CN109821535A - Rare earth oxide supports the bimetallic hydrophobic catalyst of platinum ruthenium and its preparation method and application - Google Patents
Rare earth oxide supports the bimetallic hydrophobic catalyst of platinum ruthenium and its preparation method and application Download PDFInfo
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Abstract
The invention discloses rare earth oxides to support the bimetallic hydrophobic catalyst of platinum ruthenium and its preparation method and application, and catalytic performance is low in the prior art for solution, the bad problem of economy.Rare earth oxide of the present invention supports the bimetallic hydrophobic catalyst of platinum ruthenium, is support carrier with metal fiber felt using polytetrafluoroethylene (PTFE) as bonding agent and hydrophobic medium to support the bimetallic rare earth oxide of platinum ruthenium as active component；Described to support in the bimetallic rare earth oxide of platinum ruthenium, the load capacity of platinum is 0.1wt%~10wt%, and the atomic ratio of ruthenium and platinum is 1: 1~10；The bimetallic rare earth oxide of platinum ruthenium and the weight ratio of polytetrafluoroethylene (PTFE) of supporting is 1: 1~4；For the quality of the catalyst based on 100%, the quality accounting of the metal fiber felt is 30%~70%.Design science of the present invention, method is simple, and catalyst of the invention has excellent catalytic properties, good economy performance.
Description
Technical field
The invention belongs to HYDROGEN-WATER ISOTOPE EXCHANGE catalyst technical fields, and in particular to it is double that rare earth oxide supports platinum ruthenium
The hydrophobic catalyst and its preparation method of metal and application.
Background technique
Greatly developing nuclear power is that China relies on to mitigate fossil energy, ensures the strategy that national energy security is made
Selection.But the cores such as nuclear reactor (fusion reactor including all types of fission-type reactors and plan construction in the future) and spentnuclear fuel reprocessing plant
The operation of facility can generate a large amount of tritium-containing liquid waste (containing HTO, DTO or T2O).Compared with gaseous state tritium, tritiated water is to organism
Toxicity will significantly increase about 25000 times.In view of the radiological hazard containing surabaya, for light-water containing tritium (as pressurized water reactor produces
Raw waste water), tritiated processing is being gone to water should be carried out before environmental emission, to mitigate its danger to ecological environment and public health
Evil.At this stage, since the nuclear power station in China build coastal area in, light-water containing tritium generally all directly arranges Xiang great Hai, utilizes flood tide
Seawater be diluted, to achieve the purpose that harm reduction.But the inland of addressing and demonstration is set about for China in recent years
For nuclear power station, light-water containing tritium is directly arranged to rivers then may bring potential danger to the ecological environment and public health in downstream
Evil.On the other hand, for heavy water reactor, being used for the heavy water of moderation of neutrons also must be into after reactor operation for a period of time
Row proposes tritium processing, otherwise can reduce the moderation of neutrons efficiency of heavy water, or even influence the safe operation of nuclear power station.Therefore, develop
Water goes tritiated (or heavy water detritiation) technology to have a very important significance the development of China's nuclear industry.
Currently, can be used for water to remove tritiated technological approaches mainly including hydrogen-water isotope liquid-phase catalysis exchange (Liquid
Phase Catalytic Exchange, is abbreviated as LPCE), vapor phase catalysis exchange (VaporPhase Catalytic
Exchange is abbreviated as VPCE) and combination electrolysis/catalysis exchange (Combined Electrolysis Catalytic
Exchange is abbreviated as CECE) etc..Wherein, LPCE refers to that hydrogen isotope gas and liquid water occur together under the action of catalyst
The plain exchange reaction in position；VPCE refers to that isotope occurs under the action of catalyst for hydrogen isotope gas and vapor (~200 DEG C)
Exchange reaction；And CECE be substantially LPCE process is combined together with water electrolysis process, to realize higher detritiation because
Son (note: this is because the electrolytic process of water is with isotope effect, it can be achieved that the concentration of tritium).In summary, hydrogen isotope gas
Hydrogen isotopic exchange occurs between body and water (liquid or gaseous state) to react to be core reaction mistake that above-mentioned three kinds of water goes tritiated technology
Journey.In these three technological approaches, the operating condition of LPCE is most mild, energy consumption is minimum, equipment requirement is also most simple, therefore by
Universal attention.
