CN106756747A - The preparation method of porous palladium material - Google Patents
The preparation method of porous palladium material Download PDFInfo
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- CN106756747A CN106756747A CN201710007939.4A CN201710007939A CN106756747A CN 106756747 A CN106756747 A CN 106756747A CN 201710007939 A CN201710007939 A CN 201710007939A CN 106756747 A CN106756747 A CN 106756747A
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- palladium
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- sulfide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/12—Oxidising using elemental oxygen or ozone
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Abstract
The invention belongs to field of metal material surface treatment, the preparation method (1) of specially porous palladium material is cleaned to raw material, and with pure palladium or palldium alloy material, (2) are corroded using hydrogen sulfide gas to palladium surface；(3) oxidation removal is carried out to spherical palladium sulfide using purity oxygen；(4) reduced using the reacted palladium material of hydrogen pair and purity oxygen, prepare porous palladium material.The preparation method of the porous palladium material that the present invention is provided, is corroded using hydrogen sulfide gas to palladium surface, and come control corrosion rate degree by way of adjusting reaction time and reaction temperature.The palladium surface after hydrogen sulfide corrosion is aoxidized using oxygen, realizes the removal of palladium sulfide, and realize the generation of palladium material vesicular texture.Cellular oxidation palladium layers are reduced using hydrogen, by adjusting recovery time, temperature, gas concentration etc., at utmost to retain the loose structure of porous palladium material.
Description
Technical field
The invention belongs to field of metal material surface treatment, the specially preparation method of porous palladium material.
Background technology
The preparation method of porous palladium material, mainly there is following methods：
First, PM technique prepares porous palladium material
1st, conventional powder metallurgy prepares porous palladium material
Palladium powder is by the way that after screening, direct die-filling sintering obtains porous palladium materials after the last demoulding.Program process is simple, but
Material porosity is relatively low, merges serious between powder.
2nd, the PM technique of addition pore creating material prepares porous palladium material
With palladium powder as raw material, with water soluble salt powder as pore creating material, with water, ethanol or acetone as dispersant, it is aided with it
His auxiliary agent, using hand lapping and ball milling mixing mode, drying is obtained mixed powder；By mixed powder compression molding be sheet or
Block pressed compact, in vacuum or the sintering furnace filled with protective gas after pressed compact drying, is put it into, in 400 DEG C of -1200 DEG C of temperature
In the range of be sintered into sintered blank；The sintered blank that will be obtained is hydrolyzed in 40 DEG C -100 DEG C of deionized water, makes solubility
Salt is completely dissolved removal, and drying obtains porous palladium materials.Porous palladium material obtained by the preparation method has gap rate higher and big
Small adjustable the characteristics of.But there is carbon pollution in easily introducing impurity, and sintering process in process in the method.
3rd, discharge plasma sintering prepares porous palladium material
Palladium powder by screen it is die-filling after, insert in SPS agglomerating plants sinter, obtain porous palladium materials after the last demoulding.SPS burns
Knot technology has heating rate fast, and sintering time is short (normally only needing a few minutes), sintered body than more uniform, simultaneously because pulse is electric
The effect of stream, it is possible to decrease the sintering temperature of material, can effectively suppress the growing up of crystal grain, technical process controllability preferably, crystal grain
The characteristics of surface easily activates, but the program is relatively costly, and material porosity is not high.
Two using porous material for carrier prepares porous palladium material
1st, its preparation method is：(1) chemically plating is used for the palladium coating ceramic powder of core shell structure；(2) palladium is coated
Ceramic powder is made slurry, is uniformly applied to porous carrier surface, then obtains palladium coating ceramic transition by high-temperature heat treatment
Layer；(3) carry out chemical plating in palladium coating ceramic transition layer surface and form palladium or palldium alloy film.The method is using core shell structure
Palladium coating ceramic powder is conducive to the sintering of ceramic particle, ceramic interlayer mechanical strength as porous carrier buffer layer material
It is improved.Due to palladium coating ceramic transition zone for subsequent chemistry plating process palladium membranes deposition provides palladium crystal seed, biography is avoided
System chemical plating sensitization activation process introduces tin impurity, is conducive to improving the high-temperature stability of palladium or palladium alloy composite membrane.But the party
Method technique is cumbersome, porosity is relatively low.
