CN101428238B - Layered composite carrier with thermal stability - Google Patents
Layered composite carrier with thermal stability Download PDFInfo
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- CN101428238B CN101428238B CN2007100478704A CN200710047870A CN101428238B CN 101428238 B CN101428238 B CN 101428238B CN 2007100478704 A CN2007100478704 A CN 2007100478704A CN 200710047870 A CN200710047870 A CN 200710047870A CN 101428238 B CN101428238 B CN 101428238B
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- thermal stability
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Abstract
The invention relates to a layered composite carrier with thermal stability and aims to solve the technical problem that the thermal stability of layered composite carrier in the prior art is poor. The invention adopts the layered composite carrier with the thermal stability, which includes a kernel of an inert carrier and a porous coating material outer layer, wherein the kernel contains at least one of the following materials: Alpha-Al2O3, Theta-AI203, metal, SiC, cordierite, zirconia, titanium oxide, quartz, spinel, porzite, or mullite; and the porous coating material outer layer contains at least one of the following materials: Gamma-AI2O3, Delta-AI203, Eta-AI203, Theta-AI203, silica/alumina, zeolite, non-zeolite molecular sieve, titania or zirconia. Furthermore, the invention is characterized in that at least one of lanthanum, cerium, praseodymium, neodymium, erbium, ytterbium, barium, zirconium, lithium, magnesium, and zinc, is used as a promoter. Therefore, the problem of poor thermal stability is solved and the invention can be applied to industrial production for preparing thin-casing shaped catalysts with high-temperature resistance.
Description
Technical field
The present invention relates to a kind of lamellar composite carrier of heat endurance.
Background technology
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 uneven distribution in carrier can reduce the consumption of noble metal, improve the utilization rate of noble metal; Simultaneously, the catalyst of uneven 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.
Cleaning catalyst for tail gases of automobiles for example, CN1342520 has invented a kind of cleaning catalyst for tail gases of automobiles, with the cordierite honeycomb ceramic matrix is first carrier, with the aluminum oxide coating layer slurries is second carrier, it is characterized in that the aluminum oxide coating layer slurries comprise aluminium oxide, Rare Earth Lanthanum and cerium oxide, noble metal, transition metal and alkaline-earth metal.CN1502407 has reported a kind of cleaning catalyst for tail gases of automobiles and preparation method thereof, is first carrier, (mixes up Zr with aluminium oxide-lanthanum rich mischmetal with cordierite honeycomb ceramic
4+, Ba
2+Deng) coating is second carrier, be active component coating to contain transition metal, rare earth element, alkaline-earth metal and minute amount of noble metal.CN1600418 discloses a kind of cleaning catalyst for tail gases of automobiles and preparation method thereof, it promptly is carrier with the cordierite ceramic, with aluminium glue and modenite is coated substrate, with one or more oxides or composite oxides in La-Ce-Zr solid solution or La, Ce, the elements such as Zr, Mn is auxiliary agent, is main active component with Pt, Pd, Rh.
For another example 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.
A common feature of above-mentioned catalyst is to use complex carrier, promptly with inert material, as ceramic honey comb, 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.But this coating is at high temperature during (＞600 ℃) long-term operation, its physicochemical characteristics generation significant change, particularly its specific area reduction, texture destruction even recurring structure variation etc., thus catalyst performance influenced, and the long period that has limited catalyst uses.
Summary of the invention
Technical problem to be solved by this invention is lamellar composite carrier poor heat stability that exists in the prior art and the short problem in shell shaped catalyst noble metal service life made, and a kind of lamellar composite carrier of heat endurance is provided.This lamellar composite carrier has physics, chemical property is stable and thin shell shaped noble metal catalyst that make is high temperature resistant, the advantage of long service life.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of lamellar composite carrier of heat endurance comprises the kernel of an inert carrier and is combined in porous coating material outer layer on the kernel that this kernel comprises and is selected from α-Al
2O
3, θ-Al
2O
3, at least a in metal, SiC, cordierite, zirconia, titanium oxide, quartz, spinelle, mullite or the mullite; Porous coating material outer layer comprises and is selected from γ-Al
2O
3, δ-Al
2O
3, η-Al
2O
3, θ-Al
2O
3, at least a in silica, zeolite, non-zeolite molecular sieve, titanium oxide or the zirconia and be selected from least a in lanthanum, cerium, praseodymium, neodymium, erbium, ytterbium, barium, zirconium, lithium, magnesium or the zinc and be auxiliary agent.
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 75～95% of a lamellar composite carrier weight.Lamellar composite carrier coating skin comprises 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
3Or at least a in 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 auxiliary agent preferred version is selected from least a in lanthanum, cerium, barium, lithium, magnesium or the zinc, and consumption is 0.05～5% of a lamellar composite carrier weight.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 10 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, γ-Al
2O
3, δ-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 1 micron.
