CN103464171A - Regeneration method of noble metal catalyst - Google Patents
Regeneration method of noble metal catalyst Download PDFInfo
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- CN103464171A CN103464171A CN201310434818XA CN201310434818A CN103464171A CN 103464171 A CN103464171 A CN 103464171A CN 201310434818X A CN201310434818X A CN 201310434818XA CN 201310434818 A CN201310434818 A CN 201310434818A CN 103464171 A CN103464171 A CN 103464171A
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Abstract
The invention relates to a regeneration method of a noble metal catalyst, and belongs to the technical field of industrial catalysts. With the adoption of the regeneration method, the technical problems that the noble metal is high in recovering cost, pollutes the environment, is large in risk and is unfavorable for operation in the prior art are solved. The regeneration method comprises the steps of immersing noble metal catalysts into mixed solution of an oxidizing agent and a reducing agent according to the mass ratio being 1:(50-1000):(50-1000) of the noble metal catalyst, the oxidizing agent and the reducing agent; at the temperature of more than 50 DEG C, under the atmospheric pressure of 2-12Pa, reacting for more than 0.5 hours to obtain the reacted solution; and steaming the reacted solution to obtain solid, i.e., the regenerated noble metal catalyst. The regeneration method has the advantages that a low-molecular organic compound is adopted as the oxidizing agent and the reducing agent, so that the catalyst with reduced activity can be regenerated again, the requirements on the temperature and the pressure in the process are low, the cost is low, the operation is simple and convenient, the safety performance is good and the industrial production is easy.
Description
Technical field
The present invention relates to a kind of renovation process of noble metal catalyst, belong to the industrial catalyst technical field.
Background technology
The noble metal such as platinum, gold, owing to having unique physics, chemical property, has important irreplaceable effect in every field.Along with scientific and technological progress, noble metal has been not limited only to ornament and has played a role on economy and finance, and has been applied in industrial processes, especially aspect the catalyst of energy industry, is being widely used.
Noble metal catalyst is expensive, and easily causes environmental pollution, so the recycling of noble metal catalyst becomes people's research emphasis gradually.In prior art, the processing method of noble metal catalyst generally takes noble metal to reclaim, as US4331634, US5045290, CN101748284A etc., all disclose and adopted strong acid and strong base solution to reclaim the method for noble metal from different raw materials, but strong acid or highly basic not only expense are high, contaminated environment and dangerous large, be unfavorable for operation.
In prior art, gold (ACSCatal.2012 on the heavy dispersal oxide carrier of document, 2,552-560) method of the golden nanometer particle on heavy dispersal oxide carrier in a kind of gaseous environment has been proposed, its method is under 240 ℃ of temperature, pressure 16bar, heavily disperse golden nanometer particle with iodomethane, although this method can be dispersed into large nano particle little particle or atom, to the not raising of catalytic activity of catalyst.And under gas phase condition, again disperse golden nanometer particle to need HTHP, increased cost, and operation is difficult for.
Summary of the invention
The objective of the invention is to solve in prior art that to reclaim the noble metal expense high, contaminated environment, dangerous large, be unfavorable for the technical problem of operation, a kind of renovation process of noble metal catalyst is provided.
The renovation process of noble metal catalyst of the present invention comprises the following steps:
(1) noble metal catalyst is immersed in the mixed solution of Oxidizing and Reducing Agents, more than 50 ℃, under 2-12 atmospheric pressure, more than reaction 0.5h, obtain reacted solution;
Described oxidant is C
1-C
4halogenated hydrocarbons;
Described reducing agent is C
1-C
4organic Alcohol or C
1-C
4organic acid;
The mass ratio of described noble metal catalyst, oxidant, reducing agent is 1:(50-1000): (50-1000);
(2) by reacted solution evaporate to dryness, obtain solid, be the noble metal catalyst after regeneration.
Further, described step (1) be by noble metal catalyst with after the precious metal catalyst agent carrier mixes, immerse in the mixed solution of Oxidizing and Reducing Agents, more than 50 ℃, under 2-12 atmospheric pressure, more than reacting 0.5h, obtain reacted solution.
Preferably, the renovation process of described noble metal catalyst also comprises step (3), and it is ultrasonic, centrifugal that the solid that step (2) is obtained adds water, after drying, and the noble metal catalyst after being regenerated.
