CN1244177A - Composition with base of cerium oxide or cerium and circonium oxides, in extruded form, method of preparation and use as catalyst - Google Patents
Composition with base of cerium oxide or cerium and circonium oxides, in extruded form, method of preparation and use as catalyst Download PDFInfo
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- CN1244177A CN1244177A CN97181276A CN97181276A CN1244177A CN 1244177 A CN1244177 A CN 1244177A CN 97181276 A CN97181276 A CN 97181276A CN 97181276 A CN97181276 A CN 97181276A CN 1244177 A CN1244177 A CN 1244177A
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- oxyhydroxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
- C01P2006/13—Surface area thermal stability thereof at high temperatures
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Abstract
The invention relates to a composition with base of cerium oxide or cerium and zirconium oxide, in extruded form, its method of preparation and its use as catalyst. The method of preparation of this composition is characterized in that it consists in extruding a hydroxide or an oxygen hydroxide of cerium or hydroxides or oxygen hydroxides of cerium and zirconium. The composition can be used as catalyst or catalyst support, particularly in the treatment of exhaust gases of internal combustion engines, in the process of dehydrogenation of ethyl benzene into styrene, in catalytic methanation action, in the treatment of a solution or suspension of organic compounds by wet oxidation.
Description
The present invention relates to a kind of be extrude attitude, based on cerium oxide or cerium oxide and zirconic composition, its preparation method with as the purposes of catalyzer.
Composition based on cerium oxide or cerium oxide and zirconic mixture is known.They especially are used as catalyzer or support of the catalyst, especially for motor vehicle combustion back catalysis.These compositions generally adopt in paint-on technique, that is to say they are mixed with oxide adhesive such as aluminium sesquioxide or silicon-dioxide, and the mixture that the obtained form with coating is deposited on the carrier.Yet oxide adhesive can cause the rapid deactivation or the loss of its selectivity of said composition.
Because this shortcoming, it is interesting can obtaining directly to be these compositions of extruding form.Yet, just known to the applicant company, up to these compositions that also never can obtain to be at present this form.
Thereby the purpose of this invention is to provide these compositions that are the extrudate form.
Applicant company has found to use special initial substance to address this problem.
Thereby the present invention relates to based on cerium oxide or cerium oxide and zirconic preparation of compositions method, it is characterized in that the product of being extruded is based on cerium oxyhydroxide or oxyhydroxide or cerium and zirconium oxyhydroxide or oxyhydroxide.
The invention still further relates to based on cerium oxide or cerium oxide and zirconic composition, it is characterized in that said composition exists to extrude form.
At last, the present invention relates to the purposes of the composition of the above-mentioned type, generate vinylbenzene method and catalytic methanation process especially for engine exhaust gas processing, dehydrogenation of ethylbenzene as catalyzer or support of the catalyst.
Read following detailed description the in detail and be used to be described various concrete but indefiniteness embodiment can find out other characteristics of the present invention, details and advantage more completely.
At first narration is product of the present invention.
The essential feature of the present composition is its shape.
In fact, they are the extrudate form.Extrudate is meant under pressure and sprays any object that paste obtained by the extrusion mould through nozzle or selected shape.So the object that obtains can be different shape.They can be for example garden cylindricality or half garden cylindricality, square or polygonal cross-section or leaf as the trilobal(cross) section.Described object can be solid or hollow.They can have for example integral body, honeycomb or Cylinder form.
The present composition is based on cerium dioxide or cerium and Zirconium oxide.This is interpreted as being meant cerium dioxide or cerium dioxide and zirconic composition, and wherein zirconium white accounts for the 50wt% at least of composition in its entirety weight.They can be made up of cerium and Zirconium oxide basically or fully, as suitably, also can add the additive of one or more following type.
Be based at composition under the situation of cerium and Zirconium oxide, the ratio separately of cerium and zirconium can change in wide region.More particularly, this ratio of expressing with the Zr/Ce atomic ratio can change in 1/20 to 20/1 scope, and more especially 1/9 to 9/1.
The present composition can also contain additive except that cerium and zirconium.These additives are selected from known those materials that can be used for improving cerium or zirconium catalytic performance.Thereby can use additive or known those additives that increase their storage oxygen capacities that to stablize these composition specific surface areas.
As additive can mention by the material that belongs to the group of forming by aluminium, silicon, thorium, titanium, niobium, tantalum and rare earth metal.
Rare earth metal is interpreted as being meant that by yttrium and period of element atom ordinal number be element in 57 to 71 the elementary composition group.In rare earth metal, can should be mentioned that yttrium, lanthanum, niobium and praseodymium especially.
The additive that can mention belongs to those in the group of being made up of magnesium, scandium, hafnium, gallium and boron in addition.
At last, the additive that can mention is the material that belongs in the group of being made up of iron, bismuth, nickel, manganese, tin and chromium.
Obviously, all additives of enumerating here can exist in the present composition separately or with array mode, no matter they are to belong to what material group.In addition, these additives are present in the composition with the form of oxide compound usually.
