CN101491778A - Preparation method of thin shell shaped noble metal catalyst - Google Patents
Preparation method of thin shell shaped noble metal catalyst Download PDFInfo
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- CN101491778A CN101491778A CNA2008100329140A CN200810032914A CN101491778A CN 101491778 A CN101491778 A CN 101491778A CN A2008100329140 A CNA2008100329140 A CN A2008100329140A CN 200810032914 A CN200810032914 A CN 200810032914A CN 101491778 A CN101491778 A CN 101491778A
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Abstract
The invention relates to a preparation method of thin-shelled noble metal catalyst, and mainly solves the problems of the prior art of high dosage, poor selectivity and short service life of noble metal. The preparation method better solves the technical problems of the prior art by adopting the technical proposal comprising the following steps of: (a) coating the slurry of a coat porous material on the inner core of an inert carrier, drying the slurry coating and baking the slurry coating at a temperature of between 700 and 1,200 DEG C for 0.5 to 10 hours to obtain a laminar composite carrier; (b) impregnating the surface of the laminar composite carrier with a solution containing noble metal and cocatalyst components, drying the laminar composite carrier, and baking the laminar composite carrier in the air at a temperature of between 200 and 700 DEG C for 1 to 24 hours to obtain a thin-shelled catalyst precursor; and (c) reducing the thin-shelled catalyst precursor in a reducing atmosphere at a temperature between 300 and 800 DEG C for 1 to 24 hours to obtain the thin-shelled noble metal catalyst. The preparation method can be used in the industrial production of gas purification materials which are dehydrogenation-deoxidization catalysts, alkanes and aromatic hydrocarbons for selective hydrogen oxidation in a dehydrogenation process.
Description
Technical field
The present invention relates to a kind of preparation method of thin shell shaped noble metal catalyst.
Background technology
The fast development of industry such as electronics industry, semi-conducting material, modern chemical industry, metallurgy, instrument, aerospace and atomic energy needs increasing high-purity gas, as high-purity hydrogen, nitrogen, oxygen, helium, argon gas, carbon dioxide etc.These gas cleanings are usually directed to dehydrogenation, deoxidation process, as removing the hydrogen impurity in nitrogen, methane, carbon monoxide, carbon dioxide and the various inert gas (nitrogen, xenon, krypton, neon etc.) in the presence of at oxygen, or in the presence of hydrogen, remove the oxygen impurities in the above-mentioned gas.This process can adopt absorptive-type cleanser, as removing H with CuO
2, also can adopt the material of consumption-type, be to remove behind the carbon dioxide as make oxygen conversion with C deoxidiser.But purify for a large amount of gases, then adopt chemical method proper, feed another kind of reaction gas this moment usually in the unstripped gas that contains a kind of foreign gas, it is reacted under the effect of catalyst be combined to water, thereby reach the effect of purifying gas.As after utilizing the empty branch of transformation absorption to obtain purity 99～99.9% nitrogen, be further purified to handle and produce 99.9999% high-purity nitrogen, in nitrogen, add appropriate amount of hydrogen exactly, the hydrogenation deoxidation tower of catalyst is equipped with in feeding, make oxygen impurities and the hydrogen generation water that reacts at normal temperatures, thereby obtain high-purity nitrogen.Produce in that urea is synthetic in recent years for another example, the unstripped gas carbon dioxide need remove hydrogen treat, also is to aerating oxygen wherein, carries out catalytic combustion.Patent CN1006203 has reported that palladium, cupric oxide are supported on and has made inert gas engaging hydrogen oxygen cleanser on the titanium dioxide.Patent CN85102710 has reported platinum, Pd/TiO 2 deoxygenationcatalyst.Above-mentioned catalyst is shell shaped catalyst, has advantages such as activity is high, treating capacity is big, but catalyst bullion content height, thereby cost an arm and a leg.
