CN1060975A - Amorphous alloy powder catalyst - Google Patents
Amorphous alloy powder catalyst Download PDFInfo
- Publication number
- CN1060975A CN1060975A CN 90106414 CN90106414A CN1060975A CN 1060975 A CN1060975 A CN 1060975A CN 90106414 CN90106414 CN 90106414 CN 90106414 A CN90106414 A CN 90106414A CN 1060975 A CN1060975 A CN 1060975A
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- China
- Prior art keywords
- alloy
- embrittlement
- preparation process
- catalyst
- weight
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 title claims abstract description 19
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 27
- 239000000956 alloy Substances 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 230000004913 activation Effects 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 238000010791 quenching Methods 0.000 claims abstract description 7
- 230000000171 quenching effect Effects 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910021074 Pd—Si Inorganic materials 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 3
- 239000003929 acidic solution Substances 0.000 abstract 1
- 238000005096 rolling process Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000003701 mechanical milling Methods 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention discloses an amorphous alloy powder catalyst, belonging to the catalyst field, and providing three amorphous alloy powder catalysts of Ni-Pd-Si, Cu-Pd-Si and Ni-Pd-P, wherein the preparation method comprises the following steps: 1. preparing an alloy strip by a liquid quenching single-roll method; 2. carrying out embrittlement treatment on the strip in a relaxation temperature range under a vacuum condition or a protective atmosphere; 3. ball milling; 4. the catalyst provided by the invention has higher activity and selectivity by performing activation treatment in an acidic solution.
Description
The present invention system belongs to catalyst field, and the noncrystal alloy powder caltalyst of Pb system promptly is provided.
Nickel and palladium are catalyst metals commonly used, and for a long time, people use them respectively always, and be to add with the form of compound, add fashionablely, by modes such as chemistry or physics it is downloaded on the carrier, this not only makes the manufacturing process complexity, the cost height, and cause and reclaim difficulty.In recent years, there was the people that amorphous Pd80 Si20 catalyst was carried out research, but, was difficult to make fine powder, so fail to be committed to application so far because to contain Pd amount high; In addition, also the someone utilizes non-crystaline amorphous metal as catalyst, but increases this problem of specific surface because of solving, so fail should producing in catalyst.
The objective of the invention is to provide a kind of need not to support, amorphous state Ni-Pd-Si with high activity and high selectivity, Cu-Pd-Si, the catalyst of three kinds of alloy series of Ni-Pd-B, the preparation method of the noncrystal alloy powder caltalyst of above-mentioned three kinds of series is made up of following steps:
(1) with the liquisol quenching single-roller method with the alloy of molten state with 〉=10
5The cooling velocity of K/ second is made alloy strip;
(2) band that makes is being carried out the embrittlement processing under vacuum condition or the protective atmosphere in the relaxation temperature range;
(3) alloy that embrittlement is handled places ball mill ball milling under protective medium;
(4) in acid solution, carry out activation processing.
The composition of three kinds of above-mentioned Pd alloy species is:
1, Pd 10-50% Si 10-20% Ni surplus
2, Pd 50-80% Si 15-20% Cu surplus
3, Pd 10-40% P 20-40% Ni surplus.
Optimum value is respectively:
1、Pd 41.2% Si 8.8% Ni 50%
2、Pd 77.5% Si 16.5% Cu 6%
3、Pd 36.5% P 21% Ni 36.5%
Produce the best relaxation temperature scope in the step:
Ni-Pd-Si series is 500-630K;
Cu-Pd-Si; Ni-Pd-P series is 500-600K.
Acid solution in the activation processing step is preferably selected HF acid for use, and medium used during ball milling preferably adopts alcohol, acetone.
