CN109939710A - A kind of Pd/MC of Pd redispersexLoaded catalyst and its preparation method and application - Google Patents
A kind of Pd/MC of Pd redispersexLoaded catalyst and its preparation method and application Download PDFInfo
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Abstract
The invention discloses Pd/MCx loaded catalysts of a kind of Pd redisperse and its preparation method and application.Pd/MCx loaded catalyst of the present invention the preparation method comprises the following steps: Pd/MOx catalyst is placed in tube furnace, calcining carbonization is carried out under conditions of being passed through carbonaceous gas, metal oxide MOx in Pd/MOx catalyst is carbonized into metal carbides MCx, obtains the Pd/MCx loaded catalyst；Wherein the metal M in Pd/MOx catalyst is one or more of transition metal M o, Fe, W, Ti, Co, Mn, Nb, V, Ta, Zr, Cr.Not only initial catalytic activity is high for Pd/MCx catalyst prepared by the present invention, and the catalyst of sintering can carry out in-situ regeneration by oxy-carbo in fixed bed reactors, thus Reversible Cycle realizes the Pd particle redisperse in Pd/MCx catalyst, to make renewing catalyst activity；Secondly catalyst of the present invention due to Pd dispersion degree it is higher, therefore catalytic activity is higher.
Description
Technical field
The present invention relates to a kind of Pd/MC of Pd redispersexLoaded catalyst and its preparation method and application.
Background technique
Support type palladium-based catalyst is a kind of common hydrogenation catalyst, is widely used in alkane and adds hydrogen, hydrogenation of olefins, nitre
Base and nitroso add the fields such as hydrogen, catalytic selectivity oxidation.For noble metal catalyst, the dispersion degree of noble metal is very
Important index, directly determines catalyst performance.But it is often made in use since long-time uses or temperature is excessively high
At sintering deactivation, catalyst activity reduction is caused.Often lack the method for in-situ regeneration for the noble metal catalyst of sintering, most
Common method is to prepare catalyst again after being separated the noble metal in noble metal catalyst.This obvious process is not
Environmental protection, and biggish cost is economically also paid, but the in-situ regeneration technology of sintered catalyst is never breakthrough
Progress and application.
Henrik Birgersson seminar by using circulation O2,H2,Cl2In atmosphere redisperse three phase catalyst
Noble metal, the commercialized automobile three phase catalyst of successful regeneration.Polychronopoulou etc., which is prepared and characterized, uses O2-Cl2Place
Manage Pd/CeO2-Al2O3H is used again2The formation of small particle Pd may be implemented in reduction.Newton seminar uses the success of CO/NO atmosphere
Make the Pd/Al of aging2O3Redisperse occurs for the Pd particle in catalyst, and proposes the possible mechanism of Pd particle and process.
Although above method energy redisperse noble metal catalyst, there are many disadvantages, and such as redisperse low efficiency, atmosphere is not
Environmental protection, ex situ redisperse, the catalyst activity after redisperse restore undesirable etc..
Summary of the invention
To solve the problems, such as that sintering of catalyst inactivates, it is negative that the purpose of the present invention is to provide a kind of Pd/MCx of Pd redisperse
Supported catalyst and its preparation method and application, catalyst of the invention can be carbonized after sintering deactivation by in-situ oxidation-
Journey regeneration catalyzing activity, this method disperses the catalyst of sintering again, activity recovery and the advantages that can be recycled.
The preparation method of the Pd/MCx loaded catalyst of a kind of Pd redisperse, it is characterised in that by Pd/MOxIt urges
Agent is placed in tube furnace, and calcining carbonization is carried out under conditions of being passed through carbonaceous gas, the metal oxidation in Pd/MOx catalyst
Object MOxIt is carbonized into metal carbides MCx, obtain the Pd/MCxLoaded catalyst；Wherein Pd/MOxMetal in catalyst
M is one or more of transition metal M o, Fe, W, Ti, Co, Mn, Nb, V, Ta, Zr, Cr；The Pd/MOxPd in catalyst
Mass percentage be 0.05%~10%, preferably 0.5~5%.
A kind of Pd/MC of the Pd redispersexThe preparation method of loaded catalyst, it is characterised in that the carbon containing gas
Body is alkanes gas and H2Gaseous mixture or CO, the alkanes gas be CH4Or C2H6；Alkanes gas and H2Gaseous mixture
In, the volumetric concentration of alkanes gas is 5 ~ 95%, preferably 10~20%.
