organic compound, then by negative
The various metals concerted catalysis hydrodesulfurization cleaning adsorbent surface of load, has ensured lasting efficient absorption, in ultra-deep desulfurization
Hydrogen is not consumed excessively simultaneously, processing cost is reduced, while also a new field has been started in the development and application to recessed soil.
Brief description of the drawings
Fig. 1 is the electromicroscopic photograph partial enlarged drawing of MFP bases composite catalyst Ni-Ru-Pd/ MFP of the invention.
Fig. 2 is the electromicroscopic photograph partial enlarged drawing of MFP bases composite catalyst Ni-Nd-Pd/ MFP of the invention.
Specific embodiment
Further illustrate technical solution of the invention with reference to embodiment, these specific embodiments it is not intended that
It is the limitation to technical scheme.
Embodiment 1：MFP base composite catalysts are prepared according to following steps
（1）The recessed native original soils of 10g are added in the hydrochloric acid of 600ml mass concentrations 20% and are soaked, mechanical agitation 6h, centrifugation,
Deionized water is cleaned, and obtains bar-shaped attapulgite MFP；
（2）Take step（1）The bar-shaped attapulgite MFP of gained is added to the palladium chloride solution of 800ml mass concentrations 0.30%
Middle immersion absorption, room temperature mechanical stirring 3h, centrifugation is then added to the dichloro of 30 g of 1000ml/L after deionized water cleaning
Change reduction activation in solution of tin, room temperature mechanical stirring 3h, centrifugation, deionized water cleaning；
（3）Take step（2）Gained MFP soaks absorption, room temperature mechanical in being added to the nickel chloride solution of 800ml 40g/L
Stirring 2h, centrifugation is then added to reduction activation in the sodium borohydride solution of 20 g of 1000ml/L after deionized water cleaning,
Room temperature mechanical stirs 2h, centrifugation, deionized water cleaning；
（4）Circulating repeat step（2）, step（3）Each 2 times；
（5）Take step（4）Gained MFP is added in the chemically composited plating liquors of 5000ml, and machinery is stirred in 40.0 DEG C of water-baths
60min is mixed, plating terminates rear centrifugation, and deionized water cleaning obtains MFP base composite catalysts after 90 DEG C of vacuum drying 1h
（Ni-Ru-Pd / MFP）；The formula of wherein 1L chemical composite plating baths is：The g of nickel chloride 30, the ml of hydrazine hydrate 60.0, citric acid
Sodium 30g, HEDP 20ml, SPS 0.1mg, RuCl3 5g, pH 8.0, remaining water.
Embodiment 2：MFP base composite catalysts are prepared according to following steps
（1）The recessed native original soils of 5g are added in the hydrochloric acid of 300ml mass concentrations 30% and are soaked, mechanical agitation 6h, centrifugation is gone
Ionized water is cleaned, and obtains bar-shaped attapulgite MFP；
（2）Take step（1）The bar-shaped attapulgite MFP of gained is added to the palladium chloride solution of 400ml mass concentrations 0.30%
Middle immersion absorption, room temperature mechanical stirring 3h, centrifugation is then added to the dichloro of 30 g of 500ml/L after deionized water cleaning
Change reduction activation in solution of tin, room temperature mechanical stirring 3h, centrifugation, deionized water cleaning；
（3）Take step（2）Gained MFP soaks absorption, room temperature mechanical in being added to the nickel chloride solution of 400ml 40g/L
Stirring 2h, centrifugation is then added to reduction activation in the sodium borohydride solution of 20 g of 500ml/L after deionized water cleaning,
Room temperature mechanical stirs 2h, centrifugation, deionized water cleaning；
（4）Circulating repeat step（2）, step（3）Each 2 times；
（5）Take step（4）Gained MFP is added in the chemically composited plating liquors of 2500ml, and machinery is stirred in 70.0 DEG C of water-baths
60min is mixed, plating terminates rear centrifugation, and deionized water cleaning obtains MFP base composite catalysts after 90 DEG C of vacuum drying 1h
（Ni-Ce-Pd / MFP）；The formula of wherein 1L chemical composite plating baths is：The g of nickel chloride 50, the ml of hydrazine hydrate 15.0, citric acid
Sodium 25g, HEDP 60ml, SPS 0.7mg, CeCl3 2 g, pH 10.5, remaining water.