Ni-Pd-Si provided by the present invention, Cu-Pd-Si, the basic principle that the catalyst of three kinds of series of Ni-Pd-B is produced is with high cooling velocity (〉=10 with liquid alloy
5K/ second) form amorphous alloy by liquid quenching, through suitable Temperature Treatment generation embrittlement, it is decrystallized when the alloy after the embrittlement is ground in mechanical milling process secondary to take place again again, through forming the nano level amorphous powder of hundreds of.So the formation mechanism of fine-powder mainly is after the amorphous relaxation atomic rearrangement to have taken place, producing tiny nucleus and bond energy diminishes, thereby band is become fragile be easy to fragmentation, in mechanical milling process,, promptly return to amorphous state from the relaxation attitude because the mechanical alloying effect has caused secondary decrystallized.In addition, because amorphous catalyst has produced porous surface after acid treatment, and node and cay are arranged on these surfaces, its specific surface is far longer than crystalline, powder, so the activity of amorphous alloy catalyst provided by the present invention is much higher than the crystalline, powder catalyst, moreover, since integrated application of the present invention Ni-Pd-Si, utilize Si to promote the disordering of alloy, thereby brought into play unordered Pd or unordered Ni characteristics and comprehensive advantage thereof separately, make catalyst promptly have high activity that high selectivity is arranged again.
Provide embodiment 1-provided by the present invention amorphous Ni-Pd-Si alloy powder caltalyst below
1, composition: Ni5% Pd41.2% Si8.8%(weight)
2, preparation method, step:
(1) the liquisol quenching single-roller method is produced in the amorphous Ni-Pd-Si band;
(2) with amorphous ribbon (10
-5Holder) under the temperature of 623K, handled 2 hours in the vacuum drying oven;
(3) place common star formula ball mill, ball milling 20 hours is used the alcohol media protection during ball milling, and (specific surface is 10 meters to obtain＜500 nanometers
2/ gram) amorphous powder;
(4) place the HF liquation to carry out activation processing at last.
The Ni-Pd-Si alloy powder caltalyst that provides by embodiment 1, result of the test shows, at room temperature demonstrates high activity, the corresponding crystalline-state catalyst of its specific activity active high six times, than the present industrial high 1-2 of activation times of using the Pd-c catalyst, selectivity is 100%.
Embodiment 2-Cu-Pd-Si noncrystal alloy powder caltalyst.
1, composition Cu 6% Pd 77.5 Si 16.5%(weight);
2, preparation process, except relaxation temperature be 596K, all the other are all identical with embodiment 1.Obtaining the result is that the corresponding crystalline-state catalyst of specific activity is active high 3 times, and selectivity is 100%
Embodiment 3-Ni-Pd-P noncrystal alloy powder caltalyst
1, composition Ni 36.5% Pd 36.5% P 27%(weight)
2, preparation process, except relaxation temperature was 585K, all the other were all the same with embodiment 1.
The result who obtains is that the corresponding crystalline-state catalyst of specific activity is active high 1 times.Selectivity is 100%
In sum as can be seen, amorphous alloy catalyst provided by the present invention has higher activity and selectivity, and preparation technology is simple, cost is low, is comparatively desirable catalyst up to now.
Claims (7)
1, a kind of noncrystal alloy powder caltalyst agent is characterized in that:
(1) composition: Pd 10-50%, Si 10-20% Ni surplus; (weight)
(2) preparation process:
1. use the liquisol quenching single-roller method with the alloy of molten state with 〉=10
5The cooling velocity of K/ second is made alloy strip;
2. the band that makes is being carried out the embrittlement processing under the vacuum condition or under the protective atmosphere in the relaxation temperature scope;
3. the alloy that embrittlement is handled places the ball mill ball milling with protective medium;
4. in acid solution, carry out activation processing.
2,, it is characterized in that the composition optimum value is according to the described catalyst of claim 1:
Ni 50% Pd 41.2% Si 8.8%(weight) the relaxation temperature optimum value of the processing of the embrittlement in the preparation process is 500-600K.
3, a kind of noncrystal alloy powder caltalyst is characterized in that:
1) composition: Pd 50-80%, Si 15-20%, Cu surplus (weight)
2) preparation process:
(1) with the liquisol quenching single-roller method with the alloy of molten state with 〉=10
5The cooling velocity of K/ second is made alloy strip;
(2) band that makes is being carried out the embrittlement processing under the vacuum condition or under the protective atmosphere in the relaxation temperature scope;
(3) alloy that embrittlement is handled places the ball mill ball milling with protective medium;
(4) in acid solution, carry out activation processing.