A kind of Pd/MC of the Pd redispersexThe preparation method of loaded catalyst, it is characterised in that calcine carbonization
Temperature is 300 ~ 700 DEG C, and the time for calcining carbonization is 0.5-12h.
A kind of Pd/MC of the Pd redispersexThe preparation method of loaded catalyst, it is characterised in that further include following
Process: Pd/MC obtainedxLoaded catalyst is also loaded the metal promoter of 0.05 ~ 5 wt%, the metal promoter be Cu, K,
At least one of Ba.
A kind of Pd/MC of the Pd redispersexThe preparation method of loaded catalyst, it is characterised in that the Pd/MOx
The preparation process of catalyst are as follows: using excessive infusion process or equi-volume impregnating, by MOxCarrier is in the aqueous solution of Pd presoma
Dipping is stood, dry and roasting, then through H at a temperature of 200 ~ 300 DEG C2Reduction makes Pd be in metallic state, obtains described
Pd/MOxCatalyst；Wherein Pd presoma is one or more of chlorine palladium acid, palladium acetate, palladium nitrate, palladium amine complex.
According to the Pd/MC of Pd redisperse prepared by above-mentioned methodxLoaded catalyst.
The Pd/MC of the Pd redispersexThe application of loaded catalyst, it is characterised in that the Pd/MCxSupport type is urged
Agent is used to be catalyzed the selective oxidation of the hydrogenation-dechlorination reaction of halogenated hydrocarbons, the selective hydrogenation of alkynes or alcohol compound
Reaction.
The Pd/MC of the Pd redispersexThe application of loaded catalyst, it is characterised in that the Pd/MCxSupport type is urged
After agent the phenomenon that sintering deactivation occurs in catalysis reaction, in-situ regeneration is carried out to catalyst using following procedure:
1) catalyst of sintering deactivation is roasted into 0.5-12h under an oxygen-containing atmosphere, the metal carbides MC in catalystxAnd carbon distribution
It is converted to metal oxide MO togetherx, obtain Pd/MOxCatalyst；
2) by Pd/MO obtained by step 1)xCatalyst carries out calcining and activating, Pd/MO under carbon-containing atmospherexMetal oxygen in catalyst
Compound MOxAgain it is carbonized into metal carbides MCx, obtain Pd/MCxLoaded catalyst, i.e. in-situ regeneration process are completed.
The Pd/MC of the Pd redispersexThe application of loaded catalyst, it is characterised in that in step 1), oxygen-containing atmosphere
Gas be oxygen and inert gas gaseous mixture, the volumetric concentration of oxygen is 5 ~ 95%, and inert gas is nitrogen or argon gas；Step
It is rapid 2) in, the gas of carbon-containing atmosphere is alkanes gas and H2Gaseous mixture or CO, the alkanes gas be CH4Or C2H6；Alkane
Hydrocarbon gas and H2Gaseous mixture in, H2Volumetric concentration is 5-95%.
The Pd/MC of the Pd redispersexThe application of loaded catalyst, it is characterised in that in step 1), the temperature of roasting
Degree is 300 ~ 650 DEG C, preferably 400 ~ 500 DEG C；In step 2, the temperature of calcining and activating is 300 ~ 700 DEG C, calcining and activating when
Between be 0.5-12h.
Compared with the existing technology, the beneficial effect that the present invention obtains is:
1, Pd/MC prepared by the present inventionxNot only initial catalytic activity is high for catalyst, but also the catalyst being sintered can be in fixed bed
In-situ regeneration is carried out by oxy-carbo in reactor, thus Reversible Cycle realizes Pd/MCxPd particle in catalyst divides again
It dissipates, to make renewing catalyst activity；
2, when catalyst of the invention carries out oxy-carbo progress in-situ regeneration, regeneration atmosphere environmental protection, catalyst activity can restore
To 90% or more of initial activity；
3, Pd/MC of the present inventionxThe preparation method of loaded catalyst is simple, lower production costs；
4, by loading type Pd/MC prepared by the present inventionxCatalyst is used in the reaction such as hydrogenation-dechlorination, selective hydrogenation, oxidation,
Have many advantages, such as good catalytic activity, excellent selectivity, high catalyst efficiency and long service life.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the scope of protection of the present invention is not limited thereto.