A kind of in the mixture of mixture, Ag and the carrier loaded Ag catalyst of mixture, Pd and carrier loaded Pd catalyst, Ru and the carrier loaded Ru catalyst of mixture, Au and carrier loaded Au catalyst that preferably, described noble metal catalyst is platinum (Pt), gold (Au), palladium (Pd), ruthenium (Ru), silver (Ag), carrier loaded Pt catalyst, carrier loaded Au catalyst, carrier loaded Pd catalyst, carrier loaded Ru catalyst, carrier loaded Ag catalyst, Pt and carrier loaded Pt catalyst;
Described carrier is C (carbon), SiO
2(silica), TiO
2(titanium dioxide) or Al
2o
3(alundum (Al2O3)).
Preferably, described oxidant is monochloro methane, carrene or monochlorethane.
Preferably, described reducing agent is methyl alcohol, formic acid, ethanol, acetic acid, isopropyl alcohol or ethylene glycol.
Preferably, the described reaction time is 1-10h.
Preferably, described reaction temperature is 80 ℃ to 200 ℃, and pressure is 2-10 atmospheric pressure.
Preferably, described precious metal catalyst agent carrier is C, SiO
2, TiO
2perhaps Al
2o
3.
Preferably, described noble metal catalyst and precious metal catalyst agent carrier mass ratio be 1:(0.1-5).
Beneficial effect of the present invention:
(1) the present invention adopts in the mixed solution coexisted at Oxidizing and Reducing Agents, utilize the method for dissolving simultaneously and precipitating, noble metal on the noble metal catalyst of inactivation is disperseed again, make activity decreased catalyst again regenerate, catalyst activity can recover even to surpass the front level of inactivation, catalyst can be utilized again, not only can reduce production costs, and can improve the utilization rate of noble metal;
(2) renovation process of the present invention carries out in liquid phase, disperse golden nanometer particle with respect to the available technology adopting vapor phase method, the present invention can improve the catalytic activity of catalyst in dispersed particle, and to temperature and pressure require low, with low cost, easy and simple to handle, security performance is good, is easy to suitability for industrialized production;
(3) the present invention has adopted little molecular organic compound as Oxidizing and Reducing Agents, operates easylier, has avoided in prior art using the strong acid and strong base expense high, and contaminated environment and dangerous large is unfavorable for the technical problem of operation.
(4) the present invention especially can be used for the regeneration of electrode catalyst of fuel cell.
The accompanying drawing explanation
The cyclic voltammetry curve of the noble metal catalyst that Fig. 1 is Comparative Examples of the present invention and embodiment.
The specific embodiment
The renovation process of noble metal catalyst comprises the following steps:
(1) noble metal catalyst is immersed in the mixed solution of Oxidizing and Reducing Agents, more than 50 ℃, under 2-12 atmospheric pressure, more than reaction 0.5h, obtain reacted solution;
Noble metal catalyst comprises the mixture of non-loading type noble metal catalyst, loaded noble metal catalyst and unsupported catalyst and similar loaded noble metal catalyst, the non-loading type noble metal catalyst is Pt, Au, Pd, Ru or Ag, and loaded noble metal catalyst is C loaded Pt catalyst, C load Au catalyst, C Pt-supported catalyst, C load Ru catalyst, C loaded Ag catalyst, SiO
2loaded Pt catalyst, SiO
2load Au catalyst, SiO
2pt-supported catalyst, SiO
2load Ru catalyst, SiO
2loaded Ag catalyst, TiO
2loaded Pt catalyst, TiO
2load Au catalyst, TiO
2pt-supported catalyst, TiO
2load Ru catalyst, TiO
2loaded Ag catalyst, Al
2o
3loaded Pt catalyst, Al
2o
3load Au catalyst, Al
2o
3pt-supported catalyst, Al
2o
3load Ru catalyst or Al
2o
3the loaded Ag catalyst, the mixture that mixture is Pt and C loaded Pt catalyst, Pt and SiO
2the mixture of loaded Pt catalyst, Pt and TiO
2the mixture of loaded Pt catalyst, Pt and Al
2o
3mixture, Au and the SiO of the mixture of loaded Pt catalyst, Au and C load Au catalyst
2mixture, Au and the TiO of load Au catalyst
2mixture, Au and the Al of load Au catalyst
2o
3mixture, Pd and the SiO of the mixture of load Au catalyst, Pd and C Pt-supported catalyst
2the mixture of Pt-supported catalyst, Pd and TiO
2the mixture of Pt-supported catalyst, Pd and Al
2o
3mixture, Ru and the SiO of the mixture of Pt-supported catalyst, Ru and C load Ru catalyst
2mixture, Ru and the TiO of load Ru catalyst
2mixture, Ru and the Al of load Ru catalyst
2o
3mixture, Ag and the TiO of the mixture of the mixture of load Ru catalyst, Ag and C loaded Ag catalyst, Ag and Ag loaded Ag catalyst
2the mixture of loaded Ag catalyst or Ag, Al
2o
3a kind of in the mixture of loaded Ag catalyst;
Wherein, the material of C load comprises the carbon black of carbon black or modified;
Oxidant is C
1-C
4halogenated hydrocarbons, be preferably monochloro methane, carrene or monochlorethane;
Reducing agent is C
1-C
4organic Alcohol or C
1-C
4organic acid, preferably methyl alcohol, formic acid, ethanol, acetic acid, isopropyl alcohol or ethylene glycol;
The mass ratio of noble metal catalyst, oxidant, reducing agent is 1:(50-1000): (50-1000);
(2) by reacted solution evaporate to dryness, obtain solid;
(3) step (2) being obtained to solid, to add water ultrasonic, centrifugal, after drying, and the noble metal catalyst after being regenerated.