Embodiment 3：MFP base composite catalysts are prepared according to following steps
（1）The recessed native original soils of 1g are added in the hydrochloric acid of 60ml mass concentrations 5% and are soaked, mechanical agitation 6h, centrifugation, go from
Sub- water cleaning, obtains bar-shaped attapulgite MFP；
（2）Take step（1）The bar-shaped attapulgite MFP of gained is added in the palladium chloride solution of 80ml mass concentrations 0.30%
Immersion absorption, room temperature mechanical stirring 3h, centrifugation is then added to the dichloride of 30 g of 100ml/L after deionized water cleaning
Reduction activation in solution of tin, room temperature mechanical stirring 3h, centrifugation, deionized water cleaning；
（3）Take step（2）Gained MFP soaks absorption in being added to the nickel chloride solution of 80ml 40g/L, and room temperature mechanical is stirred
2h is mixed, centrifugation is then added to reduction activation in the sodium borohydride solution of 20 g of 100ml/L, room after deionized water cleaning
Warm mechanical agitation 2h, centrifugation, deionized water cleaning；
（4）Circulating repeat step（2）, step（3）Each 2 times；
（5）Take step（4）Gained MFP is added in the chemically composited plating liquors of 500ml, the mechanical agitation in 60.0 DEG C of water-baths
60min, plating terminates rear centrifugation, and deionized water cleaning obtains MFP base composite catalysts after 90 DEG C of vacuum drying 1h
（Ni-Ru-Pd / MFP）；The formula of wherein 1L chemical composite plating baths is：The g of nickel chloride 10, the ml of hydrazine hydrate 40, sodium citrate
10g, HEDP 60ml, SPS 1mg, RuCl3 2 g, pH 9.0, remaining water.
Embodiment 4：MFP base composite catalysts are prepared according to following steps
（1）The recessed native original soils of 10g are added in the hydrochloric acid of 300ml mass concentrations 20% and are soaked, mechanical agitation 6h, centrifugation,
Deionized water is cleaned, and obtains bar-shaped attapulgite MFP；
（2）Take step（1）The bar-shaped attapulgite MFP of gained is added to the palladium chloride solution of 800ml mass concentrations 0.30%
Middle immersion absorption, room temperature mechanical stirring 3h, centrifugation is then added to the dichloro of 30 g of 1000ml/L after deionized water cleaning
Change reduction activation in solution of tin, room temperature mechanical stirring 3h, centrifugation, deionized water cleaning；
（3）Take step（2）Gained MFP soaks absorption, room temperature mechanical in being added to the nickel chloride solution of 800ml 40g/L
Stirring 2h, centrifugation is then added to reduction activation in the sodium borohydride solution of 20 g of 1000ml/L after deionized water cleaning,
Room temperature mechanical stirs 2h, centrifugation, deionized water cleaning；
（4）Circulating repeat step（2）, step（3）Each 2 times；
（5）Take step（4）Gained MFP is added in the chemically composited plating liquors of 5000ml, and machinery is stirred in 55.0 DEG C of water-baths
60min is mixed, plating terminates rear centrifugation, and deionized water cleaning obtains MFP base composite catalysts after 90 DEG C of vacuum drying 1h
（Ni-Ce-Pd / MFP）；The formula of wherein 1L chemical composite plating baths is：The g of nickel chloride 40, the ml of hydrazine hydrate 35, sodium citrate
10 g, HEDP 35ml, SPS 0.3mg, CeCl3 8 g, pH 8.0, remaining water.