3rd, processed using atmosphere and palladium surface is modified
Oxidation processes are carried out to palladium surface using oxygen, vapor etc., palladium Surface Creation is aoxidized palladium layers, then use hydrogen
Oxidation palladium layers are reduced, it is possible to achieve 1) palladium surface impurity, the particularly removal of organic carbonaceous impurity；2) palladium surface is improved
Surface area；3) hydrogenolysis of palladium film is improved from activity.The method can realize the roughening of palladium surface topography, real to a certain extent
The modifying function on existing palladium surface, but palladium surface cannot be made to form orderly porous state, also cannot the size of device to hole enter with quantity
Row control.
The content of the invention
For above-mentioned technical problem, a kind of cost of present invention offer is relatively low, and process is simple, material porosity is high and controllable
The preparation method of porous palladium material.
Specifically technical scheme is：
The preparation method of porous palladium material, including procedure below：
(1) raw material are cleaned, with pure palladium or palldium alloy material, is cleaned repeatedly using acetone, alcohol, deionized water
Afterwards, dried for standby；
(2) palladium surface is corroded using hydrogen sulfide gas, in the spherical palladium sulfide corrosion product of palladium Surface Creation；
(3) oxidation removal is carried out to spherical palladium sulfide under specific reaction temperature using purity oxygen.Spherical palladium sulfide is gone
Hole is left after removing；
(4) reduced using the reacted palladium material of hydrogen pair and purity oxygen, prepare pure porous palladium material.
Specifically, described step (2), detailed process is that being positioned over palladium material can be passed through the reaction of mobility gas
In stove, hydrogen sulfide gas are passed through with the speed of 2ml-100ml/s and are reacted with palladium material, hydrogen sulfide forms spherical with palladium surface
Or granular palladium sulfide, according to spherical or graininess palladium sulfide quantity, the difference of size of required generation, select different
Reaction temperature is arranged in pairs or groups with the time, and it is 260 DEG C -740 DEG C that reaction temperature is interval, and the reaction time is 20s-60min.
Described step (3), detailed process is, the Surface Creation palladium material of palladium sulfide conversion zone after being reacted with hydrogen sulfide
Used as raw material, being positioned over can be passed through in the reacting furnace of mobility gas material, and pure oxygen gas is passed through with the speed of 2ml-100ml/s
Reacted with palladium material；Reaction temperature is 520 DEG C -650 DEG C, and the reaction time is 5min-30min；Spherical palladium sulfide is by oxygen
Palladium oxide is formed after oxidation, and because there is hole in volume contraction.
Described step (4), detailed process is, will with pure oxygen solid/liquid/gas reactions after, the Surface Creation palladium material of oxidation palladium layers
Directly it is soaked in the mixed gas of hydrogen or hydrogen and inert gas, or using hydrogen or the gaseous mixture of hydrogen and inert gas
Body is purged to it, to control reaction rate.Reaction temperature is subzero 20 DEG C to 20 DEG C above freezing, and the reaction time is 30s-
20min。
The preparation method of the porous palladium material that the present invention is provided, key problem in technology is：
1st, palladium surface is corroded using hydrogen sulfide gas, and by way of adjusting reaction time and reaction temperature come
Control corrosion rate degree.
2nd, the palladium surface after hydrogen sulfide corrosion is aoxidized using oxygen, realizes the removal of palladium sulfide, and realize palladium
The generation of material vesicular texture.
3rd, cellular oxidation palladium layers are reduced using hydrogen, by adjusting recovery time, temperature, gas concentration etc.,
At utmost to retain the loose structure of porous palladium material.