At last, 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.
The lamellar composite carrier of above-described heat endurance is generally used for preparing resistant to elevated temperatures thin shell shaped noble metal catalyst.
Among the present invention, be auxiliary agent owing to adopt at least a in lanthanum, cerium, praseodymium, neodymium, erbium, ytterbium, barium, zirconium, lithium, magnesium, the zinc, its at high temperature with active A l
2O
3And molecular sieve generation chemical reaction, generate the higher chemical substance of heat endurance, as MgAl
2O
4, ZnAl
2O
4, CeAlO
3, LaAlO
3, LiAl
5O
8Deng, thereby the heat endurance of raising coating.In addition, adopt the coating ingredients ultrafine particle not only can increase the specific area of coating, help the dispersion of active component, can delay the gathering and the sintering of aluminium oxide simultaneously, prolonged the use longevity of carrier, obtained better technical effect with the catalyst of making.
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
With 40 gram alumina sols (aluminium oxide that contains 15% mass ratio), 4.0 gram La
2O
3, 0.2 gram MgO, 60 grams, 2% glycerite, 0.5 gram sorbester p17 make slurries.The particle diameter that adds 0.5 gram potassic feldspar, 40 gram process air-flows pulverizing then in this mixed liquor is in (230 meters of the specific areas of the gamma oxidation aluminium powder below 10 microns
2/ gram).Stir about ten minutes, then with slurries 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, the coating load capacity is controlled by the control spray time.After spraying finishes, 80 ℃ of dryings 2 hours, then be warming up to 100 ℃ dry 2 hours once more, in 900 ℃ of roastings 6 hours, obtain lamellar composite carrier A at last, physico-chemical property sees Table 1.
[embodiment 2]
With θ-Al
2O
3(180 meters of specific areas
2/ gram) powder is pulverized and screening is controlled at particle diameter and makes ultra-fine θ-Al below 5 microns through air-flow
2O
3Powder.With 40 gram alumina sols (aluminium oxide that contains 15% mass ratio), 5.0 gram Ce
2O
3, 1.1 gram zinc nitrates, 60 grams, 3% polyacrylamide solutions, 0.4 gram betaines make slurries.In this mixed liquor, add 0.3 gram calcium silicates, the ultra-fine θ-Al of 30 grams then
2O
3Powder.Stir about ten minutes, then with slurries at room temperature ball milling made that particle size was controlled at below 10 microns in 2 hours.Slurries spray to the MgAl of 4 millimeters of particle diameters
2O
4On 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 B at last, physico-chemical property sees Table 1.
[embodiment 3]
Cyclodextrin solution solution, the 1.0 gram softex kws of 35 gram alumina sols (aluminium oxide that contains 25% mass ratio), 1.2 gram barium monoxide, 2 grams, 40% Ludox, 60 grams 4% are made slurries.The particle diameter that adds 0.4 gram calcium silicates, 0.3 gram potash and 36 gram process ball mill grindings then in this mixed liquor is at the δ-Al below 1 micron
2O
3Powder (160 meters of specific areas
2/ gram).Stir about 20 minutes, then with slurries at room temperature ball milling made that particle size was controlled at below 1 micron in 3 hours.Slurries spray on the mullite spheroid of 4 millimeters of particle diameters, in 80 ℃ 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 C at last, physico-chemical property sees Table 1.
[embodiment 4]
Cyclodextrin solution solution, the 1.0 gram ceteths of 42 gram alumina sols (aluminium oxide that contains 20% mass ratio), 2.5 gram lithium carbonates, 60 grams 4% are made slurries.The particle diameter that adds 0.2 gram calcium silicates, 40 gram process air-flows pulverizing then in this mixed liquor is at the δ-Al below 2 microns
2O
3Powder (130 meters of specific areas
2/ gram).The slurries that obtain at room temperature ball milling made that particle size was controlled at below 5 microns in 4 hours.Slurries spray on the cordierite spheroid of 4 millimeters of particle diameters, in 80 ℃ of dryings 2 hours, then be warming up to 150 ℃ dry 2 hours once more, in 1000 ℃ of roastings 4 hours, obtain lamellar composite carrier D at last, physico-chemical property sees Table 1.
[embodiment 5]
40 gram Ludox (silica that contains 40% mass ratio), 10.0 gram lanthanas are mixed, stir and made coating paste in 1.0 hours, the carborundum 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 2 hours once more, at last in 1100 ℃ of roastings 3 hours, obtain lamellar composite carrier E, physico-chemical property sees Table 1.
[comparative example 1]
According to patent CN1479649A embodiment 2 preparation lamellar composite carriers, just do not introduce SnCl4 in the process, and supported catalyst not, nuclear diameter is 4 millimeters in the carrier, and other conditions are constant, and carrier indicium is F, and physico-chemical property sees Table 1.
