CN103223348A - Preparation method for alpha-alumina supported nickel phosphide catalyst - Google Patents
Preparation method for alpha-alumina supported nickel phosphide catalyst Download PDFInfo
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- CN103223348A CN103223348A CN2013101353400A CN201310135340A CN103223348A CN 103223348 A CN103223348 A CN 103223348A CN 2013101353400 A CN2013101353400 A CN 2013101353400A CN 201310135340 A CN201310135340 A CN 201310135340A CN 103223348 A CN103223348 A CN 103223348A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 30
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 101
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- 230000009467 reduction Effects 0.000 claims abstract description 27
- 238000005470 impregnation Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000002803 maceration Methods 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 101150003085 Pdcl gene Proteins 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 27
- 238000006722 reduction reaction Methods 0.000 abstract description 26
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 3
- 229910052763 palladium Inorganic materials 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000001603 reducing effect Effects 0.000 abstract description 2
- 238000011946 reduction process Methods 0.000 abstract description 2
- 239000002351 wastewater Substances 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 229910052594 sapphire Inorganic materials 0.000 abstract 1
- 239000002912 waste gas Substances 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
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Abstract
The invention provides a preparation method for an alpha-alumina supported nickel phosphide catalyst. The preparation method comprises the following steps of preparing an impregnation liquid, equivalent-volume impregnating, drying, calcining, carrying out the procedures again and reducing. The preparation method is improved based on a temperature-programmed reduction method. Nickel and phosphor precursors are transferred into nickel phosphide under the catalytic reduction action of a trace amount of Pd or Ru (less than or equal to 0.1 wt.%) by using the alpha-Al2O3 as a carrier. A core of the preparation method lies in that a reduction temperature is reduced to below a 500 DEG C by using catalytic action of Pd or Ru in the temperature-programmed reduction process, thereby effectively preventing the disadvantages brought by high temperature reduction. The preparation method has good practicability and usage effects without forming three wastes (waste gas, waste water and waste residues), and is safe and environment-friendly.
Description
Technical field
The present invention relates to a kind of preparation of catalysis material, be specifically related to a kind of preparation method of catalyst of phosphatizing nickel.
Background technology
In recent years, the researcher finds the nickel phosphide excellent performance, can be applied to deep hydrodesulfurizationof, denitrogenation, dehalogenation and take off the aromatic hydrocarbons field, is a kind of novel high-activity hydrogenation catalyst material.The key of new catalytic material commercial Application is feasible industrial preparation process.This comprises feasibility, engineering economy and the environmental protection of engineering.
At present, the preparation method commonly used of catalyst of phosphatizing nickel comprises solvent-thermal method, temperature-programmed reduction method and hypophosphites decomposition method:
1, solvent-thermal method
Solvent-thermal method is a kind of common method of prepared in laboratory Ni2P crystal grain.It is in enclosed system such as autoclave, is solvent with organic matter or non-water-soluble matchmaker, under certain temperature and the self-generated pressure in the solution, and a kind of synthetic method that original stock reacts.Can obtain the nanometer Ni2P crystal (branch type, hollow sphere and tubulose etc.) of some special appearances by this method, have good hydrogenation catalyst performance, but can generate a large amount of waste liquids in the preparation process, very important environmental issue occur.
2, temperature-programmed reduction method
The most simple and practical method in laboratory is a temperature-programmed reduction method, and it is that phosphoric acid (two) hydrogen ammonium with high valence state is the phosphorus source, and nickel salt is the nickel source, and temperature programmed reduction is prepared nickel phosphide in hydrogen.When adopting this method to prepare gama-alumina support type nickel phosphide, the phosphate radical in the presoma can form AlPO4 mutually with gamma-aluminium oxide carrier commonly used.Therefore, during preparation gama-alumina support type nickel phosphide, the P/Ni mol ratio in the presoma requires usually greater than 2/1, and reduction temperature is more than 700 ℃.For silicon dioxide carried type nickel phosphide, phosphate radical can form polyphosphate radical, and the P/Ni mol ratio in the presoma requires usually greater than 0.8/1, and reduction temperature is more than 600 ℃.
Obviously, 600 ℃ of high temperature reductions (〉) there is very important shortcoming, comprising: (1) equipment requires high, and engineering economy is poor; (2) be higher than the self-ignition point of hydrogen, the process poor stability; (3), can cause mechanical strength to reduce, or make the silica distillation above the serviceability temperature upper limit of gama-alumina and silica.
3, hypophosphites decomposition method
The phosphorus that ortho states is gone back in use is done phosphorus source (PH3 or organic phosphine) and is had very high reaction activity, can form nickel phosphides down at 350 ℃ with NiO, and can effectively avoid the formation of AlPO4 phase.This method for bonderizing laboratory is feasible, but the price in phosphorus source is far above phosphate, and this increases the production cost of made catalyst of phosphatizing nickel undoubtedly, reduces engineering economy.Particularly the hypertoxic character in PH3 and organophosphor source has reduced the process security, does not meet the requirement of Green Development.