Due to hereinafter, water exists in liquid form, hindering hydrogen to reach to prevent water to be covered on active metal surface at 100 DEG C
To active site (causing catalyst poisoning), needed in LPCE technique using hydrophobic catalyst.Currently, in countries in the world
LPCE device in be widely used that with the hydrophobic catalyst of platinum active metal, there are mainly three types of type: the first kind is direct
Platinum is supported on hydrophobic medium, such as Pt/SDBC (Styrene Divinylbenzene Copolymer, i.e. polyethylene-diethyl
Alkenyl benzene polymer)；Second class is that first platinum is supported on the carrier with high-specific surface area (mainly to include Carbon Materials, aoxidize
Aluminium, silica), silicic acid anhydride system is then carried out using PTFE (Polytetrafluoroethene, i.e. polytetrafluoroethylene (PTFE))
Obtain hydrophobic catalyst；Third class is that first platinum is supported on the carrier with high-specific surface area, is then coated to together with PTFE
Hydrophobic catalyst is made on stainless steel fibre felt.Noble metal platinum is HYDROGEN-WATER ISOTOPE EXCHANGE hydrophobic catalyst due to expensive
The prime cost constituent element of agent.In above-mentioned three classes hydrophobic catalyst, the noble metal platinum of third class hydrophobic catalyst utilizes effect
Rate is relatively higher.But there is also following both sides problems for the type hydrophobic catalyst: one, only using platinum as active metal, catalysis is lived
The regulation of property improves the dispersion degree of nano platinum particle by using high surface area carrier mainly to realize, regulating effect is limited；
Two, currently used carrier is inert to HYDROGEN-WATER ISOTOPE EXCHANGE reaction, and main function is to improve noble metal platinum
Dispersion degree, there is no substantial promoting catalysis.
Therefore it provides a kind of hydrophobic catalyst for HYDROGEN-WATER ISOTOPE EXCHANGE, has excellent catalytic properties and has
Good economy becomes those skilled in the art's urgent problem to be solved.
Summary of the invention
Technical problem solved by the present invention is providing rare earth oxide supports the bimetallic hydrophobic catalyst of platinum ruthenium, solve
Catalytic performance is low in the prior art, the bad problem of economy.
The present invention also provides the preparation methods that the rare earth oxide supports the bimetallic hydrophobic catalyst of platinum ruthenium.
Invention further provides the applications that the rare earth oxide supports the bimetallic hydrophobic catalyst of platinum ruthenium.
The technical solution adopted by the invention is as follows:
Rare earth oxide of the present invention supports the bimetallic hydrophobic catalyst of platinum ruthenium, bimetallic dilute to support platinum ruthenium
Native oxide is active component, is support carrier with metal fiber felt using polytetrafluoroethylene (PTFE) as bonding agent and main hydrophobic medium；
Described to support in the bimetallic rare earth oxide of platinum ruthenium, the load capacity of platinum is 0.1wt%~10wt%, and the atomic ratio of ruthenium and platinum is
1:1~10；The bimetallic rare earth oxide of platinum ruthenium and the weight ratio of polytetrafluoroethylene (PTFE) of supporting is 1:1~4, the catalyst
Quality based on 100%, the quality accounting of the metal fiber felt is 30%~70%.
Further, described to support in platinum ruthenium bimetallic rare earth oxide, the load capacity of platinum is 2wt%, the original of ruthenium and platinum
Son is than being 1:2；Or/and the bimetallic rare earth oxide of platinum ruthenium and the weight ratio of polytetrafluoroethylene (PTFE) of supporting is 1:2；Or/and
The content of the metal fiber felt is 50wt%.