In the renovation process of noble metal catalyst of the present invention, step (1) can for by noble metal catalyst with after the precious metal catalyst agent carrier mixes, immerse in the mixed solution of Oxidizing and Reducing Agents, more than 50 ℃, 2-12 atmospheric pressure, more than reaction 0.5h, obtain reacted solution; When noble metal catalyst comprises loaded noble metal catalyst, the precious metal catalyst agent carrier is identical with the carrier of loaded noble metal catalyst, and for example: when loaded noble metal catalyst is Pt/C, the precious metal catalyst agent carrier is C; Noble metal catalyst and precious metal catalyst agent carrier mass ratio be 1:(0.1-5), described precious metal catalyst agent carrier is C, SiO
2, TiO
2perhaps Al
2o
3, wherein, the carbon black that the C carrier is carbon black or modified, as the BP200 after the XC-72 after XC-72, BP200, modification or modification, described XC-72 and BP200 all can be by commercially available, and can prepare by document by the BP200 after the XC-72 after modification and modification, be prior art.
In the renovation process of noble metal catalyst of the present invention, in the mixed solution of Oxidizing and Reducing Agents, Oxidizing and Reducing Agents coexists, and when oxidant is gas, can take to reduce the method for temperature, and oxidant liquefaction is blended in reducing agent.
In the renovation process of noble metal catalyst of the present invention, the recovery time is preferably 1-10h, and reaction temperature is preferably 50-200 ℃, 80-200 ℃ more preferably, and pressure is preferably 2-10 atmospheric pressure.
In the renovation process of noble metal catalyst of the present invention, preferably adopt the pure water excusing from death, centrifugation rate is restriction not, can reach centrifugal effect and get final product.
The accurate atmospheric pressure of atmospheric pressure index of the present invention.
The catalytic performance of the noble metal catalyst after the regeneration that adopts method of the present invention to obtain adopts electrochemical catalysis property detection method to detect, as cyclic voltammetry curve, but be not limited to this, method is as follows: get the noble metal catalyst after 2.5mg regenerates, add 475uL ethanol, 25uLNafion solution, ultrasonic mixing half an hour, make ink; Get the 10uL ink, drop on glass-carbon electrode, after room temperature is dried, obtain membrane electrode; Using the SCE electrode as reference electrode, Pt sheet as electrode is formed to three-electrode system, at the H of the 0.5mol/L through the nitrogen deoxygenation
2sO
4-CH
3carry out cyclic voltammetry in OH solution, sweep speed is 50mV/s.
Below in conjunction with drawings and Examples, the present invention will be further described.
Comparative Examples 1
In conjunction with Fig. 1, Comparative Examples 1 is described
Pt/C catalyst before inactivation is carried out to the test of electrochemical catalysis character, test result is as shown in Fig. 1 curve 1.
Comparative Examples 2
In conjunction with Fig. 1, Comparative Examples 2 is described
Pt/C catalyst after inactivation is carried out to the test of electrochemical catalysis character, test result is as shown in Fig. 1 curve 2.
Embodiment 1
In conjunction with Fig. 1, embodiment 1 is described
The oxidized black of the Pt/C catalyst after the 6mg inactivation and the doping of 6mg iron is joined in high voltage bearing teat glass, add the methyl alcohol of 2mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 2g; Room temperature to be returned to, 2-12 atmospheric pressure, put into 160 ℃ of stirring reaction 7h of oil bath pan; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 1 is obtained carries out the test of electrochemical catalysis character, and test result is as shown in Fig. 1 curve 3.