By contrast, the hypophosphites decomposition method is used the hypophosphites (as sodium hypophosphite) with reducing activity to do the decomposition of phosphorus source and is generated PH3, and this can make reduction temperature be reduced to 300-400 ℃ equally.This method for preparing the Ni2P catalyst by the hypophosphites thermal decomposition only needs simple heat treatment under the normal pressure; Raw materials used low price, safety have the excellent engineering economy.
But the unit step of the preparation process of hypophosphites decomposition method is obviously more than temperature-programmed reduction method, and implementation process is comparatively complicated, and simultaneously, the phosphorus-containing wastewater that produces in the course of reaction is difficult to handle the environmental issue that formation can't be ignored.
Summary of the invention
Deficiency at the prior art existence, technical problem to be solved by this invention is, a kind of preparation method of Alpha-alumina support type catalyst of phosphatizing nickel is provided, on the basis of temperature-programmed reduction method, improve, reduce reduction temperature, effectively avoid the shortcoming that high temperature reduction brought, had good feasibility and result of use.
For solving the problems of the technologies described above, the technical solution adopted in the present invention is that a kind of preparation method of Alpha-alumina support type catalyst of phosphatizing nickel is characterized in that, comprises the steps:
The first step, maceration extract preparation: with PdCl
2Or RuCl
3, mix Ni (NO
3)
26H
2O, NH
4H
2PO
4, be dissolved in ultra-pure water, [Ni in the feasible solution of being prepared
2+] be 2.0-3.0mol/L, P/Ni mol ratio≤0.8 in the presoma;
Second step, incipient impregnation: under vacuum or normal pressure, with α-Al
2O
3The carrier incipient impregnation is in maceration extract;
The 3rd step, drying: dry 2-6h under 60 ℃-120 ℃;
The 4th step, roasting: 500 ℃ of following roasting 3-5h;
In the 5th step, two secondary programs: incipient impregnation is in maceration extract once more with prepared presoma, and repeating step three is to step 4 then;
In the 6th step, reduction: reduce in normal pressure hydrogen, temperature conditions is 450-500 ℃, and heating rate is 15 ℃/h, and hydrogen (99.5%) air speed is 20-800h
-1, promptly.
The preparation method of above-mentioned Alpha-alumina support type catalyst of phosphatizing nickel, the nickel phosphide crystal formation is Ni in the Alpha-alumina support type catalyst of phosphatizing nickel that above-mentioned steps makes
3P, Ni
12P
5Or Ni
2P.
The preparation method of above-mentioned Alpha-alumina support type catalyst of phosphatizing nickel, the nickel phosphide particle diameter is less than 20nm in the Alpha-alumina support type catalyst of phosphatizing nickel that above-mentioned steps makes.
The present invention has following advantage and useful technique effect:
1, the preparation method of Alpha-alumina support type catalyst of phosphatizing nickel of the present invention is with sphere, trifolium-shaped or column type alpha-Al
2O
3Be carrier, trace P d or Ru (≤0.1wt.%) under the catalytic reduction effect, nickel, phosphorus presoma are transformed into nickel phosphide; Its core is to have utilized the catalytic action of trace Pd in the temperature programmed reduction process or Ru, and reduction temperature is reduced to below 500 ℃, has effectively avoided the shortcoming that high temperature reduction brought, and the no three wastes form, safety and environmental protection.
2, the preparation method of Alpha-alumina support type catalyst of phosphatizing nickel of the present invention, step is simple, is convenient to operation, makes to prepare α-Al
2O
3The industrial preparation process of support type catalyst of phosphatizing nickel has good feasibility.
3, the preparation method of Alpha-alumina support type catalyst of phosphatizing nickel of the present invention, the preparation process mild condition is suitable for industrial production, has excellent Catalytic Hydrogenation Properties simultaneously.
Description of drawings
Fig. 1 is preparation method's flow chart of the present invention;
Fig. 2 is the XRD figure of the Alpha-alumina support type nickel phosphide of temperature programming catalytic reduction method preparation.