In addition, being applied to chemical industry and oil refining process catalyst at present, quite a few is arranged is to adopt the loaded catalyst of noble metal as active component.Because noble metal costs an arm and a leg, so its content in catalyst is often lower.Discover that active component non-uniform Distribution in carrier can reduce the consumption of noble metal, improve the utilization rate of noble metal; Simultaneously, the catalyst of non-uniform Distribution also showed than the better activity of equally distributed catalyst, selectivity and life-span in many reactions.This wherein most important a kind of be exactly egg-shell catalyst, it is the surperficial thin-shell type that active component concentrates on the carrier top layer, be mainly used in the selectivity that improves the cascade reaction intermediate product or improve the rapid-action selectivity, promptly when interior diffusion rate＜＜during the intrinsic reaction rate, if reaction rate is very fast, reactant molecule has just diffused in the duct a bit apart from just having reacted away, and diffusion rate does not catch up with, make the inner surface of catalyst center part not obtain utilizing like this, thereby the catalyst activity component is prepared into the distribution of shell shape.In addition, because active component concentrates on the carrier extexine, for some exothermic reactions, more help the transfer of reaction heat, with the stability that keeps catalyst and prolong life of catalyst, thereby be widely used, and obtain good effect industrial.
As in the producing phenyl ethylene by ethyl benzene catalytic dehydrogenation process, because dehydrogenation reaction is the endothermic reaction, thereby the bed temperature of catalyst can obviously reduce in course of reaction, thereby caused the reduction of feed stock conversion.A kind of method of control reaction temperature is an aerating oxygen or contain the gas-selectively oxidizes hydrogen gas of oxygen in reaction, be the hydrogen that catalytic combustion produces in certain embodiments, thereby raising reaction temperature, impel balance to move, and then improve the conversion ratio that unsaturated hydrocarbon is produced in the saturated hydrocarbon dehydrogenation.For the selective oxidation reaction of hydrogen, patent US6177381 and CN1479649A have reported the layered catalyst composition.This catalyst has for example coating gama-alumina for example of Alpha-alumina and an inorganic oxide of a kernel.On the skin equably load platinum metal such as platinum and co-catalyst such as tin.And for example patent US6858769 and CN1705510A have reported that a kind of is the H 2 selective oxidation catalyst of carrier with the lithium aluminate.This catalyst is a kernel with the cordierite, is coating with the lithium aluminate, load platinum metal and modified metal on coating, for example, platinum and tin.Oxidation has good effect to this catalyst to hydrogen selective in dehydrogenation reaction, and the consumption of Pt obviously reduces in the catalyst.When the catalyst of above-mentioned patent preparation was used for the hydrogen selective oxidation, raw material saturated hydrocarbon loss late height particularly under the situation of resource, energy growing tension, reduced consumption of raw materials and just seems more important.
The characteristics of above-mentioned catalyst are to use complex layered carrier, promptly with inert material, as cordierite, Alpha-alumina is the kernel of carrier, because these inert material specific areas are little, in order to improve activity of such catalysts, patent all adopts the coating material that applies one deck bigger serface on carrier to enlarge the method for carrier effective surface area.When the shell shaped catalyst of above-mentioned patent preparation was used for the hydrogen selective oxidation, raw material saturated hydrocarbon loss late height particularly under the situation of resource, energy growing tension, reduced consumption of raw materials and just seems more important.
Summary of the invention
Technical problem to be solved by this invention be prior art when preparation thin shell shaped noble metal catalyst noble metal dosage height, poor selectivity, short problem of life-span provides a kind of preparation method of new thin shell shaped noble metal catalyst.This method has that preparation technology is simple, the noble metal load capacity is low, units activity component effective rate of utilization height, selectivity height, long advantage of life-span.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of preparation method of thin shell shaped noble metal catalyst may further comprise the steps successively:
A) will contain and be selected from γ-Al
2O
3. δ-Al
2O
3, η-Al
2O
3, θ-Al
2O
3, at least a coating porous material in silica, zeolite, non-zeolite molecular sieve, titanium oxide or the zirconia slurries be coated in and be selected from α-Al
2O
3, θ-Al
2O
3, at least a inert carrier in metal, SiC, cordierite, zirconia, titanium oxide, quartz, spinelle, mullite or the mullite kernel on, following dry 1～24 hour prior to 50～250 ℃, make coating and the effective combination of carrier kernel in 0.5～10 hour 700～1200 ℃ of roastings then, obtain lamellar composite carrier;
B) with the solution surface dipping lamellar composite carrier that contains noble metal, cocatalyst component, prior to 100～150 ℃ of dryings 1～24 hour, roasting 1～24 hour in 200～700 ℃ of air then obtained the shell shaped catalyst presoma;
C) with the shell shaped catalyst presoma under hydrogen or other reducing atmospheres, in 300～800 ℃ the reduction 1～24 hour, promptly make thin shell shaped noble metal catalyst.