Embodiment 5：MFP base composite catalysts are prepared according to following steps
（1）The recessed native original soils of 10g are added in the hydrochloric acid of 600ml mass concentrations 15% and are soaked, mechanical agitation 6h, centrifugation,
Deionized water is cleaned, and obtains bar-shaped attapulgite MFP；
（2）Take step（1）The bar-shaped attapulgite MFP of gained is added to the palladium chloride solution of 800ml mass concentrations 0.30%
Middle immersion absorption, room temperature mechanical stirring 3h, centrifugation is then added to the dichloro of 30 g of 1000ml/L after deionized water cleaning
Change reduction activation in solution of tin, room temperature mechanical stirring 3h, centrifugation, deionized water cleaning；
（3）Take step（2）Gained MFP soaks absorption, room temperature mechanical in being added to the nickel chloride solution of 800ml 40g/L
Stirring 2h, centrifugation is then added to reduction activation in the sodium borohydride solution of 20 g of 1000ml/L after deionized water cleaning,
Room temperature mechanical stirs 2h, centrifugation, deionized water cleaning；
（4）Circulating repeat step（2）, step（3）Each 2 times；
（5）Take step（4）Gained MFP is added in the chemically composited plating liquors of 5000ml, the mechanical agitation in 70 DEG C of water-baths
60min, plating terminates rear centrifugation, and deionized water cleaning obtains MFP base composite catalysts after 90 DEG C of vacuum drying 1h
（Ni-Ru-Pd / MFP）；The formula of wherein 1L chemical composite plating baths is：The g of nickel chloride 50, the ml of hydrazine hydrate 15, sodium citrate
40g, HEDP 40ml, SPS 0.5mg, RuCl3 4 g, pH10.0, remaining water.
Embodiment 6：MFP base composite catalysts are prepared according to following steps
（1）The recessed native original soils of 5g are added in the hydrochloric acid of 300ml mass concentrations 10% and are soaked, mechanical agitation 6h, centrifugation is gone
Ionized water is cleaned, and obtains bar-shaped attapulgite MFP；
（2）Take step（1）The bar-shaped attapulgite MFP of gained is added to the palladium chloride solution of 400ml mass concentrations 0.30%
Middle immersion absorption, room temperature mechanical stirring 3h, centrifugation is then added to the dichloro of 30 g of 500ml/L after deionized water cleaning
Change reduction activation in solution of tin, room temperature mechanical stirring 3h, centrifugation, deionized water cleaning；
（3）Take step（2）Gained MFP soaks absorption, room temperature mechanical in being added to the nickel chloride solution of 400ml 40g/L
Stirring 2h, centrifugation is then added to reduction activation in the sodium borohydride solution of 20 g of 500ml/L after deionized water cleaning,
Room temperature mechanical stirs 2h, centrifugation, deionized water cleaning；
（4）Circulating repeat step（2）, step（3）Each 2 times；
（5）Take step（4）Gained MFP is added in the chemically composited plating liquors of 2500ml, the mechanical agitation in 40 DEG C of water-baths
60min, plating terminates rear centrifugation, and deionized water cleaning obtains MFP base composite catalysts after 90 DEG C of vacuum drying 1h
（Ni-Ce-Pd / MFP）；The formula of wherein 1L chemical composite plating baths is：Nickel chloride 20g, the ml of hydrazine hydrate 30, sodium citrate
15g, HEDP 20ml, SPS 1mg, CeCl310 g, pH 11.0, remaining water.