The quantity of additive can change in wide proportional range.Maximum quantity is expressed as maximum 50% with the additive oxide weight with respect to composition in its entirety weight.Minimum quantity is to reach required effect and necessary quantity.In general, this quantity is at least 0.1%.More particularly, the quantity of additive can be 1 to 20%, and more especially 1 to 10%.
The present composition can show high-specific surface area, even also like this after the roasting at high temperature.This surface-area depends on the character of composition component.In being the composition of main component, zirconium obtained maximum surface area.
More specifically, have cerium and zirconium simultaneously and cerium is a main component, that is to say the Ce/Zr atomic ratio greater than 1 the present composition, 900 ℃ of following roastings after 6 hours its specific surface area be at least 20m
2/ g more especially is at least 30m
2/ g.Add one or more additive, particularly as scandium and rare earth metal, especially lanthanum, praseodymium or niobium, after the roasting, these surface-area can be at least 35m under the same conditions
2/ g, or 40m at least
2/ g more particularly is at least 45m
2/ g.These compositions with additive also can show after 6 hours 1000 ℃ of following roastings and be at least 20m
2The surface-area of/g more especially is at least 30m
2/ g.
Moreover, have cerium and zirconium simultaneously and zirconium is a main component, that is to say the Ce/Zr atomic ratio less than 1 the present composition 900 ℃ of following roastings after 6 hours, its specific surface area is at least 30m
2/ g more especially is at least 40m
2/ g.Add one or more additive, particularly rare earth metal, especially lanthanum, praseodymium or niobium, after the roasting, these surface-area can be at least 50m under the same conditions
2/ g, or 55m at least
2/ g more especially is at least 60m
2/ g.These compositions with additive also can show after 6 hours 1000 ℃ of following roastings and be at least 30m
2The surface-area of/g more especially is at least 40m
2/ g.
Specific surface area is meant with based on the B.E.T. specific surface area of determining by nitrogen absorption according to ASTM standard D3663-78 in Brunauer-Emmett-Teller method described in the periodical " JACS (The Journal of theAmerican Chemical Society); 60,309 (1938) ".
Narrate the preparation method of extrusion compositions of the present invention now.
The principal character of the inventive method is to be raw material with the special outcome.This product can define in two ways.
At first, can be based on cerium oxyhydroxide or oxyhydroxide with being defined as or based on the product of cerium and zirconium oxyhydroxide or oxyhydroxide through the product extruded.This hydroxide generally can be passed through general formula (1) M (OH)
X(X)
YNH
2O represents that wherein M represents cerium or zirconium, and X represents negatively charged ion, and the x+y maximum equals 4, and x is not 0, and y and n can be 0.Negatively charged ion X is generally used for preparing the cerium of oxyhydroxide or the negatively charged ion of zirconium compounds, particularly salt, as following narration.Can also be with based on general formula (2) MO
z(OH)
x(X)
YNH
2The product of O oxyhydroxide is as raw material, and wherein M and X meaning are with above identical, and wherein the x+y+z maximum equals 4, and x and z are not 0, and y and n can be 0.This class oxyhydroxide can obtain by the oxyhydroxide of dry general formula (1).
Be to be noted that in general formula (1) and (2) x, y, the corresponding numerical value of z and n can be especially change according to the preparation method who is used for obtaining oxyhydroxide or oxyhydroxide.Therefore, for instance, it is about 0 to 20 that n can be, and can be 0.5 to the maximum, and X is in particular nitrate ion.What here emphasize is, these numerical value right and wrong are determinate, and essential feature of the present invention is to use the product that contains hydroxide radical anion in extruding operation.
To also can define through the product of extruding operation by its preparation method.
Preparation for this class product, the document that can mention is the patent application EP-A-300852 of applicant company especially, its content is here introduced, the document has been narrated by cerium solution and alkali reaction and has been prepared ceric hydroxide, can have oxygenant in the reaction process, the ratio of alkali is to make the pH value of reaction mixture greater than 7.So the cerous hydroxide that obtains can be handled through hot solvent subsequently, and wherein it is suspended in the water or in the decomposable alkali, and is heated to the critical temperature that is lower than reaction mixture respectively and the temperature and pressure of emergent pressure in the chamber of sealing.Can obtain cerium (IV) oxyhydroxide (the patent application FR-A-2596380 of applicant company) by hydrolysis cerium (IV) aqueous solution in acidic medium.
About being suitable for that the present invention extrudes the cerium of operation and zirconium oxyhydroxide or oxyhydroxide or based on the preparation of cerium and zirconium product, the document that can mention has the patent application FR-A-2699524 and the FR-A-2714370 of applicant company, its content is here introduced, and has wherein narrated the method that obtains this class product when its some steps finish especially.
First kind of these class methods that therefore, can be described comprise the steps.Formation comprises the liquid mixture of cerium and zirconium compounds, as suitably, also can comprise at least a additive compound; The mixture that heating is obtained; Reclaim the throw out that forms; And can dry described throw out.The product that obtains when these steps finish is suitable for the present invention and extrudes operation.