In conjunction with Fig. 1, embodiment 2 is described
The carbon black of the Pt/C catalyst after the 6mg inactivation and the doping of 6mg fluorine is joined in high voltage bearing teat glass, add the methyl alcohol of 2mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 2 is obtained carries out the test of electrochemical catalysis character, and test result is as shown in Fig. 1 curve 4.
In Fig. 1, the cyclic voltammetry curve of Pt/C before the inactivation that curve 1 is Comparative Examples 1, the cyclic voltammetry curve of the Pt/C that curve 2 is inactivation, the cyclic voltammetry curve of the mixture of the Pt/C of curve 3 inactivation after processing for renovation process and the carbon black of fluorine doping, the cyclic voltammetry curve of the Pt/C of curve 4 inactivation after processing for renovation process and the mixture of the oxidized black that iron adulterates; As can be seen from Figure 1, the power of the oxidation peak current of methyl alcohol is curve 3>curve 4>curve 1>curve 2, illustrate renovation process of the present invention make activity decreased catalyst again regenerate, activity can recover even to surpass the level before inactivation.
Pt/C catalyst after the 6mg inactivation is joined in high voltage bearing teat glass, add the methyl alcohol of 2mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 3 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.6mA.
Embodiment 4
The carbon black of the Pt/C catalyst after the 6mg inactivation and the doping of 6mg fluorine is joined in high voltage bearing teat glass, add the methyl alcohol of 2mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 80 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 4 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.8mA.
Embodiment 5
The carbon black of the Pt/C catalyst after the 6mg inactivation and the doping of 6mg fluorine is joined in high voltage bearing teat glass, add the methyl alcohol of 2mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 200 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 5 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.85mA.
Embodiment 6
The carbon black of the Pt/C catalyst after the 6mg inactivation and the doping of 3mg fluorine is joined in high voltage bearing teat glass, add the methyl alcohol of 2mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 6 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.6mA.
Embodiment 7
The carbon black of the Pt/C catalyst after the 6mg inactivation and the doping of 9mg fluorine is joined in high voltage bearing teat glass, add the methyl alcohol of 2mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 7 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.6mA.
Embodiment 8
The carbon black of the Pt/C catalyst after the 6mg inactivation and the doping of 6mg fluorine is joined in high voltage bearing teat glass, add the methyl alcohol of 1mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 8 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.7mA.
Embodiment 9
The carbon black of the Pt/C catalyst after the 6mg inactivation and the doping of 6mg fluorine is joined in high voltage bearing teat glass, add the methyl alcohol of 4mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 9 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.8mA.
Embodiment 10
The carbon black of the Pt/C catalyst after the 6mg inactivation and the doping of 6mg fluorine is joined in high voltage bearing teat glass, add the methyl alcohol of 2mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 1g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 10 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.7mA.
Embodiment 11
The carbon black of the Pt/C catalyst after the 6mg inactivation and the doping of 6mg fluorine is joined in high voltage bearing teat glass, add the methyl alcohol of 2mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 4g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 11 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.7mA.
Embodiment 12
By the Au/SiO after the 6mg inactivation
2catalyst joins in high voltage bearing teat glass, adds the methyl alcohol of 2mL, puts into magnetic stir bar, stirs, and passes into monochloro methane 30s, gets rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collects monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 12 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.6mA.
Embodiment 13
Pt catalyst after the 6mg inactivation is joined in high voltage bearing teat glass, add the methyl alcohol of 2mL, put into magnetic stir bar, stir, pass into monochlorethane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochlorethane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 120 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochlorethane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 13 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.8mA.
Embodiment 14
Au catalyst after the 6mg inactivation is joined in high voltage bearing teat glass, add the formic acid of 2mL, put into magnetic stir bar, stir, pass into monochlorethane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochlorethane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 180 ℃ of stirring reaction 2h; Be cooled to room temperature, discharge unnecessary monochlorethane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 14 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.7mA.
Embodiment 15
Pd catalyst after the 6mg inactivation is joined in high voltage bearing teat glass, add the ethanol of 1mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 10h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 15 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.8mA.