Rare earth oxide of the present invention supports the preparation method of the bimetallic hydrophobic catalyst of platinum ruthenium, comprising the following steps:
Step 1. preparation supports the bimetallic rare earth oxide of platinum ruthenium: platinum ruthenium bimetallic is loaded to rare earth oxide carrier
On；
Step 2. prepares suspension: the bimetallic rare earth oxide of platinum ruthenium and polytetrafluoroethylene (PTFE) will be supported made from step 1
It is mixed in a certain ratio, is configured to suspension；
Step 3. coating: suspension made from step 2 is coated on metal fiber felt, is then dried, obtains coating
Sample；
Step 4. heat treatment: the coated sample is placed in atmosphere heat treatment furnace, be passed through after vacuumizing hydrogen with it is lazy
Property gas gaseous mixture, with certain heating rate heating, constant temperature for a period of time after, stop heating, sample under atmosphere protection with
Furnace is cooled to room temperature.
Further, the metal fiber felt is stainless steel fibre felt, and aperture is 20 mesh.
Further, in the step 1, platinum ruthenium bimetallic is loaded to using the technique of " dipping+calcining+gas reduction "
On rare earth oxide carrier.
Further, the specific operation process of the step 1 are as follows:
A. it impregnates: chloroplatinic acid hydrate and ruthenic chloride is dissolved into respectively in deionized water and are made into chloroplatinic acid and ruthenic chloride water
Solution, wherein platinum ion and ruthenium ion concentration are 0.01~0.1mol/L；Ceria or other rare earth oxides are weighed, then
A certain amount of chloroplatinic acid and ruthenium chloride aqueous solution are sought after evenly mixing according to load capacity, be added to ceria or other are dilute
In native oxide, it is sufficiently stirred, it is dry；
B. it calcines: the sample after step A is dry being put into tube furnace and is calcined, in the zero level that flow is 300ml/min
Be heated to 400 DEG C, constant temperature 2h under air atmosphere with 10K/min, after cool to room temperature with the furnace；
C. it restores: will be through the calcined sample reduction treatment of step B, it is 300ml/min's that treatment conditions, which are in flow,
10%H2Be heated to 400 DEG C, constant temperature 2h under/Ar gaseous mixture atmosphere with 5K/min, it is rear to stop heating, sample under atmosphere protection with
Furnace is cooled to room temperature.
Further, in the step 2, the bimetallic rare earth oxide of platinum ruthenium and polytetrafluoroethylene (PTFE) in mass ratio 1 are supported:
2 mixing are added deionized water and form mixture aqueous solution, then surfactant is added into mixture aqueous solution, are configured to hang
Turbid.
Further, in the step 2, resistivity >=15M Ω of the deionized water, additive amount is to support platinum ruthenium pair
10~20 times of the rare-earth oxidation amount of substance of metal；The surfactant is triton X-100, and additive amount is to support platinum ruthenium
5~10 times of bimetallic rare-earth oxidation amount of substance.
Further, in the step 3, using multiple coating processes, suspension made from step 2 is coated to metal fibre
After tieing up on felt, heated baking water removal, after preliminarily dried, coating, heated baking again, until reaching required load capacity, institute
The temperature for stating baking is 110-130 DEG C.
Further, in the step 4, the volume content of hydrogen is 1~10% in the gaseous mixture of hydrogen and inert gas, is mixed
The flow for closing gas is 100~500ml/min；Heating rate is 1~10 DEG C/min, is heated to 350-380 DEG C.
Rare earth oxide of the present invention supports the bimetallic hydrophobic catalyst of platinum ruthenium in HYDROGEN-WATER ISOTOPE EXCHANGE
Using.