Thereby the first step of this method comprises the preparation liquid mixture, generally is aqueous mixture, wherein contains cerium and zirconium compounds, as suitably, also can contain at least a additive compound.These compounds generally are the salt and the preferred soluble salts of above-mentioned element.Described liquid mixture can be by being initially that the solid compound obtains or being that raw material mixes described solution with any order then and obtains with the solution of these compounds directly in the original mixture that will be introduced into water for example subsequently.
As cerium compound, can should be mentioned that cerium salt such as cerium (IV) salt especially, for example nitrate or ceric ammonium nitrate, their particularly suitables in this case.The preferred ceric nitrate that uses.Cerium (IV) salts solution can contain the cerium that is three valence state ceriums, but preferably it contains at least 85% cerium (IV).The ceric nitrate aqueous solution can for example obtain by nitric acid and cerium dioxide hydrate reaction, and described cerium dioxide hydrate reacts in the presence of hydrogen peroxide by cerous salt such as cerous nitrate and ammonia soln usually and prepares.Can also use by the resulting ceric nitrate solution of the cerous nitrate solution electrolytic oxidation method described in document FR-A-2570087, it is a kind of favourable initial substance.
Zirconium compounds is optional from zirconium sulfate, Zircosol ZN or zirconyl chloride.Particularly suitable be Zircosol ZN.The Zircosol ZN that more particularly can should be mentioned that use to corrode zirconium carbonate and produce by nitric acid.Described zirconium compounds can also be organic acid salt such as acetate or Citrate trianion.
Be to be noted that here cerium (IV) salt and oxygen zirconium saline solution can show initial free acidity to a certain degree.According to the present invention, can effectively show to a certain degree cerium of free acidity (IV) and zirconates initial soln as mentioned above with using roughly complete in advance the same use of neutral solution.This neutralization can be undertaken by add basic cpd in said mixture, to limit this acidity.This basic cpd can be for example ammonia soln or basic metal (sodium, potassium etc.) hydroxide solution, but ammonia soln preferably.In fact can define initial cerium and zirconium solution degree of neutralization (r) by following formula:
r＝(n3-n2)/n1
The cerium (IV) that in solution, exists after wherein the n1 representative neutralizes and the total mole number of zirconium; The required OH of initial free acidity that the n2 representative effectively neutralizes and introduced by cerium (IV) and zirconium saline solution
-The ionic mole number; The n3 representative is by adding the OH that alkali is introduced
-The ionic total mole number.When implementing " neutralization " scheme, the consumption of alkali definitely must be less than and makes cerium zirconium oxyhydroxide class precipitate required alkali number fully in all cases, and this quantity depends on the synthetic composition.Thereby the boundary of the degree of neutralization of in fact setting is for being no more than 2.
According to specific embodiment, as the zirconium compounds use is the zirconium solution with following characteristic.Determining that quantitatively the quantity that reaches the required alkali of point of equivalent in this solution acid/basicity process must satisfy OH
-The condition of/Zr mol ratio≤1.65.More particularly, this ratio is the highest to can be 1.5, more more particularly, is up to 1.3.
Carry out quantitatively determining of acid/basicity with known manner.For under top condition, carrying out, can reach 3 * 10 to the concentration of expressing with element zirconium
-2The solution that mol/ rises carries out quantitatively determining.Under agitation condition to wherein adding the 1N sodium hydroxide solution.Under these conditions, can distinct definite point of equivalent (variation of pH value of solution value).This point of equivalent is with OH
-/ Zr mole is recently expressed.
As the additive compound that can be used for the inventive method, that can mention has for example organic or inorganic hydrochlorate such as vitriol, nitrate, muriate or an acetate salt.What be to be noted that particularly suitable is nitrate.The form of all right colloidal sol of these compounds is introduced.These colloidal sols for example can obtain by the salt of these compounds that neutralize with alkali.
The stoichiometric ratio that the quantity of the cerium that exists in mixture, zirconium and the additive that may add must require corresponding to obtaining required final composition.
So the original liquid mixture that obtains heats according to second step of described method subsequently.
This heat treated temperature that is called as thermal hydrolysis simultaneously can be 80 ℃ of critical temperatures to reaction mixture, is in particular 80 to 350 ℃, is preferably 90 to 200 ℃.
According to the temperature condition that is adopted, this processing can be depressed or for example pressurizes at normal atmospheric, depresses corresponding to the saturated vapo(u)r of this thermal treatment temp and carries out.When being chosen as the reflux temperature that is higher than reaction mixture, treatment temp (that is to say, generally be higher than 100 ℃) time, for example be chosen as 150 to 350 ℃, then be incorporated into the chamber (closed reactor of sealing by the aqueous mixture that will contain mentioned kind, more generally be called autoclave) carry out described operation, at this moment only produce required pressure (autogenous pressure) by the reacting by heating mixture.Under the above temperature condition that provides, and in water-bearing media, for purposes of illustration, the pressure range that can indicate in closed reactor is greater than 1 crust (10
5Pa) to 165 crust (165 * 10
5Pa), be preferably 5 crust (5 * 10
5Pa) to 165 crust (165 * 10
5Pa).Certainly, can also apply external pressure, this pressure is superimposed with the pressure that heating is produced.