The specific embodiment
Embodiment 1
As shown in Figure 1, the Alpha-alumina support type catalyst of phosphatizing nickel (Ni of present embodiment
2P) preparation method comprises the steps:
The first step, maceration extract preparation: with PdCl
2Mix Ni (NO
3)
26H
2O, NH
4H
2PO
4, be dissolved in ultra-pure water, [Ni in the feasible solution of being prepared
2+] be 3.0mol/L, [Pd
2+] be 0.05 mol/L, P/Ni mol ratio=0.8 in the presoma;
Second step, incipient impregnation: under vacuum or normal pressure, with α-Al
2O
3Carrier 50g incipient impregnation is in the 25ml maceration extract;
The 3rd step, drying: dry 6h under 60 ℃;
The 4th step, roasting: 500 ℃ of following roasting 3h;
In the 5th step, two secondary programs: incipient impregnation is in the 25ml maceration extract once more with prepared presoma, and repeating step three is to step 4 then;
In the 6th step, reduction: reduce in normal pressure hydrogen, temperature conditions is 495 ℃, and heating rate is 15 ℃/h, and hydrogen (99.5%) air speed is 400h
-1, promptly.
The XRD figure of the made nickel phosphide of present embodiment is shown in a line among Fig. 2, and the nickel phosphide crystalline phase is Ni
2P calculates particle diameter by the Scherrer formula＜20nm, w (Ni
2P)/[w (Ni
2P)+w (α-Al
2O
3)] * 100%=15wt.%, Pd content is 0.05wt.%.
As shown in Figure 1, the Alpha-alumina support type catalyst of phosphatizing nickel (Ni of present embodiment
12P
5Type) preparation method repeats no more with embodiment 1 same steps as, and difference is:
The first step, maceration extract preparation: with PdCl
2Mix Ni (NO
3)
26H
2O, NH
4H
2PO
4, be dissolved in ultra-pure water, [Ni in the feasible solution of being prepared
2+] be 3.0mol/L, [Pd
2+] be 0.05 mol/L, P/Ni mol ratio=0.5 in the presoma.
The XRD figure of the made nickel phosphide of present embodiment is shown in b line among Fig. 2, and the nickel phosphide crystalline phase is Ni
12P
5, calculate particle diameter by the Scherrer formula＜15nm, catalyst P d content are 0.05 wt.%.
Embodiment 3
As shown in Figure 1, the Alpha-alumina support type catalyst of phosphatizing nickel (Ni of present embodiment
3The P type) preparation method repeats no more with embodiment 1 same steps as, and difference is:
The first step, maceration extract preparation: with PdCl
2Mix Ni (NO
3)
26H
2O, NH
4H
2PO
4, be dissolved in ultra-pure water, [Ni in the feasible solution of being prepared
2+] be 3.0mol/L, [Pd
2+] be 0.05 mol/L, P/Ni mol ratio=0.4 in the presoma.
The XRD figure of the made nickel phosphide of present embodiment sees among Fig. 2 that shown in the c line, the nickel phosphide crystalline phase is Ni
3P calculates particle diameter by the Scherrer formula＜15nm, catalyst P d content are 0.05 wt.%.
Embodiment 4
As shown in Figure 1, the Alpha-alumina support type catalyst of phosphatizing nickel (Ni of present embodiment
2The P type) preparation method repeats no more with embodiment 1 same steps as, and difference is:
The first step, maceration extract preparation: with RuCl
3Mix Ni (NO
3)
26H
2O, NH
4H
2PO
4, be dissolved in ultra-pure water, [Ni in the feasible solution of being prepared
2+] be 3.0mol/L, [Ru
3+] be 0.10mol/L, P/Ni mol ratio=0.4 in the presoma.
The XRD figure of the made nickel phosphide of present embodiment sees among Fig. 2 that shown in the d line, the nickel phosphide crystalline phase is Ni
2P calculates particle diameter by the Scherrer formula＜15nm, catalyst Ru content is 0.1 wt.%.
As shown in Figure 1, the Alpha-alumina support type catalyst of phosphatizing nickel (Ni of present embodiment
2P) preparation method comprises the steps:
The first step, maceration extract preparation: with PdCl
2Mix Ni (NO
3)
26H
2O, NH
4H
2PO
4, be dissolved in ultra-pure water, [Ni in the feasible solution of being prepared
2+] be 2.0mol/L, [Pd
2+] be 0.05 mol/L, P/Ni mol ratio=0.7 in the presoma;
Second step, incipient impregnation: under vacuum or normal pressure, with α-Al
2O
3Carrier 50g incipient impregnation is in the 25ml maceration extract;
The 3rd step, drying: dry 2h under 120 ℃;
The 4th step, roasting: 500 ℃ of following roasting 5h;
In the 5th step, two secondary programs: incipient impregnation is in the 25ml maceration extract once more with prepared presoma, and repeating step three is to step 4 then;
In the 6th step, reduction: reduce in normal pressure hydrogen, temperature conditions is 450 ℃, and heating rate is 15 ℃/h, and hydrogen (99.5%) air speed is 800h
-1, promptly.
The crystalline phase of the made nickel phosphide of present embodiment is Ni
2P calculates particle diameter by the Scherrer formula＜20nm, Pd content are 0.05wt.%.