In the technique scheme, check in the lamellar composite carrier catalyst precursor adsorption capacity a little less than, preferred version is selected from α-Al
2O
3, at least a in SiC, mullite, spinelle or the cordierite, consumption is 80～95% of a lamellar composite carrier weight; The coating of lamellar composite carrier is heat-resisting porous oxide material, and preferably the sorptive material of porous is stronger to the catalyst precursor adsorption capacity, and has high specific area, and preferred version is selected from θ-Al
2O
3, δ-Al
2O
3, γ-Al
2O
3, at least a in silica or the molecular sieve, consumption is 5～20% of a lamellar composite carrier weight, coating layer thickness is 50～200 microns, 50～200 meters of specific areas
2/ gram.The kernel of lamellar composite carrier can be made different shapes as required, and as cylindric, spherical, sheet, tubular, cellular or Raschig ring etc., but spherical inner core is reasonable selection, and its diameter is preferably 1～5 millimeter, so that commercial Application.
Although the control of the particle shape of ball type carrier and composition is important factor for preparing carriers, but since the inert core of carrier to the chemical substance absorption affinity a little less than, therefore the preparation for the ball type carrier kernel there is no special requirement, can adopt preparing carriers method commonly used to carry out, as rolling balling, forming oil column, extrusion molding etc.But add an amount of pore-foaming agent usually in the preparation, as graphite, sesbania powder, coconut husk, active carbon etc. so that the preparation the carrier kernel have big aperture and little specific area, and when roasting usually above 1200 ℃.
At first, the preparation of coating ingredients ultrafine particle.It is more even that ultrafine particle helps the coating coating on the one hand, can increase the specific area of coating simultaneously, helps the dispersion of active component, can delay the gathering and the sintering of aluminium oxide simultaneously.Methods such as the coating ingredients ultrafine particle can be pulverized by air-flow, ball milling are controlled at its particle diameter below 100 microns.
Secondly, the preparation of coating ingredients slurries.With in coating ingredients such as aluminium oxide, molecular sieve and the auxiliary agent one or more, distilled water stirred according to a certain percentage, mixed, and makes slurries.Aluminium oxide can be used θ-Al
2O
3, δ-Al
2O
3, γ-Al
2O
3Also need to add a kind of organic adhesive in the slurries to increase the intensity of coating material on kernel.Polyvinyl alcohol, CMC, hydroxypropyl cellulose, methyl or ethyl or carboxyethyl cellulose, ring essence etc. recklessly for example, but be not limited to these.The addition of organic adhesive is controlled at 0.3～5% of slurries gross mass.Also contain inorganic binder in the slurries, as inorganic clay, aluminium colloidal sol, Ludox, waterglass, calcium silicates, potassic feldspar etc., addition is controlled at 0.1～20% of slurries gross mass.In addition, also need add surfactant in the slurries, kind to surfactant there is no particular restriction, can be anionic surfactant, cationic surface active agent, amphoteric surfactant and non-ionic surface active agent, as tween, sapn, softex kw, tetraethylammonium bromide etc., to reduce the surface tension of slurries, addition is controlled at 0.01～1.0% of slurries gross mass.
Once more, the control of coating slurries particle diameter.In order to strengthen the firmness of coating, need to reduce particle size in the slurries, obtain the slurries that particle size is little, distribution is narrow.This can be undertaken by ball-milling method, but is not limited to this method.The ball milling time was controlled at 30 minutes～5 hours, preferably was controlled at 1.5～3 hours, thereby the slurries particle diameter is controlled at below 10 microns.
Then, slurries form coating by the surface that sprays, methods such as glue is coated with, spin, dipping, dip-coating cover kernel, preferred spraying process.The thickness of coating can change as required, but should be controlled between 40～300 microns, preferably is controlled between 50～200 microns.After the coated material of the kernel of lamellar composite carrier applies, 50～250 ℃ of dryings 1～24 hour, then 700～1200 ℃ of roastings 0.5～10 hour so that coating and the effective combination of carrier kernel, thereby obtain lamellar composite carrier.