Heating can be carried out in air atmosphere or inert atmosphere, preferred nitrogen.
The time of described processing is undemanding, thereby can change in wide region, for example is 1 to 48 hour, is preferably 2 to 24 hours.
When heating steps finishes, reclaim solid sediment, described solid sediment can be by any general solid/liquid separation technique, as filtration, sedimentation, discharge opeing or centrifugal the separation.
When this second step finishes, advantageously make the reaction mixture of acquisition like this reach the alkaline pH value.Carry out this operation by interpolation alkali such as ammonia soln in described mixture.
The alkaline pH value is interpreted as being meant greater than 7 and is preferably greater than 8 pH value.
Behind heating steps, can also same way as add aqueous hydrogen peroxide solution.
Be to be noted that certainly and reclaiming product and after possible interpolation alkali or hydrogen peroxide, can identical or different mode repeat above-mentioned heating steps one or several, and then product is placed particularly water of liquid medium, and carry out for example heating cycle.
The product that is reclaimed subsequently can be through the washing operation that makes water and/or ammoniacal liquor that carries out to the boiling temperature in room temperature.For removing remaining water, the product after the washing can be finally with for example dry air, and the drying temperature scope can be 80 to 300 ℃, is preferably 100 to 150 ℃, and drying may persist to and reaches constant weight.
Can also atomize by the throw out that will be obtained and carry out drying.In this case, then do not need throw out is separated from obtain this sedimentary reaction mixture.Reaction mixture can be placed with by settlement separate, the supernatant liquor sucking-off at last, can be carried out drying by atomizing then.
Can also adopt the second method of wherein carrying out sedimentary preparation cerium and zirconium oxyhydroxide or oxyhydroxide.According to this second method, form a kind of liquid mixture, wherein comprise cerium compound or cerium and zirconium compounds, and, also can comprise at least a additive compound as suitably; In the mixture that is obtained, add alkali; Reclaim the throw out that forms; And can dry described throw out.The product that so obtains when these steps finish is suitable for the present invention and extrudes operation.
Above with reference to cerium, zirconium and additive compound narration content also here be suitable for.
In second step of this second method, in the liquid mixture of previous formation, add alkali.Oxyhydroxide class product can be used as alkali.Can should be mentioned that basic metal or alkaline earth metal hydroxides.Also can use the second month in a season, uncle or quaternary amine.But preferred amines and ammonia are because they have reduced the danger that is caused pollution by basic metal or alkaline earth metal cation.Can also should be mentioned that urea.Reactant can be introduced by any order, alkali can be incorporated in the reaction mixture, and perhaps order is opposite, also reactant can also be incorporated in the reactor simultaneously.
Can be disposable, add gradually or continuously, preferably under agitation carry out.This operation can be carried out to the reflux temperature of reaction mixture at room temperature (18-25 ℃), and described reflux temperature for example can reach 120 ℃.Preferably at room temperature carry out.
When adding the alkali end, reaction mixture can be continued to stir for some time again, so that precipitation is carried out fully.
When continue adding alkali, the pH value of reaction mixture preferably maintains about 7 to about 11, more particularly is 7.5 to 9.5.
Can narrate the another kind of form of this second method here, this alternative form is corresponding to the content of above-mentioned FR-A-2714370.In this alternative form, carry out with being reflected under carbonate or the supercarbonate existence of alkali.Term carbonate it must be understood that to comprising subcarbonate.That can mention for instance, has volatile salt or bicarbonate of ammonia.Moreover, this pH value that is reflected at reaction mixture remain on neutrality or alkalescence condition under carry out.The pH value of described reaction mixture generally is at least 7, and is 7 to 7.5 under the situation of neutral mixture, is at least 8 more especially under the alkaline mixt condition.More particularly, this numerical value can be 7.5 to 14, is in particular 8 to 11, is more particularly 8 to 9.
According to a kind of specific embodiments of this alternative form, the liquid mixture that will comprise cerium and zirconium compounds and also may comprise additive compound is incorporated in the basic solution with carbonate or supercarbonate.Thereby, for example can form original mixture, to wherein introducing liquid mixture with basic solution.
In this alternative form, can also operate continuously.In this case, comprise cerium and zirconium compounds and also may comprise the liquid mixture of additive compound and alkali and carbonate or supercarbonate are introduced in the reactor simultaneously, provide excessive alkali to satisfy the pH condition.
When the settling step of described second method finishes, reclaim solid sediment, this throw out can separate from its mixture and can be by the described drying of carrying out of above first method.