Embodiment 16
Ru catalyst after the 6mg inactivation is joined in high voltage bearing teat glass, add the acetic acid of 2mL, the 2ml carrene, put into magnetic stir bar, stirs; Put into 160 ℃ of stirring reaction 10h of oil bath pan; Be cooled to room temperature, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 16 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.8mA.
Embodiment 17
Ag catalyst after the 6mg inactivation is joined in high voltage bearing teat glass, add the isopropyl alcohol of 2mL, the 2ml carrene, put into magnetic stir bar, stirs; Put into 200 ℃ of stirring reaction 1h of oil bath pan; Be cooled to room temperature, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 17 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.7mA.
Embodiment 18
By the SiO after the 6mg inactivation
2loaded Pt catalyst joins in high voltage bearing teat glass, adds the methyl alcohol of 2mL, and 2mL mono-chloropropane, put into magnetic stir bar, stirs; Put into oil cauldron and bathe, under 2-12 atmospheric pressure, 160 ℃ of stirring reaction 0.5h; Be cooled to room temperature, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 18 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.7mA.
Embodiment 19
By the TiO after the 6mg inactivation
2load Ru catalyst joins in high voltage bearing teat glass, adds the isopropyl alcohol of 1mL, puts into magnetic stir bar, stirs, and passes into monochlorethane 30s, gets rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collects monochlorethane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 7h; Be cooled to room temperature, discharge unnecessary monochlorethane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 19 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.7mA.
Embodiment 20
By the TiO after the 6mg inactivation
2pt-supported catalyst joins in high voltage bearing teat glass, adds the ethylene glycol of 5mL, puts into magnetic stir bar, stirs, and passes into monochloro methane 30s, gets rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collects monochloro methane 6g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 50 ℃ of stirring reaction 10h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 20 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.8mA.
Embodiment 21
By the Al after the 6mg inactivation
2o
3load Au catalyst joins in high voltage bearing teat glass, adds the propionic acid of 2mL, and the 2mL carrene, put into magnetic stir bar, stirs; Put into 100 ℃ of stirring reaction 8h of oil bath pan; Be cooled to room temperature, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 21 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.7mA.
Embodiment 22
By the Al after the 6mg inactivation
2o
3the loaded Ag catalyst joins in high voltage bearing teat glass, adds the n-butanol of 2mL, puts into magnetic stir bar, stirs, and passes into monochloro methane 30s, gets rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collects monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 130 ℃ of stirring reaction 9h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 22 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.7mA.
Embodiment 23
By the TiO after the 6mg inactivation
2loaded Ag and 6mgTiO
2join in high voltage bearing teat glass, add the formic acid of 2mL, 3mL mono-chlorobutane, put into magnetic stir bar, stirs; Put into oil cauldron and bathe, under 2-12 atmospheric pressure, 160 ℃ of stirring reaction 7h; Be cooled to room temperature, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 23 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.7mA.
Embodiment 24
The Pt catalyst of the Pt/C catalyst after the 6mg inactivation and 6mg inactivation is joined in high voltage bearing teat glass, add the methyl alcohol of 2mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 2g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 160 ℃ of stirring reaction 5.5h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 24 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.8mA.
Embodiment 25
By the Al after the 2mg inactivation
2o
3load Ru, the Ru after the 2mg inactivation and 2mgAl
2o
3join in high voltage bearing teat glass, add the propionic acid of 6mL, put into magnetic stir bar, stir, pass into monochloro methane 30s, get rid of invisible spectro air, then under the condition of cooled with liquid nitrogen, collect monochloro methane 4.5g; Room temperature to be returned to, put into oil cauldron and bathe, under 2-12 atmospheric pressure, and 130 ℃ of stirring reaction 9h; Be cooled to room temperature, discharge unnecessary monochloro methane, evaporate to dryness solution, add water ultrasonic, then 12000rpm is centrifugal, repeats ultrasonic and centrifugally operated three times, in order to obtain clean catalyst, final drying is spent the night, the catalyst after being regenerated.
Catalyst after the regeneration that embodiment 25 is obtained carries out the test of electrochemical catalysis character, records its cyclic voltammetry curve, and the oxidation peak current of methyl alcohol is 0.8mA.
