CN106756747B - The preparation method of porous palladium material - Google Patents
The preparation method of porous palladium material Download PDFInfo
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- CN106756747B CN106756747B CN201710007939.4A CN201710007939A CN106756747B CN 106756747 B CN106756747 B CN 106756747B CN 201710007939 A CN201710007939 A CN 201710007939A CN 106756747 B CN106756747 B CN 106756747B
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- palladium
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- sulfide
- hydrogen
- porous
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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
-
- 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
Abstract
The invention belongs to the preparation methods (1) of field of metal material surface treatment, specially porous palladium material to clean to raw material, and with pure palladium or palldium alloy material, (2) corrode palladium surface using hydrogen sulfide gas；(3) oxidation removal is carried out to spherical palladium sulfide using purity oxygen；(4) it is restored using hydrogen pair with the palladium material after pure oxygen solid/liquid/gas reactions, porous palladium material is prepared.The preparation method of porous palladium material provided by the invention corrodes palladium surface using hydrogen sulfide gas, and carrys out control corrosion rate degree by adjusting the mode in 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 restored using hydrogen, by adjusting recovery time, temperature, gas concentration etc., utmostly to retain the porous 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 technique
The preparation method of porous palladium material, mainly there is following methods:
One, PM technique prepares porous palladium material
1, conventional powder metallurgy prepares porous palladium material
After palladium powder is by screening, direct die-filling sintering obtains porous palladium materials after finally demoulding.Program simple process, but
Material porosity is relatively low, merges between powder serious.
2, the PM technique for adding pore creating material prepares porous palladium material
Using palladium powder as raw material, using water soluble salt powder as pore creating material, using water, ethyl alcohol or acetone as dispersing agent, it is aided with it
His auxiliary agent is dried and mixed powder is made using hand lapping and ball milling mixing mode；Mixed powder is pressed and molded as sheet or
Blocky green compact is put it into vacuum or sintering furnace filled with protective gas, after green compact is dry in 400 DEG C of -1200 DEG C of temperature
Sintered blank is sintered into range；Obtained sintered blank 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.The resulting porous palladium material of the preparation method has gap rate higher and big
Small adjustable feature.But this method is easy to introduce in impurity and sintering process carbon pollution occur in process.
3, discharge plasma sintering prepares porous palladium material
Palladium powder by screen it is die-filling after, be placed in SPS agglomerating plant in be sintered, finally demould after obtain porous palladium materials.SPS is burnt
Knot technology has heating rate fast, and sintering time is short (generally only needing a few minutes), and sintered body is relatively uniform, simultaneously because pulse is electric
The effect of stream can reduce the sintering temperature of material, can effectively inhibit the growing up of crystal grain, the controllability of technical process preferably, crystal grain
Surface is easy the characteristics of activation, but program higher cost, material porosity be not high.
Two prepare porous palladium material using porous material for carrier
1, preparation method are as follows: (1) using chemically plating for the palladium coating ceramic powder of core-shell structure；(2) palladium is coated
Slurry is made in ceramic powder, is uniformly applied to porous carrier surface, then obtains the transition of palladium coating ceramic by high-temperature heat treatment
Layer；(3) chemical plating is carried out in palladium coating ceramic transition layer surface form palladium or palldium alloy film.This 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.Palladium crystal seed is provided since palladium coating ceramic transition zone plates process palladium membranes deposition for subsequent chemistry, avoids biography
Chemical plating of uniting sensitization activation process introduces tin impurity, is conducive to the high-temperature stability for improving palladium or palladium alloy composite membrane.But the party
Method technique is cumbersome, porosity is lower.
Three, it is handled using atmosphere and palladium surface is modified
Oxidation processes are carried out to palladium surface using oxygen, vapor etc., so that palladium Surface Creation is aoxidized palladium layers, then uses hydrogen
Oxidation palladium layers are restored, 1) palladium surface impurity, the especially removal of organic carbonaceous impurity may be implemented；2) palladium surface is improved
Surface area；3) hydrogenolysis of palladium film is improved from activity.The roughening of palladium surface topography may be implemented in this method, real to a certain extent
The modifying function on existing palladium surface, but palladium surface can not be made to form orderly porous state, also can not device to hole size and quantity into
Row control.
Summary of the invention
In view of the above technical problems, the present invention provide it is a kind of cost is relatively low, simple process, material porosity is high and controllable
The preparation method of porous palladium material.
Specific technical solution are as follows:
The preparation method of porous palladium material, including following procedure:
(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) it is restored using hydrogen pair with the palladium material after pure oxygen solid/liquid/gas reactions, pure porous palladium material is prepared.
Specifically, the step (2), detailed process is that palladium material is placed in the reaction that can be passed through mobility gas
In furnace, hydrogen sulfide gas is passed through with the rate of 2ml-100ml/s and is reacted with palladium material, hydrogen sulfide forms spherical with palladium surface
Or granular palladium sulfide selects different according to spherical or the graininess palladium sulfide quantity, the difference of size of required generation
Reaction temperature is arranged in pairs or groups with the time, and reaction temperature section is 260 DEG C -740 DEG C, reaction time 20s-60min.
The step (3), detailed process be, rear surface will be reacted with hydrogen sulfide generates the palladium material of palladium sulfide conversion zone
Material is used as raw material, is placed in the reacting furnace that can be passed through mobility gas, is passed through pure oxygen gas with the rate of 2ml-100ml/s
It is reacted with palladium material；Reaction temperature is 520 DEG C -650 DEG C, reaction time 5min-30min；Spherical palladium sulfide is by oxygen
Palladium oxide is formed after oxidation, and because hole occurs in volume contraction.