Product that obtains by aforesaid method and cerium and zirconium oxyhydroxide or oxyhydroxide are subsequently by extruding shaping.
They can directly be extruded or to extrude with the form of mixtures of acidic solution.The existence of acidic solution can promote to be shaped.As acid, can use for example nitric acid, stearic acid, oxalic acid or acetate.Mole number with acid is expressed with respect to the mole number sum of cerium and zirconium, and the consumption of acid is generally about 0.1 to 5%.
Cerium that obtains by aforesaid method and zirconium oxyhydroxide or oxyhydroxide and product can also be extruded described shaping additive such as Mierocrystalline cellulose, carboxymethyl cellulose, carboxyethyl cellulose, xanthan gum and succinoglycan glue (succinoglycan gums), tensio-active agent, flocculation agent such as polyacrylamide, carbon black, starch, POLYPROPYLENE GLYCOL, polyvinyl alcohol, glucose or polyoxyethylene glycol with the form of the mixture of known shaping additive.
A significant advantage of the present invention is that the product that will extrude can be in not existing in this class technology be extruded under the condition of normally used tackiness agent.Certainly, use tackiness agent also not depart from scope of the present invention, described tackiness agent can be selected from silicon-dioxide, aluminium sesquioxide, clay, silicate, titanium sulfate or ceramic fiber, particularly with general ratio, that is to say up to about 30wt%.
Cerium and zirconium oxyhydroxide or oxyhydroxide and product by the aforesaid method acquisition, with separately or to be the loss on ignition that the form of mixtures with above-mentioned acidic solution or shaping additive or tackiness agent preferably shows extruding before be 25 to 75%, be more particularly 40 to 65%.Loss on ignition (LOI) is measured with the weight loss corresponding to following ratio:
LOI=(w in %
0-w
1)/w
0, wherein:
-w
0It is the initial weight of initial substance
-w
1Be that this initial substance is 1000 ℃ of following roastings 2 hours and the weight be cooled to room temperature in no hydroecium after.
Before extruding, cerium that will obtain by aforesaid method and zirconium oxyhydroxide or oxyhydroxide and product are kneaded.Time of kneading can change in wide region, for example is 1 minute to 3 hours.
Extrude in any suitable device and carry out.
Product through extruding can carry out drying and carry out roasting subsequently.
The temperature of carrying out roasting is generally 200 to 1200 ℃, is preferably 300 to 900 ℃, more especially 500 ℃ to 900 ℃.It is oxide compound that this maturing temperature must be enough to described precursor conversion, and this temperature is also selected with the purpose use temperature of this catalyst composition fact that to be function and the specific surface area of considering product reduce with the increase of the maturing temperature that is adopted.Roasting time can change in wide region, for example is 1 to 24 hour, is preferably 4 to 10 hours.Generally in air, carry out roasting, carry out roasting in the rare gas element but obviously be not precluded within.
So the extrudate that obtains can use with the precious metal catalytically-active metals.The character of these metals and the technology that is introduced in these compositions belong to content as well known to those skilled in the art.For example, described metal can be platinum, rhodium, palladium, ruthenium or iridium; They can be introduced in the described composition by dipping especially.
Extrudate of the present invention can be used in particular for being used for ethylbenzene dehydrogenation and generating vinylbenzene or methanation catalysis process in the engine exhaust gas processing.
More in general, they can be used for the various reactions of catalysis, as, for instance, that the dehydration of hydrocarbon or other organic compound, hydrogen sulfuration, hydrodenitrification, desulfurization, hydrogenating desulfurization, dehydrohalogenation, reformation, steam are given birth to is whole, cracking, hydrocracking, hydrogenation, dehydrogenation, isomerization, disproportionation, oxychlorination, dehydrocyclization, oxidation and/or reduction reaction, Claus reaction, the treating processes that demetalization, dislocation transform or solution of organic compound or suspension carried out by wet oxidation.
The aqueous solution of a pair of organic compound in back or treating processes that suspension carries out are the chemical oxygen demand (COD) of described solution or suspension is reduced to preset value to finish by with oxygen-containing gas organic compound being carried out oxidation in the presence of oxide catalyst under high temperature and high pressure.The feature of described catalyzer is to comprise the catalytic activity phase that is present on the carrier, and described carrier is by forming based on cerium dioxide and zirconic composition, and wherein cerium/atomic percent zirconium is at least 1, and this carrier is at least 35m in the specific surface area of 900 ℃ of following roastings after 6 hours
2/ g, the storage oxygen capacity under 400 ℃ is at least 1.5ml O
2/ g.This carrier is the form of extrudate.Catalytic activity is made up of ruthenium that is metal or oxide form or iridium.
By adopting as the oxygen-containing gas of oxidizing gas for example pure oxygen, air, oxygen-rich air or contain the oxygen residual gas and carry out oxidizing reaction.
The quantity of definite gas that is provided is provided by the chemical oxygen demand (COD) that pending solution is arranged (COD).Generally speaking, the quantity of employed oxygen-containing gas is 1 to 1.5 times of theoretical oxygen demand.