The preparation method of the porous palladium material that the present invention is provided, the technique effect having has：
1st, existing PM technique uses powder directly or adds thermal sintering porous palladium material, the material after pore creating material
There is a problem of that relatively low porosity, surface contamination, the smaller catalysis activity of surface area be not strong.This method is using hydrogen sulfide to palladium table
Face is corroded, and then it is surface-treated again using redox mode, during by controlling reaction temperature with reaction
Between can more accurately control palladium surface pore structure and hole quantity, it is possible to achieve porosity is further improved, surface contamination
The purposes such as removal, surface area increase, so as to further improve the performance of material.
2nd, have using dioxygen oxidation and hydrogen reducing thick with palladium surface to realize the removal of palladium surface organic matter in the prior art
The increased relevant report of rugosity, but it aims at the purification for realizing palladium surface, rather than the architectural characteristic for changing palladium surface.We
Method is first corroded using hydrogen sulfide to palladium surface, and then carries out oxidation removal to the palladium sulfide for generating using oxygen, then is used
Hydrogen to generate palladium oxide reduce, the palladium surface topography of loose structure can be prepared, with surface roughness with
Surface cleanliness is further improved, the characteristics of the catalysis activity of material is greatly improved.
Brief description of the drawings
Fig. 1 is pure palladium surface texture in embodiment：
Fig. 2 is surface texture after pure palladium hydrogen sulfide corrosion in embodiment；
Fig. 3 is surface texture after pure palladium redox in embodiment.
Specific embodiment
Technical scheme is elaborated in conjunction with the embodiments.
(1) raw material are cleaned；Idiographic flow is：With pure palladium as raw material, such as Fig. 1 is pure palladium surface texture.Adopt
After more than 3 times being cleaned repeatedly with acetone, alcohol, deionized water, dried for standby.
(2) palladium surface is corroded using hydrogen sulfide gas；Concrete technology is：Palladium material is positioned over can be passed through flowing
In the reacting furnace of property gas, be passed through hydrogen sulfide gas with the speed of 2ml-100ml/s is reacted with palladium material, hydrogen sulfide and palladium
Surface forms spherical or granular palladium sulfide, and spherical or graininess palladium sulfide quantity, the size according to required generation are not
Together, different reaction temperatures are selected to be arranged in pairs or groups with the time, it is 260 DEG C -740 DEG C that reaction temperature is interval, and the reaction time is 20s-
60min；Surface picture such as Fig. 2 after pure palladium hydrogen sulfide corrosion.
(3) oxidation removal is carried out to spherical palladium sulfide using purity oxygen；Concrete technology is：Will be with surface after hydrogen sulfide reaction
The palladium material of palladium sulfide conversion zone is generated as raw material, being positioned over can be passed through in the reacting furnace of mobility gas, with 2ml-
The speed of 100ml/s is passed through pure oxygen gas and is reacted with palladium material；Reaction temperature is 520 DEG C -650 DEG C, and the reaction time is
5min-30min；Spherical palladium sulfide forms palladium oxide after being oxidized by oxygen, hole occurs in volume contraction.
(4) reduced using the reacted palladium material of hydrogen pair and purity oxygen, prepare porous palladium material；Specific work
Skill is：Will with pure oxygen solid/liquid/gas reactions after, the palladium material of Surface Creation oxidation palladium layers is directly soaked in hydrogen or hydrogen and indifferent gas
In the mixed gas of body, or it is purged with the mixed gas of inert gas using hydrogen or hydrogen, to control reaction speed
Rate.Reaction temperature is subzero 20 DEG C to 20 DEG C above freezing, and the reaction time is 30s-20min.Pure palladium material surface after redox
Structure such as Fig. 3.
