CN100457935C - Palladium-base alloy for recovering platinum catalyst and recovering net - Google Patents
Palladium-base alloy for recovering platinum catalyst and recovering net Download PDFInfo
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- CN100457935C CN100457935C CNB2005100486129A CN200510048612A CN100457935C CN 100457935 C CN100457935 C CN 100457935C CN B2005100486129 A CNB2005100486129 A CN B2005100486129A CN 200510048612 A CN200510048612 A CN 200510048612A CN 100457935 C CN100457935 C CN 100457935C
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Abstract
The invention relates to Pd-base alloy and recovery net for Pt catalyst in ammonoxidation process. Wherein, the constituents with wt% of alloy comprise: Ni 3~8, Cu 8~15, Fe 0~5, Ce 0~0.5, and residual Pd. This alloy has well high-temperature strength with high bond strength. The recovery net has the 0.08~0.15mm Pt-base alloy diameter and 248~992 holes/(cm)2 mesh density, has high recovery rate, needs low Pt consumption and cost, and obtains obvious economic benefit.
Description
Technical field
The present invention relates to palladium-base alloy and reclaim net, particularly in the ammonia oxidation process, reclaim platinum catalyst loss platinum with palladium-base alloy and the recovery net that makes thereof.
Background technology
In nitric acid production, the ammonia oxidation process is used in 780～950 ℃ of scopes with platinum alloy catalyst, and element such as platinum volatilizees with oxide form in the platinum alloy, and runs off with air-flow, forms loss.The loss of platinum makes catalyst activity reduction in the platinum alloy catalyst, influences the ordinary production of nitric acid, and the nitric acid production cost is risen.Because noble metal platinum costs an arm and a leg, the work of reclaiming platinum catalyst loss platinum is subjected to people's common concern, has produced different recovery methods.The mechanical filter absorption method is to make air communication cross filtration unit, reaches the purpose that captures the platinum particulate.This kind method increases systemic resistance, and the rate of recovery is low.The collecter ring absorption method is that the palldium alloy silk is made netted placing under the platinum guaze, reclaims loss platinum.Nineteen sixty-eight, a kind of Pd20Au alloy has been invented by German Degssa company, and makes collecter ring with it, is placed in the platinum guaze below, and collecter ring is used heat-resistance stainless steel mesh liner pad up and down.It is directly effective that this kind method reclaims loss platinum, the rate of recovery is improved, but cost is higher.At present, the collecter ring absorption method is applied in the nitric acid production all over the world.Chinese patent CN1036189A is made into the recovery net with the palladium Cerium alloy wire that contains 0～0.2% Cerium, forms retrieving arrangement by recovery net, separation net, support mesh, tightly is put in platinum catalysis net below, reclaims loss platinum.Chinese patent CN1139155A provides a kind of adsorptive palladium-alloy net, and content is palladium 85～97%, nickel 1～10%, and Cerium 0.0001～5%, and the adsorptive palladium-alloy net filament diameter is 0.098～0.132mm, and the mesh of being knitted is 40～60 orders.Above palladium-base alloy cost height, mechanical and physical performance has the possibility of further improvement, and the cracking phenomenon is serious in the use of recovery net, and it reclaims net platinum rate of recovery and can further improve.
Summary of the invention
The present invention can solve reclaim net intensity low, reclaim that network capacity easily becomes fragile, the technical problem of oxidation, cracking phenomenon, provide a kind of recovery platinum catalyst with palladium-base alloy and reclaim net, this palladium-base alloy has hot strength and absorption platinum intensity preferably, can be used to produce aforementioned recovery net, this recovery netting gear has that the cost of material is low, platinum rate of recovery height, advantages of high strength.
In the nitric acid production process, the pressure of oxidative ammonolysis is 0.1～1.0MPa, and temperature of reaction is 780～950 ℃, and used catalysis net material is PtRh or PtPdRh alloy.Under this thermodynamic condition, Pt is oxidized to PtO
2, Rh is oxidized to RhO
2, Rh
2O
3, Pd is oxidized to PdO, and generates the gaseous state volatile oxidn, forms the direct weightlessness of platinum guaze.In the metal of loss, main body is a platinum, also has a small amount of rhodium and palladium.Therefore, reduce cost, reduce the platinum loss, the utilization of strengthening comprehension improves whole economic efficiency, is the target that the nitric plant is pursued always.