Advantageously the pressure of oxygen is 1 to 50 crust, and the total pressure of gas should be enough high to keep solution or suspension to be in a liquid state under temperature of reaction.
Advantageously this temperature of reaction is 100 ℃ to 400 ℃, is preferably 120 ℃ to 200 ℃.This temperature especially depend on the character of the organic compound that exists in the ejecta to be processed.
The aqueous solution that can handle by this method or suspension are liquid, aqueous, wherein preferably contain oxidable organic substance, as have the intermediate concentration chemical oxygen demand (COD), advantageously less than the moisture ejecta of 200g/l.
The example of waste water is as deriving from the waste water of industrial plants such as chemical industry or refinery, the city discharge, oily(waste)water or derive from method for gas purification or activated sludge process in waste water.For avoiding equipment and catalyzer incrustation, advantageously before handling with these liquid, aqueous filtrations.
Below provide embodiment.
Embodiment 1
This embodiment illustrates that general formula is Ce
0.62Zr
0.38O
2The preparation of the oxide carrier that is the extrudate form.
To obtain the required stoichiometry of above mixed oxide recently high cerium solution of mixed nitrate and zirconyl nitrate solution.Obtain zirconyl nitrate solution by using concentrated nitric acid to corrode carbonate.On the meaning of above definition, this solution satisfies OH
-The condition of/Zr mol ratio=0.94.
The concentration (in the oxide compound of various elements) of this mixture is adjusted into 80g/l.Subsequently this mixture was heated to 150 ℃ through 4 hours.
In this reaction mixture, add ammonia soln subsequently, make pH greater than 8.5.So the reaction mixture that obtains was heated to boiling point through 2 hours.Behind settlement separate and decant, with the solid product resuspending, and the mixture that will so obtain was handled 1 hour down at 100 ℃.This product subsequent filtration.So the loss on ignition of filter cake under 1000 ℃ that obtains is 60.6%.Before 3.2mm mould extrusion molding, cerium/zirconium oxyhydroxide or oxyhydroxide were being mediated 15 minutes.Employed equipment is the single screw extrusion machine of being sold by Lhomargie company.Resulting extrudate is shaped as the garden cylindricality, and its diameter is 1.2mm.Subsequently it before roasting, is being descended them dry 1 hour at 100 ℃ in 600 ℃ of following air.
The oxide compound of formed thereby is handled the specific surface area that is had after 6 hours in 900 ℃ of following air be 39m
2/ g, processing is after 6 hours down at 1000 ℃, and specific surface area is 17m
2/ g.
Embodiment 2
This embodiment illustrates that general formula is Ce
0.17Zr
0.83O
2The preparation of the oxide carrier that is the extrudate form.
Corresponding weight ratio 20/80 with oxide compound is added zirconyl nitrate solution (corroding carbonic acid Zr by nitric acid obtains) in cerous nitrate (IV) solution to, makes that the ratio r of above definition is 0.5.This concentration is adjusted into 80g/l, then this solution was warming up to 150 ℃ through 6 hours.After the cooling, use ammonia solution that the pH value of reaction mixture is adjusted into 8.5.Temperature is warming up to 100 ℃ subsequently.After the cooling, remove mother liquor, and add the water of equivalent by sedimentation.Reaction mixture is warming up to 100 ℃ again.After settlement separate, remove supernatant liquor, product passes through atomization drying.Resulting powder and aqueous nitric acid are mediated, and its concentration is for making HNO
3The ratio of/Zr+Ce equals 0.025, and the loss on ignition of paste under 1000 ℃ is 45%.The cerium that is obtained/zirconium oxyhydroxide is shaped by embodiment 1 subsequently, in the roasting in 500 ℃ of air after 1 hour of 100 ℃ of dryings.
So the oxide compound that obtains is 45m in the specific surface area of 900 ℃ of following roastings after 6 hours
2/ g.
X-ray diffraction analysis revealed, resulting oxide compound are pure solid solution phase.
Embodiment 3
This embodiment illustrates that general formula is Ce
0.75Zr
0.25O
2The preparation of the oxide carrier that is the extrudate form.
Two kinds of following solution constitute initial substance.
The cerous nitrate of-solution 1:116.7g (III) (29.5%CeO
2)
24.7g Zircosol ZN (19.9%ZrO
2)
124g?H
2O
-solution 2:47.4g bicarbonate of ammonia
35.2g?NH
4OH(29％NH
3)
240.4g?H
2O
Solution 1 is preheated to 80 ℃.In its solution 2 through adding to initially to remain on 25 ℃ in 5 minutes.Through diameter is Bu Shi (Buchner) the funnel filtering mixt of 15cm, and with 500ml water washing resistates.Product is dry down in 125 ℃ in ventilated drying oven subsequently.
Gained powder such as embodiment 1 are shaped, and add acetic acid aqueous solution in described powder, and its concentration is for making CH
3CO
2H/Zr+Ce ratio equals 0.030, and paste is 51% 1000 ℃ of following loss on ignitions.