Claims (4)
1. the preparation method of porous palladium material, it is characterised in that including procedure below：
(1) with pure palladium or palldium alloy as raw material, after being cleaned repeatedly using acetone, alcohol, deionized water, dried for standby；
(2) palladium surface is corroded using hydrogen sulfide gas, in the spherical palladium sulfide corrosion product of palladium Surface Creation；
(3) oxidation removal is carried out to spherical palladium sulfide under specific reaction temperature using purity oxygen.After spherical palladium sulfide is removed
Leave hole；
(4) reduced using the reacted palladium material of hydrogen pair and purity oxygen, prepare pure porous palladium material.
2. the preparation method of porous palladium material according to claim 1, it is characterised in that described step (2), specific mistake
Cheng Wei, palladium material is positioned over can be passed through in the reacting furnace of mobility gas, and stink damp is passed through with the speed of 2ml-100ml/s
Body is reacted with palladium material, and hydrogen sulfide forms spherical or granular palladium sulfide with palladium surface, according to the ball of required generation
Shape or graininess palladium sulfide quantity, the difference of size, select different reaction temperatures to be arranged in pairs or groups with the time, and reaction temperature is interval
It it is 260 DEG C -740 DEG C, the reaction time is 20s-60min.
3. the preparation method of porous palladium material according to claim 1, it is characterised in that described step (3), specific mistake
Cheng Wei, used as raw material, to be positioned over can be passed through stream to the palladium material of Surface Creation palladium sulfide conversion zone after being reacted with hydrogen sulfide
In the reacting furnace of dynamic property gas, pure oxygen gas is passed through with the speed of 2ml-100ml/s and is reacted with palladium material；Reaction temperature is
520 DEG C -620 DEG C, the reaction time is 5min-30min；Spherical palladium sulfide forms palladium oxide, and because volume after being oxidized by oxygen
There is hole in contraction.
4. the preparation method of porous palladium material according to claim 1, it is characterised in that described step (4), specific mistake
Cheng Wei, will with pure oxygen solid/liquid/gas reactions after, the palladium material of Surface Creation oxidation palladium layers is directly soaked in hydrogen or hydrogen and indifferent gas
In the mixed gas of body, or it is purged with the mixed gas of inert gas using hydrogen or hydrogen, to control reaction speed
Rate.Reaction temperature is subzero 20 DEG C to 20 DEG C above freezing, and the reaction time is 30s-20min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467948A (en) * | 2018-04-19 | 2018-08-31 | 上海泰坦科技股份有限公司 | A kind of palladium and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009144563A2 (en) * | 2008-05-29 | 2009-12-03 | Politecnico Di Milano | Methods for obtaining an open-pore metal foam, composite material and open-pore metal foam |
| CN105506336A (en) * | 2015-12-23 | 2016-04-20 | 哈尔滨工业大学 | Method for preparing porous metal through high-temperature oxidation and reduction |
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2017
- 2017-01-05 CN CN201710007939.4A patent/CN106756747B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009144563A2 (en) * | 2008-05-29 | 2009-12-03 | Politecnico Di Milano | Methods for obtaining an open-pore metal foam, composite material and open-pore metal foam |
| CN105506336A (en) * | 2015-12-23 | 2016-04-20 | 哈尔滨工业大学 | Method for preparing porous metal through high-temperature oxidation and reduction |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108467948A (en) * | 2018-04-19 | 2018-08-31 | 上海泰坦科技股份有限公司 | A kind of palladium and its preparation method and application |
| CN108467948B (en) * | 2018-04-19 | 2020-05-22 | 上海泰坦科技股份有限公司 | Palladium and preparation method and application thereof |
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Effective date of registration: 20230906 Address after: 423000 Xiaobu Village Committee Garden, Baohe Yao Township, Beihu District, Chenzhou City, Hunan Province Patentee after: Chenzhou Zhexuan Metal Co.,Ltd. Address before: 230000 floor 1, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee before: Dragon totem Technology (Hefei) Co.,Ltd. Effective date of registration: 20230906 Address after: 230000 floor 1, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee after: Dragon totem Technology (Hefei) Co.,Ltd. Address before: 610106 No. 1, Shangjie, waidong Shiling Town, Chengdu, Sichuan Patentee before: CHENGDU University |