At present, use palladium, porpezite or Pd-Ni alloy material both at home and abroad, be drawn into filament, be woven into net, supporting with the separation of refractory alloy nets such as stainless steel again, be put under the platinum guaze, carry out the recovery of platinum, obtained certain effect.Evaporable PtO in the catalysis net
2Steam is delivered to palldium alloy by air-flow and is reclaimed net surface, and the diffusion back forms alloy makes platinum obtain reclaiming.Metal Pd has the high rate of recovery to Pt, but the recovery net intensity of making is low.After adding elements such as Au, Ni, Ce respectively in Pd in the prior art, improved recovery net intensity, but in use become fragile easily, oxidation, cracking phenomenon are serious, influence the rate of recovery and stable the use.Therefore, obtain rate of recovery height, the recovery net approach that mechanical and physical performance is good is exactly that an amount of Ni, Cu, Fe, Ce are added among the Pd, thereby obtain the described recovery platinum catalyst of the object of the invention palladium-base alloy, and on this basis, utilize aforementioned alloy production to go out the described recovery net of the object of the invention.
The described recovery platinum catalyst of the object of the invention with the composition weight percent of palladium-base alloy is: Ni is 3%～8%, and Cu is 8%～15%, and Fe is 0%～5%, and Ce is 0%～0.5%, the Pd surplus.Recovery platinum catalyst of the present invention is 0.08～0.15 millimeter with the recovery mesh wire diameter that the palladium-base alloy braiding makes.
Recovery platinum catalyst of the present invention can be used the general preparation method's production of field of alloy material with palladium-base alloy.
The recovery net that described recovery platinum catalyst of the present invention makes with palladium-base alloy braiding, its mesh density be 248～992 holes/(centimetre)
2
Add an amount of Ni, Cu, Fe, Ce in Pd after, because Ni, Cu, Fe, the special role separately of Ce element make the mechanical and physical performance of alloy of the present invention improve, embrittlement in the application, cracking phenomenon are controlled.
Palladium-base alloy silk of the present invention can be woven into the plain weave net or knitted net uses.Knitted net, compares with the plain weave net under square one owing to have the three-dimensional structure characteristics, the gas-solid surface in contact is long-pending to be increased more than 10%, the rate of recovery is improved, and the thermal shock resistance of knitted net and tearing toughness are better than the plain weave net, can slow down the check crack trend that reclaims greatly.Because palladium content reduces than prior art in the palladium-base alloy of the present invention, cost recovery reduces, and economic benefit is obvious.This reclaim net fully can with the supporting use of platinum alloy catalysis net, surpass 1 year work-ing life on atmospheric pressure kiln, surpass half a year work-ing life on medium pressure furnace, over-all properties is better than prior art.
Embodiment
Embodiment 1
With purity be 99.95% Pd and other metallic element by the content proportioning after, founding becomes alloy in vacuum melting furnace, its each constituent content is: Ni4%, Cu10%, Fe2%, Ce0.2, Pd surplus.
This palladium-base alloy is drawn into diameter 0.09mm filament, is woven into 2 on plain weave net, mesh density be 760～992 holes/(centimetre)
2With three on heat-resistance stainless steel net palladium is reclaimed net and separate, form and reclaim the net group, be put under the platinum alloy catalysis net group.Oxidative ammonolysis pressure 0.5～0.55MPa, 870～880 ℃ of temperature of reaction are moved 180 days, catalysis net platinum loss 2300 grams, being recovered to the platinum amount is 1390 grams, the rate of recovery is 60%.
Embodiment 2
With purity be 99.95% Pd and other metallic element by the content proportioning after, founding becomes alloy in vacuum melting furnace, its each constituent content is: Ni4%, Cu10%, Fe2%, Ce0.2, Pd surplus.
This palladium-base alloy is drawn into diameter 0.09mm filament, is woven into 2 of knitted nets, quite mesh density be 760～992 holes/(centimetre)
2With three on heat-resistance stainless steel net palladium is reclaimed net and separate, form and reclaim the net group, be put under the platinum alloy catalysis net group.Oxidative ammonolysis pressure 0.5～0.55MPa, 870～880 ℃ of temperature of reaction are moved 180 days, catalysis net platinum loss 1940 grams, being recovered to the platinum amount is 1340 grams, the rate of recovery is 69%.