Embodiment 1
By the Pd/FeC that 1g is fresh and Pd load capacity is 3%xCatalyst is fitted into fixed bed reactors, is passed through hydrogen in 250 DEG C of items
Reductase 12 h under part.CFC-115 gas is then passed in 300 DEG C of reaction temperature, air speed 720h-1Under the conditions of reacted, CFC-115
The raw materials components mole ratio of raw material and hydrogen is 1:1.5.After reacting 80h, when the conversion ratio of CFC-115 is lower than 65%, it is denoted as catalyst hair
Raw sintering deactivation.
The O for being 8% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 450 DEG C of roasting temperature 0.5h are obtained
Pd/FeOxThen catalyst is passed through 10% CH at a temperature of 300 DEG C4/H2Gaseous mixture (i.e. CH4/H2In gaseous mixture, CH4Volume
Content is that 10%) calcining carbonization 1h restores Pd/FeCxCatalyst activity to get arrive regenerated catalyst.In identical reaction condition
Under, hydrogenation-dechlorination reaction of the CFC-115 under regenerated catalyst effect is carried out again.
When fresh catalyst and regenerated catalyst in embodiment 1 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Embodiment 2
By the Pd/FeC that 1g is fresh and Pd load capacity is 9%xCatalyst is fitted into fixed bed reactors, is passed through hydrogen in 250 DEG C of items
Reductase 12 h under part.CFC-115 gas is then passed in 300 DEG C of reaction temperature, air speed 720h-1Under the conditions of reacted, CFC-115
The raw materials components mole ratio of raw material and hydrogen is 1:1.5.After reacting 80h, when the conversion ratio of CFC-115 is lower than 65%, it is denoted as catalyst hair
Raw sintering deactivation.
The O for being 16% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 400 DEG C of roasting temperature 8h are obtained
Pd/FeOxThen catalyst is passed through 20% CH at a temperature of 650 DEG C4/H2Gaseous mixture calcining carbonization 10h restores Pd/FeCxCatalysis
Agent activity to get arrive regenerated catalyst.Under the same conditions, CFC-115 adding under regenerated catalyst effect is carried out again
Hydrogen dechlorination reaction.
When fresh catalyst and regenerated catalyst in embodiment 2 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Embodiment 3
By the Pd/FeC that 1g is fresh and Pd load capacity is 5%xCatalyst is fitted into fixed bed reactors, is passed through hydrogen in 250 DEG C of items
Reductase 12 h under part.CFC-115 gas is then passed in 300 DEG C of reaction temperature, air speed 720h-1Under the conditions of reacted, CFC-115
The raw materials components mole ratio of raw material and hydrogen is 1:1.5.After reacting 80h, when the conversion ratio of CFC-115 is lower than 65%, it is denoted as catalyst hair
Raw sintering deactivation.
The O for being 6% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 500 DEG C of roasting temperature 1h are obtained
Pd/FeOxThen catalyst is passed through CO calcining carbonization 3h at a temperature of 300 DEG C and restores Pd/FeCxThe activity of catalyst is to get arriving
Regenerated catalyst.Under the same conditions, hydrogenation-dechlorination reaction of the CFC-115 under regenerated catalyst effect is carried out again.
When fresh catalyst and regenerated catalyst in embodiment 3 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Embodiment 4
By the Pd/FeC that 1g is fresh and Pd load capacity is 10%xCatalyst is fitted into fixed bed reactors, is passed through hydrogen at 250 DEG C
Under the conditions of reductase 12 h.CFC-115 gas is then passed in 300 DEG C of reaction temperature, air speed 720h-1Under the conditions of reacted, CFC-
The raw materials components mole ratio of 115 raw materials and hydrogen is 1:1.5.After reacting 80h, when the conversion ratio of CFC-115 is lower than 65%, it is denoted as catalysis
Sintering deactivation occurs for agent.
The O for being 12% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 420 DEG C of roasting temperature 6h are obtained
Pd/FeOxThen catalyst is passed through CO calcining carbonization 6h at a temperature of 650 DEG C and restores Pd/FeCxThe activity of catalyst is to get arriving
Regenerated catalyst.Under the same conditions, hydrogenation-dechlorination reaction of the CFC-115 under regenerated catalyst effect is carried out again.