Compared with prior art, the invention has the following advantages:
(1) design science of the present invention, method is simple, and catalyst of the invention has excellent catalytic properties, regeneration frequency
Low, stability is good.
(2) present invention to be to support the bimetallic rare earth oxide of platinum ruthenium as active component, polytetrafluoroethylene (PTFE) be bonding agent and
Main hydrophobic medium, metal fiber felt are support carrier, the hydrophobic catalyst being prepared.Since rare earth oxide surface has
Lacking oxygen abundant can play the role of activated water molecule, and then promote the isotope exchange reaction between hydrogen and water, rare earth oxygen
Compound base hydrophobic catalyst is better than same type dredging using platinum charcoal as active component to the catalytic efficiency that HYDROGEN-WATER ISOTOPE EXCHANGE is reacted
Water catalyst.For example, under the test condition that temperature is 80 DEG C, gas liquid ratio is 1, Pt/CeO2Hydrophobic catalyst is in noble metal platinum
Dosage still less than Pt/C hydrophobic catalyst half under the premise of, to HYDROGEN-WATER ISOTOPE EXCHANGE reaction catalysis react column efficiency
It has been better than the latter.Further, using relatively cheap ruthenium (one third that its market price is only platinum) to Pt/CeO2It is hydrophobic to urge
After the active metal of agent is modified, PtRu obtained0.5/CeO2The catalytic efficiency of hydrophobic catalyst is again compared with Pt/CeO2It is hydrophobic
Catalyst improves 15% or more, and economy is more prominent.
(3) cost performance of the present invention is high, catalytic performance is good, can remove tritiated, heavy water detritiation and heavy water production in tritium-containing liquid waste
Commercial applications are realized in equal fields, therefore the present invention has very high practical value and promotional value.
Detailed description of the invention
Fig. 1 is the Contact-angle measurement knot for the bimetallic hydrophobic catalyst of cerium dioxide-bound platinum ruthenium that the present invention is prepared
Fruit.
Fig. 2 is the PtRu that the present invention is prepared0.5/CeO2Hydrophobic catalyst and Pt/CeO2And tradition Pt/C hydrophobic catalyst
The catalysis reaction column efficiency that HYDROGEN-WATER ISOTOPE EXCHANGE is reacted is compared in agent.
Specific embodiment
The invention will be further described with embodiment for explanation with reference to the accompanying drawing, and mode of the invention includes but not only limits
In following embodiment.
Embodiment 1
Present embodiment discloses the preparation method that rare earth oxide of the invention supports the bimetallic hydrophobic catalyst of platinum ruthenium,
Specifically:
Step 1. preparation supports the bimetallic rare earth oxide of platinum ruthenium: chloroplatinic acid hydrate addition deionized water is configured to
Platinum ion concentration is the chloroplatinic acid aqueous solution of 0.01mol/L, and ruthenic chloride addition deionized water is configured to ruthenium ion concentration and is
The ruthenium chloride aqueous solution of 0.01mol/L；
In chloroplatinic acid aqueous solution: the ratio that the volume ratio of ruthenium chloride aqueous solution is 2:1 measures chloroplatinic acid aqueous solution and chlorination
Ruthenium aqueous solution is uniformly mixed, obtains mixed aqueous solution.
A certain amount of ceria is weighed, the load capacity according to platinum is that the 2wt% addition mixing of ceria quality is water-soluble
Liquid is sufficiently stirred.It after preliminarily dried, is put into vacuum oven and is further done at 110 DEG C in 65 DEG C of waters bath with thermostatic control after sample
Dry 12h.Then, the sample after drying is put into tube furnace and is calcined, flow be 300ml/min zero level air atmosphere under with
10K/min is heated to 400 DEG C, constant temperature 2h, after cool to room temperature with the furnace.Calcined sample then carries out reduction treatment, processing
Condition is the 10%H for being 300ml/min in flow2Be heated to 400 DEG C, constant temperature 2h under/Ar gaseous mixture atmosphere with 5K/min, after with
Furnace is cooled to room temperature, and is made and has been supported the bimetallic rare earth oxide of platinum ruthenium.