At last, supported catalyst active component on lamellar composite carrier.Catalyst activity component such as platinum-group component ruthenium, rhodium, palladium, osmium, iridium, platinum and co-catalyst can be dispersed on the lamellar composite carrier with any method that is suitable for surface impregnation.When preparation catalyst of the present invention, can use any decomposable platinum family compound, as halide, nitrate, oxide etc.Can on the lamellar composite carrier surface, flood platinum-group component earlier, follow one or more cocatalyst component of surface impregnation again, also can flood one or more cocatalyst component at carrier surface earlier, then flood platinum-group component; Certainly flood platinum-group component simultaneously and cocatalyst component also can.Co-catalyst can also be dispersed in earlier in the coating slurries, also can carry out surface impregnation after forming coating.Comparatively Chang Yong method is to spray the coating that contains co-catalyst on the kernel earlier, after dry and roasting, carrier impregnation is prepared catalyst in containing the solution of platinum-group component.At last, the catalyst that will contain active component was 100～150 ℃ of dryings 1～24 hour, and roasting is 1～24 hour in 200～700 ℃ of air, reduces in the hydrogen in 300～800 ℃ of reduction 1～4 hour, promptly makes shell shaped catalyst.
Above-described method is generally used for preparing thin shell shaped noble metal catalyst, is generally used for the selective oxidation of hydrogen in gas purification material-dehydrogenation dehydrogenation catalyst and alkane, the aromatic hydrocarbons certain embodiments.
The inventive method is based on adsorption theory, by adsorption capacity and the adsorption rate of modulation lamellar composite carrier to catalyst precursor, make the easier outer surface that is dispersed in catalyst of catalyst activity component, the concentration gradient of noble metal is littler, shell shaped catalyst thickness is thinner, more even, the eggshell state structure that presents high dispersive, units activity component effective rate of utilization height can effectively reduce the consumption of noble metal.In addition, catalyst effective active layer specific area is big, thin thickness, makes raw material and product have shorter the evolving path, reactant and the product time of staying in catalyst granules shortens, thereby the side reaction minimizing, having reduced the loss of raw material, therefore the purpose selectivity of product is improved.In addition, because the lamellar composite carrier coating is thinner, reaction occurs in the outer surface of catalyst, thereby is easy to conduct heat, and is not easy sintering and carbon distribution, has prolonged the service life of catalyst, has obtained better technical effect.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
(granularity is below 5 microns, 270 meters of specific areas with 20 gram aluminium colloidal sols (aluminium oxide that contains 15% mass ratio), 3.0 gram barium monoxide, 0.6 gram zirconyl chloride, 50 gram modenite powder
2/ gram), 12 gram 6% polyvinyl alcohol and 100 gram distilled water mix, stir and made coating paste in 1.0 hours, the cordierite bead of 4 millimeters of diameters is impregnated in the mixed coating slurry of being prepared, placement is spent the night, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry once more 2 hours, in 1100 ℃ of roastings 3 hours, obtain lamellar composite carrier at last.The analysis showed that about 120 microns of coating layer thickness, the coating specific area is 178 meters
2/ gram.
The complex layered carrier impregnation that will make again is in the chloroplatinic acid of pH=2～6, palladium chloride solution, then in 120 ℃ of dryings 2 hours, then 565 ℃ of hydrogen reducings 2 hours.Catalyst is marked as A.Elementary analysis shows with regard to whole catalyst and contains Pt 0.06% according to the mass fraction meter, and Pd 0.02%, and Ba 0.8%, and Zr 0.12%.
[embodiment 2]
Polyacrylamide solution, the 0.4 gram betaine of 40 gram alumina sols (aluminium oxide that contains 15% mass ratio), 60 grams 3% are made slurries.In this mixed liquor, add 0.3 gram calcium silicates, 40 gram θ-Al then
2O
3Powder.Stir about adds 2.0 gram 25%MgCl after ten minutes
2The aqueous solution, the slurries that obtain at room temperature ball milling made that particle size was controlled at below 20 microns in 4 hours.Slurries spray to the α-Al of 4 millimeters of particle diameters
2O
3On the bead, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours once more, in 800 ℃ of roastings 10 hours, obtain lamellar composite carrier at last.The analysis showed that about 80 microns of coating layer thickness, the coating specific area is 138 meters
2/ gram.
In Rotary Evaporators, lamellar composite carrier is immersed in the mixed solution of lithium nitrate and palladium bichloride with equi-volume impregnating.The catalyst that dipping is good heats in Rotary Evaporators up to the whole evaporates to dryness of solution, then in 100 ℃ of dryings 2 hours, and then reductase 12 hour in 565 ℃ of hydrogen.The good catalyst of reduction 150 ℃ of dryings 2 hours in air stream then are warmed up to 650 ℃, and bubbling feeds steam, continue 2 hours in this state, then are cooled to room temperature.Catalyst is marked as B.Elementary analysis shows with regard to whole catalyst and contains Pd 0.05% according to the mass fraction meter, and Li 0.41%, and Mg 0.14%.