[comparative example 2]
According to the embodiment 3 preparation lamellar composite carriers of 6858769 li of U.S. Pat, just do not introduce SnCl4 in the process, nuclear diameter is 4 millimeters in the carrier, and other conditions are constant, are labeled as G, and physico-chemical property sees Table 1.
Table 1 lamellar composite carrier physicochemical properties
As can be seen from the table, the lamellar composite carrier of this method preparation is compared with the reference carrier and is had the coating specific area and reach the better advantage of heat endurance greatly.
[embodiment 6]
With lamellar composite carrier A, D difference surface impregnation Pt, the Sn of the present invention's preparation, elementary analysis shows, contains Pt 0.14% according to the mass fraction meter with regard to whole catalyst, and Sn 0.16%.The lamellar composite carrier of comparative example 1～2 preparation is surface impregnation Pt, Sn, Li respectively.Elementary analysis shows, contains Pt 0.14% according to the mass fraction meter with regard to whole catalyst, and Sn 0.16%, and Li 0.72%.The catalyst for preparing previously is used for the reaction that the oxidation of ethyl benzene dehydrogenation preparation of styrene hydrogen selective generates water.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, and 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
The results are shown in Table 3 for activity of such catalysts and selectivity.As can be seen from the table, adopt the lamellar composite carrier of this method preparation to prepare thin shell shaped noble metal catalyst, its performance is compared with reference catalyst has higher oxygen selectivity and lower aromatic hydrocarbons loss late, thereby has the better application prospect.
The H 2 selective oxidation performance of table 3 catalyst
Annotate: conv. is a conversion ratio, and sel. is a selectivity.
[embodiment 7]
The catalyst of embodiment 6 preparations is carried 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 6 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 (1)
1. the lamellar composite carrier of a heat endurance comprises the kernel of an inert carrier and is combined in porous coating material outer layer on the kernel that this kernel is selected from mullite; Porous coating material outer layer comprises and is selected from δ-Al
2O
3And to be selected from barium be auxiliary agent; Wherein, the kernel consumption is 75～95% of a lamellar composite carrier weight, and the porous coating material outer layer consumption is 5～20% of a lamellar composite carrier weight; Lamellar composite carrier outer coating thickness is 50～200 microns, 50～200 meters of specific areas
2/ gram; Auxiliary dosage is 0.05～5% of a lamellar composite carrier weight.
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| CN101428238B true CN101428238B (en) | 2011-02-09 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102189001A (en) * | 2010-03-03 | 2011-09-21 | 中国石油化工股份有限公司 | Wear-resistant and thermally stable alumina coating carrier |
| CN103418377B (en) * | 2012-05-16 | 2016-06-08 | 中国石油化工股份有限公司 | The thin-shell catalyst of low-carbon alkene is prepared for dehydrogenating low-carbon alkane |
| CN103539614B (en) * | 2012-07-12 | 2016-04-13 | 中国石油化工股份有限公司 | The reaction method of dehydrogenating low-carbon alkane producing light olefins |
| CN108020793A (en) * | 2017-12-19 | 2018-05-11 | 湖南大学 | Special power supply exports pulse-detecting circuit and special power supply dead electricity detection method |
| 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 |
| CN113457721B (en) * | 2021-07-21 | 2022-11-15 | 昆明理工大学 | High-temperature oxygen-deficient catalytic combustion catalyst and preparation method and application thereof |
| CN113477247B (en) * | 2021-09-07 | 2021-12-03 | 中海油天津化工研究设计院有限公司 | High-activity hydrothermal-resistant stable catalyst and preparation method thereof |
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|---|---|---|---|---|
| CN1479649A (en) * | 2000-11-27 | 2004-03-03 | �Ʒ� | Layered catalyst composition and process for preparating and using the composition |
| WO2005065821A1 (en) * | 2003-12-19 | 2005-07-21 | Celanese International Corporation | Layered support material for catalysts |
| CN1705510A (en) * | 2002-10-18 | 2005-12-07 | 环球油品公司 | A lithium aluminate layered catalyst and a selective oxidation process using the catalyst |
| CN1772383A (en) * | 2005-11-03 | 2006-05-17 | 安泰科技股份有限公司 | Porous catalytic filtering metal material and its prepn |
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|---|---|---|---|---|
| CN1479649A (en) * | 2000-11-27 | 2004-03-03 | �Ʒ� | Layered catalyst composition and process for preparating and using the composition |
| CN1705510A (en) * | 2002-10-18 | 2005-12-07 | 环球油品公司 | A lithium aluminate layered catalyst and a selective oxidation process using the catalyst |
| WO2005065821A1 (en) * | 2003-12-19 | 2005-07-21 | Celanese International Corporation | Layered support material for catalysts |
| CN1772383A (en) * | 2005-11-03 | 2006-05-17 | 安泰科技股份有限公司 | Porous catalytic filtering metal material and its prepn |
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