Step 2. prepares suspension: being made after supporting the bimetallic rare earth oxide of platinum ruthenium, it is pressed with polytetrafluoroethylene (PTFE)
Mass ratio 1:2 mixing is added deionized water and forms mixture aqueous solution, then surfactant song is added into mixture aqueous solution
Logical X100 is drawn, suspension is formed.Wherein, the resistivity of deionized water >=15M Ω, additive amount are to support platinum ruthenium bimetallic rare earth
10 times of oxide mass；The additive amount of triton X-100 is 5 times for supporting platinum ruthenium bimetallic rare-earth oxidation amount of substance.
Step 3. is loaded on stainless steel fibre felt using multiple coating processes, and suspension made from step 2 is applied
After being layed on metal fiber felt, heated baking water removal, after preliminarily dried, coating, heated baking again, until reaching required
Load capacity, the temperature of the baking are 130 DEG C.The quality of manufactured catalyst is based on 100%, the quality accounting of metal fiber felt
It is 50%.
The coated sample is placed in atmosphere heat treatment furnace by step 4., is passed through after vacuumizing after vacuumizing and is passed through hydrogen
It is the 10%H of 200ml/min in flow with the gaseous mixture of inert gas2365 are heated to under/Ar gaseous mixture atmosphere with 2 DEG C/min
DEG C, constant temperature 15min, after cool to room temperature with the furnace.
Embodiment 2
Present embodiment discloses the preparation method that rare earth oxide of the invention supports the bimetallic hydrophobic catalyst of platinum ruthenium,
Specifically:
Step 1. preparation supports the bimetallic rare earth oxide of platinum ruthenium: chloroplatinic acid hydrate addition deionized water is configured to
Platinum ion concentration is the chloroplatinic acid aqueous solution of 0.1mol/L, and ruthenic chloride addition deionized water is configured to ruthenium ion concentration and is
The ruthenium chloride aqueous solution of 0.1mol/L；
In chloroplatinic acid aqueous solution: the ratio that the volume ratio of ruthenium chloride aqueous solution is 1:1 measures chloroplatinic acid aqueous solution and chlorination
Ruthenium aqueous solution is uniformly mixed, obtains mixed aqueous solution.
A certain amount of ceria is weighed, the load capacity according to platinum is that mixing water is added in the 0.1wt% of ceria quality
Solution is sufficiently stirred.It after preliminarily dried, is put into vacuum oven at 110 DEG C further in 65 DEG C of waters bath with thermostatic control after sample
Dry 12h.Then, the sample after drying is put into tube furnace and is calcined, in the case where flow is the zero level air atmosphere of 300ml/min
Be heated to 400 DEG C, constant temperature 2h with 10K/min, after cool to room temperature with the furnace.Calcined sample then carries out reduction treatment, place
Manage bar part is the 10%H for being 300ml/min in flow2400 DEG C, constant temperature 2h are heated to 5K/min under/Ar gaseous mixture atmosphere, after
It cools to room temperature with the furnace, is made and has supported the bimetallic rare earth oxide of platinum ruthenium.
Step 2. prepares suspension: being made after supporting the bimetallic rare earth oxide of platinum ruthenium, it is pressed with polytetrafluoroethylene (PTFE)
Mass ratio 1:4 mixing is added deionized water and forms mixture aqueous solution, then surfactant song is added into mixture aqueous solution
Logical X100 is drawn, suspension is formed.Wherein, the resistivity of deionized water >=15M Ω, additive amount are to support platinum ruthenium bimetallic rare earth
20 times of oxide mass；The additive amount of triton X-100 is 10 times for supporting platinum ruthenium bimetallic rare-earth oxidation amount of substance.