When fresh catalyst and regenerated catalyst in embodiment 4 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Embodiment 5
Pd-Cu/MoO is prepared using continuous infusion process3.First by the Cu content of 2.51mL be 0.4mol/L copper nitrate aqueous solution by
Drop is added dropwise in 2g MoO3On carrier, standing dipping is carried out, dry, (roasting is to increase copper for 300 DEG C of roastings in air atmosphere
Presoma and MoO3The interaction of carrier), the catalyst precarsor after being roasted；It is 0.1mol/L by the amount containing Pd of 3.85mL
Chlorine palladium aqueous acid is added dropwise on catalyst precarsor after baking dropwise and carries out ultrasonic immersing 30min, after standing and being dry, and
Through H at a temperature of 250~300 DEG C2Reduction obtains Pd-Cu/MoO3Catalyst, Pd-Cu/MoO3Catalyst is again through under carbon-containing atmosphere
Calcining carbonization obtains Pd-Cu/MoC catalyst.
By 1g is fresh and load capacity be 2%Pd-3%Cu/MoC catalyst (i.e. in 2%Pd-3%Cu/MoC catalyst, Pd load
Amount is that 2%, Cu load capacity is 3%) to be fitted into fixed bed reactors, is passed through hydrogen reductase 12 h under the conditions of 250 DEG C.It then passes to anti-
Answer unstripped gas (feed gas volume content composition: 1.09%C2H2, 1.85%H2, 87.66%C2H4, 9.40%N2, total flow is
200mL/min, gross pressure 2.1MPa), selective hydrogenation of acetylene reaction is carried out at being 100 DEG C in reaction temperature.React 100h
Afterwards, C2H2Conversion ratio be lower than 80% when, be denoted as catalyst occur sintering deactivation.
The O for being 6% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 500 DEG C of roasting temperature 1h are obtained
Pd/MoOxThen catalyst is passed through 12% CH at a temperature of 350 DEG C4/H2Gaseous mixture calcining carbonization 2h restores Pd/MoCxCatalyst
Activity to get arrive regenerated catalyst.Under the same conditions, selectivity of the acetylene under regenerated catalyst effect is carried out again to add
Hydrogen reaction.
When fresh catalyst and regenerated catalyst in embodiment 5 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Embodiment 6
By 1g is fresh and load capacity is that 8%Pd-10%Cu/MoC catalyst is fitted into fixed bed reactors, hydrogen is passed through at 250 DEG C
Under the conditions of reductase 12 h.Then pass to reactor feed gas (feed gas volume content composition: 1.09%C2H2, 1.85%H2, 87.66%
C2H4, 9.40%N2, total flow 200mL/min, gross pressure 2.1MPa), acetylene choosing is carried out at being 100 DEG C in reaction temperature
Selecting property hydrogenation reaction.After reacting 100h, C2H2Conversion ratio be lower than 80% when, be denoted as catalyst occur sintering deactivation.
The O for being 16% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 400 DEG C of roasting temperature 8h obtain Pd/
MoOxThen catalyst is passed through 20% CH at a temperature of 600 DEG C4/H2Gaseous mixture calcining carbonization 10h restores Pd/MoCxCatalyst
Activity to get arrive regenerated catalyst.Under the same conditions, selective hydrogenation of the acetylene under regenerated catalyst effect is carried out again
Reaction.
When fresh catalyst and regenerated catalyst in embodiment 6 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Embodiment 7
By 1g is fresh and load capacity is that 3%Pd-4%Cu/MoC catalyst is fitted into fixed bed reactors, hydrogen is passed through in 250 DEG C of items
Reductase 12 h under part.Then pass to reactor feed gas (feed gas volume content composition: 1.09%C2H2, 1.85%H2, 87.66%
C2H4, 9.40%N2, total flow 200mL/min, gross pressure 2.1MPa), acetylene choosing is carried out at being 100 DEG C in reaction temperature
Selecting property hydrogenation reaction.After reacting 100h, C2H2Conversion ratio be lower than 80% when, be denoted as catalyst occur sintering deactivation.
The O for being 6% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 500 DEG C of roasting temperature 1h are obtained
Pd/MoOxThen catalyst is passed through CO calcining carbonization 3h at a temperature of 350 DEG C and restores Pd/MoCxThe activity of catalyst is to get arriving
Regenerated catalyst.Under the same conditions, selective hydrogenation of the acetylene under regenerated catalyst effect is carried out again.