The cerium that is obtained/zirconium oxyhydroxide is 100 ℃ of drying roastings in 700 ℃ of air after 1 hour down.
The specific surface area that the oxide compound that is shaped is handled after 6 hours in 900 ℃ of air is 30m
2/ g.
Claims (14)
1. based on cerium dioxide or based on the composition of cerium and Zirconium oxide, it is characterized in that being the form of extrudate.
2. composition as claimed in claim 1 is characterized in that it is 1/20 to 20/1, more especially 1/9 to 9/1 cerium and Zirconium oxide based on the Zr/Ce atomic ratio.
3. as the composition of claim 1 or 2, it is characterized in that it also comprises at least a additive that is selected from aluminium, silicon, thorium, titanium, niobium, tantalum and rare earth metal.
4. the composition of each claim as described above is characterized in that it also comprises at least a additive that is selected from magnesium, scandium, hafnium, gallium and boron.
5. the composition of each claim as described above is characterized in that it also comprises the additive of at least a chosen from Fe, bismuth, nickel, manganese, tin and chromium.
6. the composition of each claim as described above is characterized in that it is at least 20m in the specific surface area that 900 ℃ of following roastings were had after 6 hours
2/ g more especially is at least 30m
2/ g.
7. the preparation of compositions method of each claim as described above is characterized in that extruding based on cerous hydroxide or cerium oxyhydroxide or based on the product of cerium and zirconium oxyhydroxide or oxyhydroxide.
8. each preparation of compositions method in the claim 1 to 6, it is characterized in that extruding the product that is obtained: form a kind of liquid mixture by following method, wherein comprise cerium compound or cerium and zirconium compounds, and, also can comprise at least a additive compound as suitably; Heat resulting mixture; Reclaim the throw out that forms; And can carry out drying to described throw out.
9. each preparation of compositions method in the claim 1 to 6, it is characterized in that extruding the product that is obtained: form a kind of liquid mixture by following method, wherein comprise cerium compound or cerium and zirconium compounds, and, also can comprise at least a additive compound as suitably; In resulting mixture, add alkali; Reclaim the throw out that forms; And can carry out drying to described throw out.
10. each preparation of compositions method in the claim 1 to 6, it is characterized in that extruding the product that is obtained by following method: wherein cerium solution and alkali react, this reaction can be carried out in the presence of catalyzer, and the ratio of alkali makes the pH of reaction mixture greater than 7.
11. each preparation of compositions method in the claim 1 to 6 is characterized in that extruding the product that is obtained by following method: wherein cerium (IV) aqueous solution is hydrolyzed in acidic medium.
12., it is characterized in that the mixture extruded is obtained by above-mentioned oxyhydroxide or oxyhydroxide or at least a product that obtains by aforesaid method on the one hand, on the other hand, is obtained by acidic solution as each method in the claim 7 to 11.
13., it is characterized in that to one or more above-mentioned oxyhydroxide or oxyhydroxide or at least a product that obtains by aforesaid method or to being 25 to 75%, being more particularly the mixture that 40 to 65% product obtains and extruding by one or more above-mentioned oxyhydroxide or oxyhydroxide or by at least a loss on ignition that obtains by aforesaid method as each method in the claim 7 to 12.
14. each composition particularly generates the purposes aspect cinnamic method, catalytic production of methane effect or wet oxidation process solution of organic compound or the suspension in engine exhaust gas processing, ethylbenzene dehydrogenation as catalyzer or support of the catalyst in the claim 1 to 6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR96/15000 | 1996-12-06 | ||
| FR9615000A FR2756819B1 (en) | 1996-12-06 | 1996-12-06 | COMPOSITION BASED ON CERIUM OXIDE OR CERIUM OXIDES AND ZIRCONIUM, IN EXTRUDED FORM, PROCESS FOR PREPARING SAME AND USE AS CATALYST |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1244177A true CN1244177A (en) | 2000-02-09 |
Family
ID=9498409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97181276A Pending CN1244177A (en) | 1996-12-06 | 1997-12-03 | Composition with base of cerium oxide or cerium and circonium oxides, in extruded form, method of preparation and use as catalyst |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0950022A1 (en) |