Step 3. is loaded on stainless steel fibre felt using multiple coating processes, and suspension made from step 2 is applied
After being layed on metal fiber felt, heated baking water removal, after preliminarily dried, coating, heated baking again, until reaching required
Load capacity, the temperature of the baking are 110 DEG C.The quality of manufactured catalyst is based on 100%, the quality accounting of metal fiber felt
It is 30%.
The coated sample is placed in atmosphere heat treatment furnace by step 4., is passed through after vacuumizing after vacuumizing and is passed through hydrogen
It is the 1%H of 100ml/min in flow with the gaseous mixture of inert gas2380 are heated to under/Ar gaseous mixture atmosphere with 2 DEG C/min
DEG C, constant temperature 15min, after cool to room temperature with the furnace.
Embodiment 3
Present embodiment discloses the preparation method that rare earth oxide of the invention supports the bimetallic hydrophobic catalyst of platinum ruthenium,
Specifically:
Step 1. preparation supports the bimetallic rare earth oxide of platinum ruthenium: chloroplatinic acid hydrate addition deionized water is configured to
Platinum ion concentration is the chloroplatinic acid aqueous solution of 0.05mol/L, and ruthenic chloride addition deionized water is configured to ruthenium ion concentration and is
The ruthenium chloride aqueous solution of 0.05mol/L；
In chloroplatinic acid aqueous solution: the ratio that the volume ratio of ruthenium chloride aqueous solution is 10:1 measures chloroplatinic acid aqueous solution and chlorination
Ruthenium aqueous solution is uniformly mixed, obtains mixed aqueous solution.
A certain amount of ceria is weighed, the load capacity according to platinum is that the 10wt% addition mixing of ceria quality is water-soluble
Liquid is sufficiently stirred.It after preliminarily dried, is put into vacuum oven and is further done at 110 DEG C in 65 DEG C of waters bath with thermostatic control after sample
Dry 12h.Then, the sample after drying is put into tube furnace and is calcined, flow be 300ml/min zero level air atmosphere under with
10K/min is heated to 400 DEG C, constant temperature 2h, after cool to room temperature with the furnace.Calcined sample then carries out reduction treatment, processing
Condition is the 10%H for being 300ml/min in flow2Be heated to 400 DEG C, constant temperature 2h under/Ar gaseous mixture atmosphere with 5K/min, after with
Furnace is cooled to room temperature, and is made and has been supported the bimetallic rare earth oxide of platinum ruthenium.
Step 2. prepares suspension: being made after supporting the bimetallic rare earth oxide of platinum ruthenium, it is pressed with polytetrafluoroethylene (PTFE)
Mass ratio 1:1 mixing is added deionized water and forms mixture aqueous solution, then surfactant song is added into mixture aqueous solution
Logical X100 is drawn, suspension is formed.Wherein, the resistivity of deionized water >=15M Ω, additive amount are to support platinum ruthenium bimetallic rare earth
15 times of oxide mass；The additive amount of triton X-100 is 8 times for supporting platinum ruthenium bimetallic rare-earth oxidation amount of substance.
Step 3. is loaded on stainless steel fibre felt using multiple coating processes, and suspension made from step 2 is applied
After being layed on metal fiber felt, heated baking water removal, after preliminarily dried, coating, heated baking again, until reaching required
Load capacity, the temperature of the baking are 120 DEG C.The quality of manufactured catalyst is based on 100%, the quality accounting of metal fiber felt
It is 70%.
The coated sample is placed in atmosphere heat treatment furnace by step 4., is passed through after vacuumizing after vacuumizing and is passed through hydrogen
It is the 5%H of 500ml/min in flow with the gaseous mixture of inert gas2350 are heated to under/Ar gaseous mixture atmosphere with 10 DEG C/min
DEG C, constant temperature 15min, after cool to room temperature with the furnace.
Embodiment 4
Present embodiment discloses the property that rare earth oxide made from embodiment 1 supports the bimetallic hydrophobic catalyst of platinum ruthenium
Energy.