When fresh catalyst and regenerated catalyst in embodiment 7 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Embodiment 8
By 1g is fresh and load capacity is that 9%Pd-10%Cu/MoC catalyst is fitted into fixed bed reactors, hydrogen is passed through at 250 DEG C
Under the conditions of reductase 12 h.Then pass to reactor feed gas (feed gas volume content composition: 1.09%C2H2, 1.85%H2, 87.66%
C2H4, 9.40%N2, total flow 200mL/min, gross pressure 2.1MPa), acetylene choosing is carried out at being 100 DEG C in reaction temperature
Selecting property hydrogenation reaction.After reacting 100h, C2H2Conversion ratio be lower than 80% when, be denoted as catalyst occur sintering deactivation.
The O for being 12% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 420 DEG C of roasting temperature 8h obtain Pd/
MoOXThen catalyst is passed through CO calcining carbonization 6h at a temperature of 600 DEG C and restores Pd/MoCxCatalyst activity to get to regeneration
Catalyst.Under the same conditions, selective hydrogenation of the acetylene under regenerated catalyst effect is carried out again.
When fresh catalyst and regenerated catalyst in embodiment 8 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Embodiment 9
The Pd/TiC catalyst that 1g is fresh and Pd load capacity is 2% is fitted into fixed bed reactors, is passed through hydrogen in 250 DEG C of items
Reductase 12 h under part.Then pass to reactor feed gas (unstripped gas composition: 5vol.%O2, 0.4 ~ 0.5 vol.% ethyl alcohol, N2For balance
Gas, total flow 100mL/min, air speed are 24000 h-1), ethanol selectivity oxidation is carried out at being 200 DEG C in reaction temperature
For CO2Reaction.After reacting 150h, when the conversion ratio of ethyl alcohol is lower than 75%, it is denoted as catalyst and sintering deactivation occurs.
The O for being 8% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 450 DEG C of roasting temperature 0.5h are obtained
Pd/TiOxThen catalyst is passed through 9% CH at a temperature of 300 DEG C4/H2Gaseous mixture calcining carbonization 1h restores Pd/TiCxCatalyst
Activity to get arrive regenerated catalyst.Under the same conditions, selective oxidation of the ethyl alcohol under regenerated catalyst effect is carried out again
For CO2Reaction.
When fresh catalyst and regenerated catalyst in embodiment 9 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Embodiment 10
The Pd/TiC catalyst that 1g is fresh and Pd load capacity is 8% is fitted into fixed bed reactors, is passed through hydrogen in 250 DEG C of items
Reductase 12 h under part.Then pass to reactor feed gas (unstripped gas composition: 5 vol.%O2, 0.4 ~ 0.5 vol.% ethyl alcohol, N2It is flat
Weigh gas, and total flow 100mL/min, air speed is 24000 h-1), ethanol selectivity oxygen is carried out at being 200 DEG C in reaction temperature
Turn to CO2Reaction.After reacting 150h, when the conversion ratio of ethyl alcohol is lower than 75%, it is denoted as catalyst and sintering deactivation occurs.
The O for being 16% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 400 DEG C of roasting temperature 8h are obtained
Pd/TiOxThen catalyst is passed through 18% CH at a temperature of 650 DEG C4/H2Gaseous mixture calcining carbonization 10h restores Pd/TiCxCatalysis
Agent activity to get arrive regenerated catalyst.Under the same conditions, selectivity of the ethyl alcohol under regenerated catalyst effect is carried out again
It is oxidized to CO2Reaction.
When fresh catalyst and regenerated catalyst in embodiment 10 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Embodiment 11
The Pd/TiC catalyst that 1g is fresh and Pd load capacity is 4% is fitted into fixed bed reactors, is passed through hydrogen in 250 DEG C of items
Reductase 12 h under part.Then pass to reactor feed gas (unstripped gas composition: 5 vol.%O2, 0.4 ~ 0.5 vol.% ethyl alcohol, N2It is flat
Weigh gas, and total flow 100mL/min, air speed is 24000 h-1), ethanol selectivity oxygen is carried out at being 200 DEG C in reaction temperature
Turn to CO2Reaction.After reacting 150h, when the conversion ratio of ethyl alcohol is lower than 75%, it is denoted as catalyst and sintering deactivation occurs.