Embodiment 6
As shown in Figure 1, the Alpha-alumina support type catalyst of phosphatizing nickel (Ni of present embodiment
3P) preparation method comprises the steps:
The first step, maceration extract preparation: with PdCl
2Mix Ni (NO
3)
26H
2O, NH
4H
2PO
4, be dissolved in ultra-pure water, [Ni in the feasible solution of being prepared
2+] be 2.0mol/L, [Pd
2+] be 0.05 mol/L, P/Ni mol ratio=0.6 in the presoma;
Second step, incipient impregnation: under vacuum or normal pressure, with α-Al
2O
3Carrier 50g incipient impregnation is in the 25ml maceration extract;
The 3rd step, drying: dry 4h under 100 ℃;
The 4th step, roasting: 500 ℃ of following roasting 4h;
In the 5th step, two secondary programs: incipient impregnation is in the 25ml maceration extract once more with prepared presoma, and repeating step three is to step 4 then;
In the 6th step, reduction: reduce in normal pressure hydrogen, temperature conditions is 500 ℃, and heating rate is 15 ℃/h, and hydrogen (99.5%) air speed is 20h
-1, promptly.
The crystalline phase of the made nickel phosphide of present embodiment is Ni
3P calculates particle diameter by the Scherrer formula＜15nm, catalyst P d content are 0.05 wt.%.
Comparative Examples 1
Adopt traditional temperature-programmed reduction method to prepare Alpha-alumina support type nickel phosphide, step is as follows:
The first step, maceration extract preparation: with Ni (NO
3)
26H
2O, NH
4H
2PO
4Be dissolved in ultra-pure water, [Ni in the feasible solution of being prepared
2+] be 3.0mol/L, P/Ni mol ratio=0.8 in the presoma;
Second step, incipient impregnation: under vacuum or normal pressure, with α-Al
2O
3Carrier 50g incipient impregnation is in the 25ml maceration extract;
The 3rd step, drying: dry 6h under 60 ℃;
The 4th step, roasting: 500 ℃ of following roasting 3h;
In the 5th step, two secondary programs: incipient impregnation is in the 25ml maceration extract once more with prepared presoma, and repeating step three is to step 4 then;
In the 6th step, reduction: reduce in normal pressure hydrogen, temperature conditions is 605 ℃, and heating rate is 15 ℃/h, and hydrogen (99.5%) air speed is 400h
-1, promptly.
The XRD figure of the made nickel phosphide of Comparative Examples is shown in e line among Fig. 2, and presoma is not reduced into nickel phosphide.
Comparative Examples adopts traditional temperature-programmed reduction method to prepare Alpha-alumina support type nickel phosphide as can be known thus, and reduction temperature is more than 600 ℃, the shortcoming that can't avoid high temperature reduction to bring.
The above only is to preferred embodiment of the present invention, is not to be that the present invention is done other forms of restriction, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every the present invention program's content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment did, still belongs to protection scope of the present invention according to technical spirit of the present invention.
Claims (3)
1. the preparation method of an Alpha-alumina support type catalyst of phosphatizing nickel is characterized in that, comprises the steps:
The first step, maceration extract preparation: with PdCl
2Or RuCl
3, mix Ni (NO
3)
26H
2O, NH
4H
2PO
4, be dissolved in ultra-pure water, [Ni in the feasible solution of being prepared
2+] be 2.0-3.0mol/L, P/Ni mol ratio≤0.8 in the presoma;
Second step, incipient impregnation: under vacuum or normal pressure, with α-Al
2O
3The carrier incipient impregnation is in maceration extract;
The 3rd step, drying: dry 2-6h under 60 ℃-120 ℃;
The 4th step, roasting: 500 ℃ of following roasting 3-5h;
In the 5th step, two secondary programs: incipient impregnation is in maceration extract once more with prepared presoma, and repeating step three is to step 4 then;
In the 6th step, reduction: reduce in normal pressure hydrogen, temperature conditions is 450-500 ℃, and heating rate is 15 ℃/h, and hydrogen (99.5%) air speed is 20-800h
-1, promptly.
2. the preparation method of Alpha-alumina support type catalyst of phosphatizing nickel according to claim 1 is characterized in that, the nickel phosphide crystal formation is Ni in the Alpha-alumina support type catalyst of phosphatizing nickel that above-mentioned steps makes
3P, Ni
12P
5Or Ni
2P.
3. the preparation method of Alpha-alumina support type catalyst of phosphatizing nickel according to claim 1 is characterized in that, the nickel phosphide particle diameter is less than 20nm in the Alpha-alumina support type catalyst of phosphatizing nickel that above-mentioned steps makes.
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| CN108714430A (en) * | 2018-05-21 | 2018-10-30 | 中国科学院山西煤炭化学研究所 | A kind of middle coalite tar hydrotreating catalyst Ni2P/SiO2Or Ni2P/Al2O3Preparation method |
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