[embodiment 3]
Cyclodextrin solution solution, 2.0 gram lanthanas, the 1.0 gram softex kws of 35 gram alumina sols (aluminium oxide that contains 25% mass ratio), 5 grams, 40% Ludox, 60 grams 4% are made slurries.In this mixed liquor, add 0.4 gram calcium silicates, 0.3 gram potash and the pretreated size of 40 gram processes then at the δ-Al below 10 microns
2O
3Powder.The slurries that obtain at room temperature ball milling made that particle size was controlled at below 10 microns in 4 hours.Slurries are sprayed on the mullite bead of 4 millimeters of particle diameters, in 100 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours once more, in 900 ℃ of roastings 6 hours, obtain lamellar composite carrier at last.The analysis showed that about 100 microns of coating layer thickness, the coating specific area is 120 meters
2/ gram.
Measuring 0.16 ml concn is 50wt%SnCl
4Solution adds water to 16 milliliters.Weigh 0.13 gram RhCl
3, it is dissolved in the tin chloride solution of front, stirred 10 minutes.With the 40 above-mentioned solution of lamellar composite carrier rotary dipping made of gram 15 minutes, vacuumize up to solution at 50 ℃ earlier and all absorb, then with catalyst in 150 ℃ of dryings 2 hours.2.17 gram lithium nitrates are dissolved in 16 ml waters, rotary dipping is 15 minutes once more, rising temperature to 50 ℃ and vacuumizing up to solution all absorbs, then with catalyst in 150 ℃ of dryings 2 hours, reductase 12 hour in 565 ℃ of hydrogen atmospheres, 650 ℃ were adopted the feeding water vapour 2 hours then, then were cooled to room temperature in moving air atmosphere, obtained catalyst.Catalyst is marked as C.Elementary analysis shows with regard to whole catalyst and contains Rh 0.06% according to the mass fraction meter, and Sn 0.15%, and Li 0.58%.
[embodiment 4]
Cyclodextrin solution solution, the 1.0 gram ceteths of 38 gram alumina sols (aluminium oxide that contains 20% mass ratio), 4 gram lanthanum nitrates, 60 grams 4% are made slurries.In this mixed liquor, add 0.2 gram calcium silicates, 40 grams then through pretreated δ-Al below 5 microns
2O
3Powder.The slurries that obtain at room temperature ball milling made that particle size was controlled at below 10 microns in 4 hours.Slurries spray on the spinelle bead of 4 millimeters of particle diameters, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours once more, at last in 1050 ℃ of roastings 5 hours, obtain lamellar composite carrier and the analysis showed that about 90 microns of coating layer thickness, the coating specific area is 118 meters
2/ gram.
Lithium nitrate is dissolved in the water, and vacuum impregnation is on the lamellar composite carrier of having made, then in 150 ℃ of dryings 2 hours.With SnCl
4And sodium chloroplatinite is dissolved in the ethanolic solution, is immersed on the carrier 150 ℃ of dryings 2 hours once more, then reductase 12 hour in 550 ℃ of hydrogen atmospheres, 650 ℃ are adopted and feed water vapours then, do not have chlorion in tail gas, then in air atmosphere, be cooled to room temperature, obtain catalyst D.Elementary analysis shows with regard to whole catalyst and contains Pt 0.05% according to the mass fraction meter, and Sn 0.08%, and Li 0.24, and La 0.03%.
[embodiment 5]
Alumina sol (aluminium oxide that contains 15% mass ratio), the glycerite of 60 grams 2%, the 0.5 gram sorbester p17 of 40 grams are made slurries.In this mixed liquor, add 0.5 gram potassic feldspar, the pretreated size of 40 gram processes then at gamma oxidation aluminium powder (the specific area 200m below 10 microns
2/ g).Stir about adds the SnCl of 1.5 grams 50% after ten minutes
4The aqueous solution, the slurries that obtain at room temperature ball milling made that particle size was controlled at below 10 microns in 4 hours.Slurries spray on the SiC bead of 4 millimeters of particle diameters, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours once more, in 1100 ℃ of roastings 6 hours, obtain lamellar composite carrier at last.The analysis showed that about 120 microns of coating layer thickness, 160 meters of coating specific areas
2/ gram.