Embodiment 7：MFP base composite catalysts are prepared according to following steps
（1）The recessed native original soils of 10g are added in the hydrochloric acid of 600ml mass concentrations 30% and are soaked, mechanical agitation 6h, centrifugation,
Deionized water is cleaned, and obtains bar-shaped attapulgite MFP；
（2）Take step（1）The bar-shaped attapulgite MFP of gained is added to the palladium chloride solution of 800ml mass concentrations 0.30%
Middle immersion absorption, room temperature mechanical stirring 3h, centrifugation is then added to the dichloro of 30 g of 1000ml/L after deionized water cleaning
Change reduction activation in solution of tin, room temperature mechanical stirring 3h, centrifugation, deionized water cleaning；
（3）Take step（2）Gained MFP soaks absorption, room temperature mechanical in being added to the nickel chloride solution of 800ml 40g/L
Stirring 2h, centrifugation is then added to reduction activation in the sodium borohydride solution of 20 g of 1000ml/L after deionized water cleaning,
Room temperature mechanical stirs 2h, centrifugation, deionized water cleaning；
（4）Circulating repeat step（2）, step（3）Each 2 times；
（5）Take step（4）Gained MFP is added in the chemically composited plating liquors of 5000ml, the mechanical agitation in 50 DEG C of water-baths
60min, plating terminates rear centrifugation, and deionized water cleaning obtains MFP base composite catalysts after 90 DEG C of vacuum drying 1h
（Ni-Ru-Pd / MFP）；The formula of wherein 1L chemical composite plating baths is：The g of nickel chloride 20, the ml of hydrazine hydrate 25, sodium citrate
20g, HEDP 30ml, SPS 0.8mg, RuCl310 g, pH 11.0, remaining water.
Embodiment 8：MFP base composite catalysts are prepared according to following steps
（1）The recessed native original soils of 2g are added in the hydrochloric acid of 120ml mass concentrations 5% and are soaked, mechanical agitation 6h, centrifugation is gone
Ionized water is cleaned, and obtains bar-shaped attapulgite MFP；
（2）Take step（1）The bar-shaped attapulgite MFP of gained is added to the palladium chloride solution of 160ml mass concentrations 0.30%
Middle immersion absorption, room temperature mechanical stirring 3h, centrifugation is then added to the dichloro of 30 g of 200ml/L after deionized water cleaning
Change reduction activation in solution of tin, room temperature mechanical stirring 3h, centrifugation, deionized water cleaning；
（3）Take step（2）Gained MFP soaks absorption, room temperature mechanical in being added to the nickel chloride solution of 160ml 40g/L
Stirring 2h, centrifugation is then added to reduction activation in the sodium borohydride solution of 20 g of 200ml/L after deionized water cleaning,
Room temperature mechanical stirs 2h, centrifugation, deionized water cleaning；
（4）Circulating repeat step（2）, step（3）Each 2 times；
（5）Take step（4）Gained MFP is added in the chemically composited plating liquors of 1000ml, the mechanical agitation in 65 DEG C of water-baths
60min, plating terminates rear centrifugation, and deionized water cleaning obtains MFP base composite catalysts after 90 DEG C of vacuum drying 1h
（Ni-Ce-Pd / MFP）；The formula of wherein 1L chemical composite plating baths is：The g of nickel chloride 10, the ml of hydrazine hydrate 60, sodium citrate
40g, HEDP 45ml, SPS 0.1mg, CeCl3 5 g, pH 9.5, remaining water.
Embodiment 9-12：MFP base composite catalysts are prepared according to following steps：Step（1）-（5）Respectively with embodiment 1,
In example 3, example 5, example 7（1）-（5）, wherein step（5）Middle RuCl3It is changed to EuCl3, finally obtain MFP base composite catalysts（Ni-
Eu-Pd / MFP）.
Embodiment 13-16：MFP base composite catalysts are prepared according to following steps：Step（1）-（5）Respectively with embodiment 2,
In example 4, example 6, example 8（1）-（5）, wherein step（5）Middle CeCl3It is changed to NbCl3, finally obtain MFP base composite catalysts（Ni-
Nb-Pd / MFP）.