Claims (3)
1, a kind of platinum catalyst palladium-base alloy that in the ammonia oxidation process, reclaims, it is characterized in that the composition weight percent of palladium-base alloy is: Ni is 3%～8%, and Cu is 8%～15%, and Fe is 2%, and Ce is 0.2%, the Pd surplus.
2, a kind of platinum catalyst that reclaims according to claim 1 is characterized in that with the recovery net that the palladium-base alloy braiding makes the palladium-base alloy filament diameter is 0.08～0.15 millimeter.
3, according to the described recovery net of claim 2, the mesh density that it is characterized in that reclaiming net be 248～992 holes/(centimetre)
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100486129A CN100457935C (en) | 2005-11-09 | 2005-11-09 | Palladium-base alloy for recovering platinum catalyst and recovering net |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100486129A CN100457935C (en) | 2005-11-09 | 2005-11-09 | Palladium-base alloy for recovering platinum catalyst and recovering net |
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| Publication Number | Publication Date |
|---|---|
| CN1766146A CN1766146A (en) | 2006-05-03 |
| CN100457935C true CN100457935C (en) | 2009-02-04 |
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| CNB2005100486129A Expired - Fee Related CN100457935C (en) | 2005-11-09 | 2005-11-09 | Palladium-base alloy for recovering platinum catalyst and recovering net |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104073640B (en) * | 2014-07-01 | 2016-04-13 | 昆明南铂再生资源技术研究有限公司 | Trapping agent and the application thereof of platinum metals is reclaimed in nitric acid industry converter for ammonia oxidation |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87108317A (en) * | 1986-12-16 | 1988-07-06 | 挪威海德罗公司 | Be used to handle the material of ammonia |
| DD267392A3 (en) * | 1987-05-20 | 1989-05-03 | Berliner Metallhuetten Und Hal | METHOD FOR THE PRODUCTION OF FINE WIRE FOR THE PRODUCTION OF FAENGERNETS |
| JPH01176045A (en) * | 1987-07-30 | 1989-07-12 | Kernforschungsanlage Juelich Gmbh | Palladium alloy as catalyst for oxidizing hydrogen in atmosphere containing hydrogen and oxygen |
| CN1036189A (en) * | 1989-04-15 | 1989-10-11 | 航空航天工业部第六二一研究所 | The recovery method of platinum catalyst |
| CN1065027A (en) * | 1991-03-16 | 1992-10-07 | 底古萨股份公司 | The manufacture method of the gas-permeable nets of noble metals that Catalytic processes is used |
| CN1139156A (en) * | 1995-06-28 | 1997-01-01 | 太原化学工业集团公司化肥厂 | Adsorptive palladium-alloy net |
| RU2119381C1 (en) * | 1997-06-27 | 1998-09-27 | Открытое акционерное общество "Екатеринбургский завод по обработке цветных металлов" | Device for trapping platinoids in catalytic oxidation of ammonia |
-
2005
- 2005-11-09 CN CNB2005100486129A patent/CN100457935C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87108317A (en) * | 1986-12-16 | 1988-07-06 | 挪威海德罗公司 | Be used to handle the material of ammonia |
| DD267392A3 (en) * | 1987-05-20 | 1989-05-03 | Berliner Metallhuetten Und Hal | METHOD FOR THE PRODUCTION OF FINE WIRE FOR THE PRODUCTION OF FAENGERNETS |
| JPH01176045A (en) * | 1987-07-30 | 1989-07-12 | Kernforschungsanlage Juelich Gmbh | Palladium alloy as catalyst for oxidizing hydrogen in atmosphere containing hydrogen and oxygen |
| CN1036189A (en) * | 1989-04-15 | 1989-10-11 | 航空航天工业部第六二一研究所 | The recovery method of platinum catalyst |
| CN1065027A (en) * | 1991-03-16 | 1992-10-07 | 底古萨股份公司 | The manufacture method of the gas-permeable nets of noble metals that Catalytic processes is used |
| CN1139156A (en) * | 1995-06-28 | 1997-01-01 | 太原化学工业集团公司化肥厂 | Adsorptive palladium-alloy net |
| RU2119381C1 (en) * | 1997-06-27 | 1998-09-27 | Открытое акционерное общество "Екатеринбургский завод по обработке цветных металлов" | Device for trapping platinoids in catalytic oxidation of ammonia |
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| CN1766146A (en) | 2006-05-03 |
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