Rare earth oxide made from embodiment 1 is supported into the bimetallic hydrophobic catalyst of platinum ruthenium and carries out Contact-angle measurement, knot
Fruit shows that the contact angle with water is at 130 ° or so, as shown in Fig. 1, shows it with good hydrophobicity.
We are cut, after moulding, contrast test present invention under conditions of 80 DEG C, hydrogen and aqueous vapor liquor ratio are 1
Prepared PtRu0.5/CeO2Hydrophobic catalyst and Pt/CeO2And traditional Pt/C hydrophobic catalyst is to HYDROGEN-WATER ISOTOPE EXCHANGE
The catalytic performance of reaction.The results show that 2wt%PtRu prepared by the present invention0.5/CeO2The catalytic performance of hydrophobic catalyst is not
Only it is better than 10wt%Pt/C hydrophobic catalyst, is also significantly better than 2wt%Pt/CeO not modified using ruthenium2Hydrophobic catalyst, such as
Shown in attached drawing 2.Compared with traditional Pt/C hydrophobic catalyst, Pt/CeO2Hydrophobic catalyst noble metal platinum dosage still it is insufficient the former
Under conditions of half, the catalysis reaction column efficiency to HYDROGEN-WATER ISOTOPE EXCHANGE reaction has been more than for the former；And it uses relatively inexpensive
Ruthenium to Pt/CeO2Hydrophobic catalyst carries out further modified, PtRu obtained0.5/CeO2The catalytic efficiency of hydrophobic catalyst
Again compared with Pt/CeO2Hydrophobic catalyst improves 15% or more, and economy is more prominent.
The above description is only a preferred embodiment of the present invention, is merely illustrative for the purpose of the present invention, and not restrictive；
Those of ordinary skill in the art understand, can carry out many to it in the spirit and scope defined by the claims in the present invention and change
Become, modification or even equivalent change, but falls in protection scope of the present invention.
Claims (10)
1. rare earth oxide supports the bimetallic hydrophobic catalyst of platinum ruthenium, which is characterized in that support the bimetallic rare earth of platinum ruthenium
Oxide is active component, is support carrier with metal fiber felt using polytetrafluoroethylene (PTFE) as bonding agent and main hydrophobic medium；Institute
It states and supports in the bimetallic rare earth oxide of platinum ruthenium, the load capacity of platinum is 0.1wt%~10wt%, and it is double that rare earth oxide carries platinum ruthenium
Metal；The bimetallic rare earth oxide of platinum ruthenium and the weight ratio of polytetrafluoroethylene (PTFE) of supporting is 1:1~4；The catalyst
For quality based on 100%, the quality accounting of the metal fiber felt is 30%~70%.
2. rare earth oxide according to claim 1 supports the bimetallic hydrophobic catalyst of platinum ruthenium, which is characterized in that described
It supports in the bimetallic rare earth oxide of platinum ruthenium, the load capacity of platinum is 2wt%, and the atomic ratio of ruthenium and platinum is 1:2；Or/and it is described
The weight ratio for supporting the bimetallic rare earth oxide of platinum ruthenium and polytetrafluoroethylene (PTFE) is 1:2；Or/and the content of the metal fiber felt
For 50wt%.
3. rare earth oxide according to claim 1 or 2 supports the preparation method of the bimetallic hydrophobic catalyst of platinum ruthenium, feature
It is, comprising the following steps:
Step 1. preparation supports the bimetallic rare earth oxide of platinum ruthenium: platinum and ruthenium are loaded on rare earth oxide carrier；
Step 2. prepare suspension: will have been supported made from step 1 the bimetallic rare earth oxide of platinum ruthenium and polytetrafluoroethylene (PTFE) by
Certain proportion mixing, is configured to suspension；
Step 3. coating: suspension made from step 2 is coated on metal fiber felt, is then dried, coated sample is obtained
Product；
Step 4. heat treatment: the coated sample is placed in atmosphere heat treatment furnace, is passed through hydrogen and indifferent gas after vacuumizing
The gaseous mixture of body, with the heating of certain heating rate, constant temperature for a period of time after, stop heating, sample is cold with furnace under atmosphere protection
But to room temperature.