The hydrogen-supplemented fuel desulphurization catalyst of the bar-shaped recessed soil matrix synergistic sorption obtained by above-described embodiment is applied to simulation combustion
In oily desulfurization, the desulphurizing ability of catalyst is investigated；Concretely comprise the following steps：Sequentially added in the autoclave of 200mL a certain amount of
Catalyst, 50 mL simulation fuel oil（Containing a certain amount of dibenzothiophenes), lead to H2 To replace the air in kettle, finally lead to for 4~5 times
H2Until required pressure；Autoclave is slowly heated, until required reaction temperature；Pressure in heating process mesohigh kettle by
Gradually rise, reach turn on agitator after balance, now hydrogenation reaction starts；To eliminate shadow of the diffusion effect to kinetics
Ring, it is 1200 more than rpm to control mixing speed；After reaction certain hour, upper oil phase is taken out, carry out the analysis of sulfur content；It is several
Plant the desulfurization results such as following table of different embodiments gained catalyst：
Claims (1)
1. the preparation method of the hydrogen-supplemented fuel desulphurization catalyst of bar-shaped recessed soil matrix synergistic sorption, it is characterised in that the preparation method
It is：With bar-shaped recessed soil as carrier, MFP base composite catalysts are obtained by immersion absorption, reduction activation, Ni-P；Its
Preparation method comprises the following steps：First, recessed native original soil carries out acidification and obtains bar-shaped attapulgite using hydrochloric acid solution
MFP；Then, bar-shaped attapulgite MFP carries out immersion absorption using different oxidation solutions, and is carried out at activation with corresponding reducing solution
Reason；Finally, the MFP after repeatedly immersion absorption and multiple reduction activation treatment is carried out into Ni-P again, obtains MFP bases compound
Catalyst；The preparation method of the MFP base composite catalysts includes step in detail below：
（1）Acidifying purification：By recessed native original soil with mass volume ratio 1:60 are added to immersion in the hydrochloric acid of mass concentration 5~30%, and machinery is stirred
6h is mixed, centrifugation, deionized water cleaning obtains bar-shaped attapulgite MFP；
（2）Once immersion absorption and reduction activation：By bar-shaped attapulgite MFP with mass volume ratio 1:80 are added to mass concentration
To soak absorption, room temperature, mechanical agitation 3h, centrifugation, deionized water cleaning in 0.30% palladium chloride solution；Then with matter
Amount volume ratio 1:100 are added to reduction activation in the stannous chloride solution of 30g/L, room temperature, mechanical agitation 3h, centrifugation, go from
Sub- water cleaning；
（3）Secondary immersion absorption and reduction activation：Will be by step（2）MFP after single treatment is with mass volume ratio 1:80 add
Enter immersion absorption in the nickel chloride solution of 40g/L, room temperature, mechanical agitation 2h, centrifugation, deionized water cleaning；Then with matter
Amount volume ratio 1:100 are added to reduction activation in the sodium borohydride solution of 20g/L, room temperature, mechanical agitation 2h, centrifugation, go from
Sub- water cleaning；
(4) repeatedly immersion absorption and reduction activation：Circulating repeat step（2）, step（3）Each 2 times；
（5）Ni-P：Will be by step（4）Repeatedly the MFP of immersion absorption and reduction activation treatment is with mass volume ratio 1:
500 are added in chemically composited plating liquor, the mechanical agitation 60min in 40~70.0 DEG C of water-baths, after plating terminates, centrifugation point
From deionized water cleaning obtains MFP base composite catalysts after 90 DEG C of vacuum drying 1h（Ni-M-Pd / MFP）；It is wherein chemical
The formula of composite plating bath is：The g/L of nickel chloride 10.0~50, hydrazine hydrate 15~60.0 ml/L, 10~40g/L of sodium citrate,
1- hydroxyls-ethylidene -1,20~60ml of 1- di 2 ethylhexyl phosphonic acids/L, sodium polydithio-dipropyl sulfonate 0.1~1mg/L, MCl3 2.0~10
G/L, M are the one kind in Ru, Ce, Eu, Nd, pH 8.0~11.0, remaining water.
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| CN115254082B (en) * | 2021-04-29 | 2024-03-26 | 中国石油化工股份有限公司 | Catalyst carrier, preparation method thereof, catalyst, preparation method thereof and application of catalyst |
| CN114749174B (en) * | 2022-04-26 | 2023-11-07 | 淮安中顺环保科技有限公司 | Preparation method of attapulgite domain-limited noble metal nanocluster catalyst |
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