Obviously, the explanation of above embodiment is just for helping to understand method of the present invention and core concept thereof.It should be pointed out that the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
Claims (10)
1. the renovation process of noble metal catalyst, is characterized in that, comprises the following steps:
(1) noble metal catalyst is immersed in the mixed solution of Oxidizing and Reducing Agents, more than 50 ℃, under 2-12 atmospheric pressure, more than reaction 0.5h, obtain reacted solution;
Described oxidant is C
1-C
4halogenated hydrocarbons;
Described reducing agent is C
1-C
4organic Alcohol or C
1-C
4organic acid;
The mass ratio of described noble metal catalyst, oxidant, reducing agent is 1:(50-1000): (50-1000);
(2) by reacted solution evaporate to dryness, obtain solid, be the noble metal catalyst after regeneration.
2. the renovation process of noble metal catalyst according to claim 1, it is characterized in that, described step (1) is with after the precious metal catalyst agent carrier mixes by noble metal catalyst, immerse in the mixed solution of Oxidizing and Reducing Agents, more than 50 ℃, under 2-12 atmospheric pressure, more than reaction 0.5h, obtain reacted solution.
3. the renovation process of noble metal catalyst according to claim 1 and 2, is characterized in that, the renovation process of described noble metal catalyst also comprises step (3), it is ultrasonic that the solid that step (2) is obtained adds water, centrifugal, after drying, the noble metal catalyst after being regenerated.
4. the renovation process of noble metal catalyst according to claim 1 and 2, it is characterized in that a kind of in the mixture of mixture, Ag and the carrier loaded Ag catalyst of the mixture of mixture, Au and carrier loaded Au catalyst that described noble metal catalyst is Pt, Au, Pd, Ru, Ag, carrier loaded Pt catalyst, carrier loaded Au catalyst, carrier loaded Pd catalyst, carrier loaded Ru catalyst, carrier loaded Ag catalyst, Pt and carrier loaded Pt catalyst, Pd and carrier loaded Pd catalyst, Ru and carrier loaded Ru catalyst;
Described carrier is C, SiO
2, TiO
2perhaps Al
2o
3.
5. the renovation process of noble metal catalyst according to claim 1 and 2, is characterized in that, the described reaction time is 1-10h.
6. the renovation process of noble metal catalyst according to claim 1 and 2, is characterized in that, described reaction temperature is 80-200 ℃, and pressure is 2-10 atmospheric pressure.
7. the renovation process of noble metal catalyst according to claim 1 and 2, is characterized in that, described oxidant is monochloro methane, carrene or monochlorethane.
8. the renovation process of noble metal catalyst according to claim 1 and 2, is characterized in that, described reducing agent is methyl alcohol, formic acid, ethanol, acetic acid, isopropyl alcohol or ethylene glycol.
9. the renovation process of noble metal catalyst according to claim 2, is characterized in that, described precious metal catalyst agent carrier is C, SiO
2, TiO
2perhaps Al
2o
3.
10. the renovation process of noble metal catalyst according to claim 2, is characterized in that, described noble metal catalyst and precious metal catalyst agent carrier mass ratio be 1:(0.1-5).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391138A (en) * | 2016-08-31 | 2017-02-15 | 中国科学院福建物质结构研究所 | In-situ regeneration method of Pd catalyst for CO dehydrogenation purification |
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| JPH08196905A (en) * | 1995-01-23 | 1996-08-06 | Kawaken Fine Chem Co Ltd | Particle size-adjusted noble metal-carbon catalyst |
| CN102921434A (en) * | 2012-10-31 | 2013-02-13 | 中国科学院长春应用化学研究所 | Recovery method of noble metal catalyst |
| CN102962446A (en) * | 2012-11-13 | 2013-03-13 | 中国科学院长春应用化学研究所 | Method for activating noble metal nano particles by liquid phase dissolving |
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|---|---|---|---|---|
| JPH08196905A (en) * | 1995-01-23 | 1996-08-06 | Kawaken Fine Chem Co Ltd | Particle size-adjusted noble metal-carbon catalyst |
| CN102921434A (en) * | 2012-10-31 | 2013-02-13 | 中国科学院长春应用化学研究所 | Recovery method of noble metal catalyst |
| CN102962446A (en) * | 2012-11-13 | 2013-03-13 | 中国科学院长春应用化学研究所 | Method for activating noble metal nano particles by liquid phase dissolving |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106391138A (en) * | 2016-08-31 | 2017-02-15 | 中国科学院福建物质结构研究所 | In-situ regeneration method of Pd catalyst for CO dehydrogenation purification |
| CN106391138B (en) * | 2016-08-31 | 2019-05-17 | 中国科学院福建物质结构研究所 | A kind of CO dehydrogenation purification in situ regeneration method of Pd catalyst |
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Application publication date: 20131225 |