Lithium nitrate and chloroplatinic acid are dissolved in the water respectively, be mixed with mixed solution, making its pH value with the HCl regulator solution is about 4, then this solution is heated to 80 ℃, is immersed on the lamellar composite carrier of having made, then in 150 ℃ of dryings 2 hours, then reductase 12 hour in 550 ℃ of hydrogen atmospheres, 650 ℃ are adopted and feed water vapours then, do not have chlorion in tail gas, then in air atmosphere, be cooled to room temperature, obtain catalyst E.Elementary analysis shows with regard to whole catalyst and contains Pt 0.09% according to the mass fraction meter, and Sn 0.12%, and Li 0.50%.
[comparative example 1]
Method according to embodiment 1 among the patent CN85102710 prepares platinum, Pd/TiO 2 deoxygenationcatalyst, is labeled as F.
[comparative example 2]
The preparation of this oxidation catalyst is shown in the embodiment 2 of 4812597 li of the U.S. Pat mentioned in the reference of front.Elementary analysis shows with regard to whole catalyst and contains Pt 0.20% according to the mass fraction meter, and Sn 0.23%, and Li 0.20%.Catalyst is marked as G.
[comparative example 3]
The preparation of this oxidation catalyst is shown in the embodiment 3 of 6858769 li of the U.S. Pat mentioned in the reference of front.Elementary analysis shows with regard to whole catalyst and contains Pt 0.14% according to the mass fraction meter, and Sn 0.16%, and Li 0.72%.Catalyst is marked as H.
[embodiment 6]
Catalyst A, the B of preparation among the embodiment 1,2 are used for gas purification material-dehydrogenation deoxidation.Unstripped gas is a high pure nitrogen, and gas pressure is a normal pressure, and temperature is a room temperature, and air speed is 10000 hours
-1, adopt the mass flowmenter control system to add hydrogen or oxygen, make in the pure nitrogen of product and contain certain oxygen or hydrogen, investigate its dehydrogenation and deoxy performance, the results are shown in Table 1.
The dehydrogenation deoxy performance of table 1 catalyst
As shown in Table 1, the catalyst of the inventive method preparation has high dehydrogenation, deoxy performance.
[embodiment 7]
The catalyst of preparation among the embodiment 3～5 is used for H 2 selective oxidation.Reactor inside diameter is 25 millimeters a stainless steel reaction pipe, in adorn 30 milliliters of catalyst.Reaction pressure is a normal pressure, liquid air speed 3 hours
-1, 580 ℃ of reaction temperatures, the reactant composition sees Table 2.
The raw material of H 2 selective oxidation is formed in table 2 ethylbenzene dehydrogenation process
| Raw material | Content (molar percentage) |
| Styrene | 2.4 |
| Ethylbenzene | 5.4 |
| Benzene and toluene | 0.08 |
| H 2 | 2.4 |
| O 2 | 1.1 |
| N 2 | 0.11 |
| Water | 88.51 |
The results are shown in Table 3 for activity of such catalysts and selectivity.As can be seen from the table, the catalyst of this method preparation is compared with reference catalyst and is had higher oxygen selectivity and lower aromatic hydrocarbons loss late.Simultaneously, catalyst bullion content of the present invention is compared remarkable reduction with reference catalyst.
The H 2 selective oxidation performance of table 3 catalyst
Annotate: conv. is a conversion ratio, and sel. is a selectivity.
In order further to investigate stability with the catalyst of this method preparation, catalyst D to embodiment 4 preparations carries out 24 hours steam burin-in process in 800 ℃, TEM result shows that the fresh and aging back of catalyst of the present invention Pt particle diameter is respectively 1～2 nanometer, do not see obvious increase, and be respectively 1～2 nanometer and 2～3 nanometers after the fresh and degradation of the Pt particle diameter of catalyst in the comparative example, agglomeration obviously takes place.Catalyst after aging and reference catalyst be loaded into once more carry out performance evaluation in the reactor, it is identical with embodiment 7 to estimate process conditions, the results are shown in Table 4.As seen from table, reference catalyst significantly descends through degradation rear catalyst performance, and catalyst performance of the present invention decline is less, shows that the catalyst that adopts preparing carriers of the present invention has good heat endurance especially.