4. rare earth oxide according to claim 3 supports the preparation method of the bimetallic hydrophobic catalyst of platinum ruthenium, feature exists
In platinum ruthenium is loaded to rare earth oxide by a certain percentage using the technique of " dipping+calcining+gas reduction " in the step 1
On carrier.
5. rare earth oxide according to claim 4 supports the preparation method of the bimetallic hydrophobic catalyst of platinum ruthenium, feature exists
In the specific operation process of the step 1 are as follows:
A. it impregnates: chloroplatinic acid hydrate and ruthenic chloride is dissolved into respectively in deionized water and are made into chloroplatinic acid and ruthenic chloride is water-soluble
Liquid, wherein platinum ion and ruthenium ion concentration are 0.01~0.1mol/L；Ceria or other rare earth oxides are weighed, then root
A certain amount of chloroplatinic acid and ruthenium chloride aqueous solution are sought after evenly mixing according to load capacity, be added to ceria or other rare earths
In oxide, it is sufficiently stirred, it is dry；
B. it calcines: the sample after step A is dry being put into tube furnace and is calcined, in the zero level air that flow is 300ml/min
Be heated to 400 DEG C, constant temperature 2h under atmosphere with 10K/min, after cool to room temperature with the furnace；
C. it restores: will be the 10%H for being 300ml/min in flow through the calcined sample reduction treatment of step B, treatment conditions2/
400 DEG C, constant temperature 2h are heated to 5K/min under Ar gaseous mixture atmosphere, it is rear to stop heating, sample furnace cooling under atmosphere protection
To room temperature.
6. rare earth oxide according to claim 3 supports the preparation method of the bimetallic hydrophobic catalyst of platinum ruthenium, feature exists
In, in the step 2, support the bimetallic rare earth oxide of platinum ruthenium and mixed with polytetrafluoroethylene (PTFE) 1:2 in mass ratio, addition go from
Sub- water forms mixture aqueous solution, then surfactant is added into mixture aqueous solution, forms suspension.
7. rare earth oxide according to claim 6 supports the preparation method of the bimetallic hydrophobic catalyst of platinum ruthenium, feature exists
In in the step 2, resistivity >=15M Ω of the deionized water, additive amount is to have supported the bimetallic rare earth oxygen of platinum ruthenium
10~20 times of compound quality；The surfactant is triton X-100, and additive amount is to support platinum ruthenium bimetallic rare earth oxygen
5~10 times of compound quality.
8. rare earth oxide according to claim 3 supports the preparation method of the bimetallic hydrophobic catalyst of platinum ruthenium, feature exists
In, in the step 3, using multiple coating processes, after suspension made from step 2 is coated on metal fiber felt, heating
Baking water removal, after preliminarily dried, coating, heated baking again, until reaching required load capacity, the temperature of the baking is
110-130℃。
9. rare earth oxide according to claim 3 supports the preparation method of the bimetallic hydrophobic catalyst of platinum ruthenium, feature exists
In in the step 4, the volume content of hydrogen is 1~10% in the gaseous mixture of hydrogen and inert gas, and the flow of gaseous mixture is
100~500ml/min；Heating rate is 1~10 DEG C/min, is heated to 350-380 DEG C.
10. rare earth oxide described in -9 any one supports the bimetallic hydrophobic catalyst of platinum ruthenium in hydrogen-according to claim 1
Application in water isotope exchange.
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| CN111359605B (en) * | 2020-02-28 | 2022-11-25 | 中国工程物理研究院材料研究所 | Preparation method and application of novel bifunctional catalyst filler |
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