The O for being 6% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 500 DEG C of roasting temperature 1h are obtained
Pd/TiOxThen catalyst is passed through CO calcining carbonization 3h at a temperature of 300 DEG C and restores Pd/TiCxThe activity of catalyst is to get arriving
Regenerated catalyst.Under the same conditions, carrying out selective oxidation of the ethyl alcohol under regenerated catalyst effect again is CO2It is anti-
It answers.
When fresh catalyst and regenerated catalyst in embodiment 11 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Embodiment 12
The Pd/TiC catalyst that 1g is fresh and Pd load capacity is 10% is fitted into fixed bed reactors, is passed through hydrogen in 250 DEG C of items
Reductase 12 h under part.Then pass to reactor feed gas (unstripped gas composition: 5 vol.%O2, 0.4 ~ 0.5 vol.% ethyl alcohol, N2It is flat
Weigh gas, and total flow 100mL/min, air speed is 24000 h-1), ethanol selectivity oxygen is carried out at being 200 DEG C in reaction temperature
Turn to CO2Reaction.After reacting 150h, when the conversion ratio of ethyl alcohol is lower than 75%, it is denoted as catalyst and sintering deactivation occurs.
The O for being 12% in oxygen volume content by the catalyst of sintering deactivation2/N2Atmosphere and 420 DEG C of roasting temperature 6h are obtained
Pd/TiOxThen catalyst is passed through CO calcining carbonization 8h at a temperature of 650 DEG C and restores Pd/TiCxThe activity of catalyst is to get arriving
Regenerated catalyst.Under the same conditions, carrying out selective oxidation of the ethyl alcohol under regenerated catalyst effect again is CO2It is anti-
It answers.
When fresh catalyst and regenerated catalyst in embodiment 12 are reacted for being catalyzed, 20h sampling analysis, reaction are reacted
Conversion ratio, selectivity see Table 1 for details.
Table 1
As it can be seen from table 1 the Pd/MC of sintering deactivationxLoaded catalyst is in CO or CH4/H2Carbon is calcined under the atmosphere of gaseous mixture
Change, the catalytic activity of obtained regenerated catalyst can be restored to 90% or more of fresh catalyst initial activity.
Whether Pd can be dispersed on carrier, depend on the power of the interaction force between carrier and precious metals pd.Generally
For, if having stronger interaction force between Pd and carrier, the dispersion degree of Pd can be higher, and stability is also preferable
(i.e. in chemical reaction or under hot conditions, the Pd of small particle does not allow easy to migrate and forms large-sized Pd, so as to avoid mistake
It is living).Because if the precious metals pd redisperse in sintering deactivation catalyst is that small Pd metallic particles depends on two conditions: Pd's
Compound (such as PdCx) can be easier to come in carrier surface drawout compared with Pd metal, and Pd compound after sprawling and carrier
The intensity of interaction is larger.If two conditions all meet, then Pd bulky grain energy redisperse is short grained Pd.If can only
Meet a condition or two conditions are not satisfied, is then difficult to occur the phenomenon that redisperse.
By Pd/MOxCatalyst carries out calcining carbonization, the Pd/MC obtained fromxLoaded catalyst can allow sintering Pd's
Redispersibility mechanism is as follows: it is well known that a kind of metal spontaneous can often be sprawled in another metal surface, forming ultra-thin wetting
Layer.The class noble metal characteristic of metal carbides ensure that the metal coating being grown on carbide also can be in another metal surface
It sprawls, forms super thin metal carbide lamella, this is the precondition of metal carbides redisperse.Therefore by the Pd/MC of sintering deactivationx
Catalyst roasts form it into Pd/MO under an oxygen-containing atmospherex, and under carbon-containing atmosphere, it is carbonized under suitable operating condition
During, the unformed Pd metal carbides of formation can be in the form of ultra-thin wetting layer existing for, and it is spontaneous surface spread
Exhibition.This is because have interfacial charge transfer between metal carbides carrier and activity component metal Pd, when electronics is from metal Pd stream
When to metal carbides carrier, strengthens the strong interaction between precious metals pd and metal carbides carrier and make noble metal
Pd carries out redisperse.
Content described in this specification is only to enumerate to inventive concept way of realization, and protection scope of the present invention is not answered
When the concrete form for being seen as limited by embodiment and being stated.