The step (4), detailed process be, will with after pure oxygen solid/liquid/gas reactions, the Surface Creation palladium material of oxidation palladium layers
It is directly 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 purges it, to control reaction rate.Reaction temperature is subzero 20 DEG C to 20 DEG C above freezing, reaction time 30s-
20min。
The preparation method of porous palladium material provided by the invention, key problem in technology are:
1, palladium surface is corroded using hydrogen sulfide gas, and come by adjusting the mode of reaction time and reaction temperature
Control corrosion rate degree.
2, 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.
3, cellular oxidation palladium layers are restored using hydrogen, by adjusting recovery time, temperature, gas concentration etc.,
Utmostly to retain the porous structure of porous palladium material.
The preparation method of porous palladium material provided by the invention, the technical effect having have:
1, thermal sintering porous palladium material after existing PM technique uses powder directly or addition pore creating material, the material
There is a problem of that lower porosity, surface contamination, the smaller catalytic activity of surface area be not strong.This method is using hydrogen sulfide to palladium table
Face is corroded, and is then surface-treated again to it using redox mode, when by control reaction temperature with reacting
Between can more accurately control palladium surface pore structure and hole quantity, may be implemented porosity further increase, surface contamination
The purpose of removal, surface area increase, to further increase the service performance of material.
2, have in the prior art using dioxygen oxidation and hydrogen reducing and realize that the removal of palladium surface organic matter is thick with palladium surface
The increased relevant report of rugosity, but it aims at the purification for realizing palladium surface, rather than change the architectural characteristic on palladium surface.We
Method first corrodes palladium surface using hydrogen sulfide, and then carries out oxidation removal using palladium sulfide of the oxygen to generation, then use
Hydrogen restores the palladium oxide of generation, and the palladium surface topography of porous structure can be prepared, have surface roughness with
The characteristics of surface cleanliness further increases, and the catalytic activity of material greatly improves.
Detailed description of the invention
Fig. 1 is pure palladium surface texture in embodiment:
Fig. 2 is pure palladium hydrogen sulfide corrosion rear surface structure in embodiment；
Fig. 3 is pure palladium redox rear surface structure in embodiment.
Specific embodiment
Technical solution of the present invention is elaborated in conjunction with the embodiments.
(1) raw material are cleaned；Detailed process are as follows: using pure palladium as raw material, such as Fig. 1 is pure palladium surface texture.It adopts
After cleaning 3 times or more repeatedly with acetone, alcohol, deionized water, dried for standby.
(2) palladium surface is corroded using hydrogen sulfide gas；Specifically comprises the processes of: flowing can be passed through by being placed in palladium material
In the reacting furnace of property gas, be passed through hydrogen sulfide gas with the rate of 2ml-100ml/s is reacted with palladium material, hydrogen sulfide and palladium
Surface forms spherical or granular palladium sulfide, not according to spherical or graininess palladium sulfide quantity, the size of required generation
Together, different reaction temperatures is selected to arrange in pairs or groups with the time, reaction temperature section is 260 DEG C -740 DEG C, reaction time 20s-
60min；Pure palladium hydrogen sulfide corrosion rear surface photo such as Fig. 2.
(3) oxidation removal is carried out to spherical palladium sulfide using purity oxygen；Specifically comprises the processes of: rear surface will be reacted with hydrogen sulfide
The palladium material of palladium sulfide conversion zone is generated as raw material, is placed in the reacting furnace that can be passed through mobility gas, with 2ml-
The rate 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) it is restored using hydrogen pair with the palladium material after pure oxygen solid/liquid/gas reactions, porous palladium material is prepared；Specific work
Skill are as follows: will be with after pure oxygen solid/liquid/gas reactions, 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 the mixed gas of hydrogen or hydrogen and inert gas is used to purge it, with control reaction speed
Rate.Reaction temperature is subzero 20 DEG C to 20 DEG C above freezing, reaction time 30s-20min.Pure palladium material surface after redox
Structure such as Fig. 3.
Claims (2)
1. the preparation method of porous palladium material, which is characterized in that including following procedure:
(1) using 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；Detailed process
For palladium material is placed in the reacting furnace that can be passed through mobility gas, is passed through hydrogen sulfide gas with the rate of 2ml-100ml/s
It is reacted with palladium material, hydrogen sulfide and palladium surface form spherical or granular palladium sulfide, according to the spherical of required generation
Or graininess palladium sulfide quantity, the difference of size, select different reaction temperatures to arrange in pairs or groups with the time, reaction temperature section is
260 DEG C -740 DEG C, reaction time 20s-60min；
(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；Detailed process is, rear surface will be reacted with hydrogen sulfide and generates the palladium material of palladium sulfide conversion zone as raw material,
It is placed in the reacting furnace that can be passed through mobility gas, pure oxygen gas is passed through with the rate of 2ml-100ml/s and palladium material carries out
Reaction；Reaction temperature is 520 DEG C -620 DEG C, reaction time 5min-30min；Spherical palladium sulfide forms oxygen after being oxidized by oxygen
Change palladium, and because hole occurs in volume contraction；
(4) it is restored using hydrogen pair with the palladium material after pure oxygen solid/liquid/gas reactions, pure porous palladium material is prepared.
2. the preparation method of porous palladium material according to claim 1, which is characterized in that the step (4), specific mistake
Cheng Wei, will be with after pure oxygen solid/liquid/gas reactions, and 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 the mixed gas of hydrogen or hydrogen and inert gas is used to purge it, with control reaction speed
Rate, reaction temperature are subzero 20 DEG C to 20 DEG C above freezing, reaction time 30s-20min.
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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 |
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