4,, it is characterized in that the best composition value of catalyst is according to the described catalyst of claim 3:
Cu 6%, and Pd 77.5%, Si 16.5%(weight)
The relaxation temperature optimum value that embrittlement in the preparation process is handled is 500-600K.
5, a kind of noncrystal alloy powder caltalyst is characterized in that:
1) composition: Pd10-40%, P20-40%, Ni surplus (weight)
2) preparation process:
(1) with the liquisol quenching single-roller method with the alloy of molten state with 〉=10
5The cooling velocity of K/ second is made alloy strip;
(2) band that makes is being carried out the embrittlement processing under the vacuum condition or under the protective atmosphere in the relaxation temperature range;
(3) alloy that embrittlement is handled places the ball mill ball milling with protective medium;
(4) in acid solution, carry out activation processing.
6, peace is characterized in that according to the described catalyst of claim 5 the composition optimum value is:
Ni 36.5%, and Pd 36.5%, P 27%(weight)
The relaxation temperature optimum value that embrittlement in the preparation process is handled is 500-600K.
7, according to claim 1,2,3,4,5,6 described catalyst, the used acid solution of activation processing is preferably selected HF acid for use in the preparation process, and medium used during ball milling preferably adopts alcohol, acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90106414 CN1060975A (en) | 1990-10-29 | 1990-10-29 | Amorphous alloy powder catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90106414 CN1060975A (en) | 1990-10-29 | 1990-10-29 | Amorphous alloy powder catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1060975A true CN1060975A (en) | 1992-05-13 |
Family
ID=4880055
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90106414 Pending CN1060975A (en) | 1990-10-29 | 1990-10-29 | Amorphous alloy powder catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1060975A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013158233A1 (en) * | 2012-04-16 | 2013-10-24 | Dow Corning Corporation | Processes for the preparation of silicon containing intermetallic compounds and intermetallic compounds prepared thereby |
| CN106216698A (en) * | 2016-09-29 | 2016-12-14 | 柳州增程材料科技有限公司 | A kind of preparation technology of 3D printing alloy powder |
| CN106492856A (en) * | 2016-10-18 | 2017-03-15 | 中国科学院深圳先进技术研究院 | NiP Pd catalyst and its preparation method and application |
| CN110093571A (en) * | 2019-05-22 | 2019-08-06 | 江苏集萃安泰创明先进能源材料研究院有限公司 | A method of regulation amorphous alloy micro-structure |
| CN112850669A (en) * | 2021-01-29 | 2021-05-28 | 杭州电子科技大学 | Preparation method of palladium-copper phosphide heterodimer material |
-
1990
- 1990-10-29 CN CN 90106414 patent/CN1060975A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013158233A1 (en) * | 2012-04-16 | 2013-10-24 | Dow Corning Corporation | Processes for the preparation of silicon containing intermetallic compounds and intermetallic compounds prepared thereby |
| CN106216698A (en) * | 2016-09-29 | 2016-12-14 | 柳州增程材料科技有限公司 | A kind of preparation technology of 3D printing alloy powder |
| CN106492856A (en) * | 2016-10-18 | 2017-03-15 | 中国科学院深圳先进技术研究院 | NiP Pd catalyst and its preparation method and application |
| CN106492856B (en) * | 2016-10-18 | 2019-02-26 | 中国科学院深圳先进技术研究院 | NiP-Pd catalyst and its preparation method and application |
| CN110093571A (en) * | 2019-05-22 | 2019-08-06 | 江苏集萃安泰创明先进能源材料研究院有限公司 | A method of regulation amorphous alloy micro-structure |
| CN110093571B (en) * | 2019-05-22 | 2021-07-13 | 江苏集萃安泰创明先进能源材料研究院有限公司 | Method for regulating and controlling amorphous alloy microstructure |
| CN112850669A (en) * | 2021-01-29 | 2021-05-28 | 杭州电子科技大学 | Preparation method of palladium-copper phosphide heterodimer material |
| CN112850669B (en) * | 2021-01-29 | 2022-03-22 | 杭州电子科技大学 | Preparation method of palladium-copper phosphide heterodimer material |
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