Claims (10)
1. a kind of preparation method of the Pd/MCx loaded catalyst of Pd redisperse, it is characterised in that by Pd/MOxCatalyst is placed in
In tube furnace, calcining carbonization, the metal oxide MO in Pd/MOx catalyst are carried out under conditions of being passed through carbonaceous gasxBy carbon
It is melted into metal carbides MCx, obtain the Pd/MCxLoaded catalyst；Wherein Pd/MOxMetal M in catalyst is transition gold
Belong to one or more of Mo, Fe, W, Ti, Co, Mn, Nb, V, Ta, Zr, Cr；The Pd/MOxThe quality percentage of Pd in catalyst
Content is 0.05%~10%, preferably 0.5~5%.
2. a kind of Pd/MC of Pd redisperse as described in claim 1xThe preparation method of loaded catalyst, it is characterised in that institute
Stating carbonaceous gas is alkanes gas and H2Gaseous mixture or CO, the alkanes gas be CH4Or C2H6；Alkanes gas and H2
Gaseous mixture in, the volumetric concentration of alkanes gas is 5 ~ 95%, preferably 10~20%.
3. a kind of Pd/MC of Pd redisperse as described in claim 1xThe preparation method of loaded catalyst, it is characterised in that forge
The temperature for burning carbonization is 300 ~ 700 DEG C, and the time for calcining carbonization is 0.5-12h.
4. a kind of Pd/MC of Pd redisperse as described in claim 1xThe preparation method of loaded catalyst, it is characterised in that also
Including following procedure: Pd/MC obtainedxLoaded catalyst is also loaded the metal promoter of 0.05 ~ 5 wt%, the metal promoted
Agent is at least one of Cu, K, Ba.
5. a kind of Pd/MC of Pd redisperse as described in claim 1xThe preparation method of loaded catalyst, it is characterised in that institute
State Pd/MOxThe preparation process of catalyst are as follows: using excessive infusion process or equi-volume impregnating, by MOxCarrier is in Pd presoma
It is impregnated in aqueous solution, stands, dries and roast, then through H at a temperature of 200 ~ 300 DEG C2Reduction makes Pd be in metallic state, that is, makes
Obtain the Pd/MOxCatalyst；Wherein Pd presoma is one of chlorine palladium acid, palladium acetate, palladium nitrate, palladium amine complex or several
Kind.
6. the Pd/MC of Pd redisperse prepared by the method as described in claim 1 ~ 5 is anyxLoaded catalyst.
7. the Pd/MC of Pd redisperse as claimed in claim 6xThe application of loaded catalyst, it is characterised in that the Pd/MCx
Loaded catalyst is used to be catalyzed hydrogenation-dechlorination reaction, the choosing of the selective hydrogenation of alkynes or alcohol compound of halogenated hydrocarbons
Selecting property oxidation reaction.
8. the use as claimed in claim 7, it is characterised in that the Pd/MCxLoaded catalyst is burnt in catalysis reaction
After the phenomenon that knot inactivation, in-situ regeneration is carried out to catalyst using following procedure:
1) catalyst of sintering deactivation is roasted into 0.5-12h under an oxygen-containing atmosphere, the metal carbides MC in catalystxAnd carbon distribution
It is converted to metal oxide MO togetherx, obtain Pd/MOxCatalyst；
2) by Pd/MO obtained by step 1)xCatalyst carries out calcining and activating, Pd/MO under carbon-containing atmospherexMetal oxygen in catalyst
Compound MOxAgain it is carbonized into metal carbides MCx, obtain Pd/MCxLoaded catalyst, i.e. in-situ regeneration process are completed.
9. application as claimed in claim 8, it is characterised in that in step 1), the gas of oxygen-containing atmosphere is oxygen and inert gas
Gaseous mixture, the volumetric concentration of oxygen is 5 ~ 95%, and inert gas is nitrogen or argon gas；In step 2, the gas of carbon-containing atmosphere is
Alkanes gas and H2Gaseous mixture or CO, the alkanes gas be CH4Or C2H6；Alkanes gas and H2Gaseous mixture in,
H2Volumetric concentration is 5-95%.
10. application as claimed in claim 8, it is characterised in that in step 1), the temperature of roasting is 300 ~ 650 DEG C, preferably
400~500℃；In step 2, the temperature of calcining and activating is 300 ~ 700 DEG C, and the time of calcining and activating is 0.5-12h.
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