The H 2 selective oxidation performance of the aging rear catalyst of table 4
Claims (5)
1, a kind of preparation method of thin shell shaped noble metal catalyst may further comprise the steps successively:
A) will contain and be selected from γ-Al
2O
3. δ-Al
2O
3, η-Al
2O
3, θ-Al
2O
3, at least a coating porous material in silica, zeolite, non-zeolite molecular sieve, titanium oxide or the zirconia slurries be coated in and be selected from α-Al
2O
3, θ-Al
2O
3, at least a inert carrier in metal, SiC, cordierite, zirconia, titanium oxide, quartz, spinelle, mullite or the mullite kernel on, following dry 1～24 hour prior to 50～250 ℃, make coating and the effective combination of carrier kernel in 0.5～10 hour 700～1200 ℃ of roastings then, obtain lamellar composite carrier;
B) with the solution surface dipping lamellar composite carrier that contains noble metal, cocatalyst component, prior to 100～150 ℃ of dryings 1～24 hour, roasting 1～24 hour in 200～700 ℃ of air then obtained the shell shaped catalyst presoma;
C) with the shell shaped catalyst presoma under hydrogen or other reducing atmospheres, in 300～800 ℃ the reduction 1～24 hour, promptly make thin shell shaped noble metal catalyst.
2,, it is characterized in that the carrier kernel is selected from α-Al according to the preparation method of the described thin shell shaped noble metal catalyst of claim 1
2O
3, at least a in SiC, mullite, spinelle or the cordierite.
3,, it is characterized in that porous coating material is selected from θ-Al according to the preparation method of the described thin shell shaped noble metal catalyst of claim 1
2O
3, δ-Al
2O
3, γ-Al
2O
3, at least a in silica or the molecular sieve.
4, according to the preparation method of the described thin shell shaped noble metal catalyst of claim 1, it is characterized in that the porous coating material consumption is 5～20% of a lamellar composite carrier weight, the kernel consumption is 80～95% of a lamellar composite carrier weight.
5,, it is characterized in that the coating material coating layer thickness is 50～200 microns, 50～200 meters of specific areas according to the preparation method of the described thin shell shaped noble metal catalyst of claim 1
2/ gram.
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2008
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| CN104109090B (en) * | 2013-04-16 | 2016-05-18 | 中国石油化工股份有限公司 | The method of CO gas-phase synthesis of oxalate |
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| CN108499586B (en) * | 2018-03-30 | 2020-09-11 | 中国石油化工股份有限公司 | Catalyst for hydrogenation reaction and preparation method thereof |
| CN109589778A (en) * | 2018-10-17 | 2019-04-09 | 南京工程学院 | It is a kind of for removing the nano material of bacterium and formaldehyde |
| CN109589778B (en) * | 2018-10-17 | 2021-09-03 | 南京工程学院 | Nano material for removing bacteria and formaldehyde |
| CN111250086A (en) * | 2018-11-30 | 2020-06-09 | 中国石油化工股份有限公司 | Non-noble metal propane dehydrogenation catalyst with modified eggshell-shaped mesoporous material as carrier and preparation method and application thereof |
| CN112892612A (en) * | 2019-12-03 | 2021-06-04 | 中国石化集团金陵石油化工有限责任公司 | Catalyst for hydrocarbon conversion reaction |
| CN114585439A (en) * | 2019-12-03 | 2022-06-03 | 中国石油化工股份有限公司 | Catalyst suitable for hydrocarbon conversion reaction, preparation method and application thereof |
| CN112892612B (en) * | 2019-12-03 | 2023-01-17 | 中国石化集团金陵石油化工有限责任公司 | Catalyst for hydrocarbon conversion reaction |
| CN114585439B (en) * | 2019-12-03 | 2024-05-14 | 中国石油化工股份有限公司 | Catalyst suitable for hydrocarbon conversion reaction, preparation method and application thereof |
| CN114425409A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for producing unsaturated aromatic hydrocarbon by dehydrogenating saturated aromatic hydrocarbon and application thereof |
| CN114425409B (en) * | 2020-10-15 | 2024-05-03 | 中国石油化工股份有限公司 | Catalyst for producing unsaturated aromatic hydrocarbon by dehydrogenation of saturated aromatic hydrocarbon and application thereof |
| CN116586120A (en) * | 2023-01-19 | 2023-08-15 | 长江三星能源科技股份有限公司 | Preparation method of multifunctional catalyst for hydrogen production purification and prepared catalyst |
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