| JP (1) | JP2000505771A (en) |
| KR (1) | KR20000057428A (en) |
| CN (1) | CN1244177A (en) |
| CA (1) | CA2274013C (en) |
| FR (1) | FR2756819B1 (en) |
| NO (1) | NO992741L (en) |
| TW (1) | TW426542B (en) |
| WO (1) | WO1998024726A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100540473C (en) * | 2003-09-04 | 2009-09-16 | 罗狄亚电子与催化公司 | Have high reductibility and high-ratio surface based on cerium oxide and zirconic composition, its preparation method and as the purposes of catalyzer |
| CN102463034A (en) * | 2010-11-15 | 2012-05-23 | 温州大学 | Oxygen storage material for purifying motorcycle tail gas |
| CN105263864A (en) * | 2013-03-19 | 2016-01-20 | 罗地亚经营管理公司 | Composition based on oxides of zirconium, cerium, niobium and tin, preparation processes and use in catalysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100394076B1 (en) * | 2000-09-16 | 2003-08-09 | 주식회사 경동도시가스 | Nickel reforming catalyst and preparing method of synthesis gas or hydrogen from natural gas by steam reforming |
| AU2001291568B2 (en) | 2000-09-18 | 2006-02-23 | Rothmans, Benson & Hedges Inc. | Low sidestream smoke cigarette with non-combustible treatment material |
| EP1425447A1 (en) | 2001-09-13 | 2004-06-09 | Rothmans, Benson & Hedges Inc. | Zirconium/metal oxide fibres |
| JP3946982B2 (en) * | 2001-11-01 | 2007-07-18 | ニッケイ・メル株式会社 | Method for producing zirconia-ceria based composite oxide |
| KR101121876B1 (en) | 2003-04-30 | 2012-03-19 | 마그네슘 일렉트론 리미티드 | Process for preparing zirconium oxides and zirconium-based mixed oxides |
| US7384888B2 (en) | 2003-09-15 | 2008-06-10 | Toyota Jidosha Kabushiki Kaisha | Cerium-zirconium composite metal oxide |
| EP1516855B1 (en) * | 2003-09-15 | 2017-03-01 | Toyota Jidosha Kabushiki Kaisha | Cerium-zirconium composite metal oxide with a cerium oxide core surrounded by zirconium oxide |
| FR2884732B1 (en) * | 2005-04-20 | 2007-08-24 | Rhodia Chimie Sa | COLLOIDAL DISPERSION OF A CERIUM COMPOUND AND ANOTHER ELEMENT SELECTED FROM ZIRCONIUM, RARE EARTHS, TITANIUM AND TIN, DISPERSIBLE SOLID BASED ON THIS COMPOUND AND METHODS OF PREPARATION |
| JP5628039B2 (en) * | 2008-09-22 | 2014-11-19 | 学校法人早稲田大学 | Dehydrogenation catalyst for alkyl aromatic compounds having high redox ability, process for producing the same, and dehydrogenation process using the same |
| FR2970254B1 (en) | 2011-01-11 | 2013-09-20 | Rhodia Operations | PROCESS FOR THE PREPARATION OF ALCOHOL CARBONATE |
| FR2993269B1 (en) | 2012-07-11 | 2014-08-08 | Rhodia Operations | PROCESS FOR THE PREPARATION OF POLYGLYCEROL (POLY) CARBONATE |
| US10112178B2 (en) | 2015-03-05 | 2018-10-30 | Shell Oil Company | Methane oxidation catalyst, process to prepare the same and method of using the same |
| AU2017318279B2 (en) | 2016-08-31 | 2019-12-05 | Shell Internationale Research Maatschappij B.V. | Methane oxidation catalyst, process to prepare the same and method of using the same |
| DK3507008T3 (en) | 2016-08-31 | 2021-11-22 | Shell Int Research | PROCEDURE FOR PREPARING A METHANE OXIDIZATION CATALYST |
| KR102243161B1 (en) | 2018-03-13 | 2021-04-22 | 주식회사 엘지화학 | Method for partial oxidation of carbonate hydrogen |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2608458B1 (en) * | 1986-12-23 | 1989-03-10 | Rhone Poulenc Chimie | CATALYST BASED ON CERIUM OXIDE AND METHOD FOR THE TREATMENT OF INDUSTRIAL GASES CONTAINING SULFUR COMPOUNDS |
| FR2699524B1 (en) * | 1992-12-21 | 1995-02-10 | Rhone Poulenc Chimie | Composition based on a mixed oxide of cerium and zirconium, preparation and use. |
| FR2701472B1 (en) * | 1993-02-10 | 1995-05-24 | Rhone Poulenc Chimie | Process for the preparation of compositions based on mixed oxides of zirconium and cerium. |
| FR2714370B1 (en) * | 1993-12-24 | 1996-03-08 | Rhone Poulenc Chimie | Precursor of a composition and composition based on a mixed oxide of cerium and zirconium, method of preparation and use. |
| FR2720295B1 (en) * | 1994-05-27 | 1996-07-12 | Rhone Poulenc Chimie | Dispersible compound based on a rare earth, colloidal suspension obtained from this compound, their methods of preparation and use in the manufacture of catalysts. |
-
1996
- 1996-12-06 FR FR9615000A patent/FR2756819B1/en not_active Expired - Fee Related
-
1997
- 1997-12-03 EP EP97948991A patent/EP0950022A1/en not_active Withdrawn
- 1997-12-03 CN CN97181276A patent/CN1244177A/en active Pending
- 1997-12-03 CA CA002274013A patent/CA2274013C/en not_active Expired - Fee Related
- 1997-12-03 WO PCT/FR1997/002190 patent/WO1998024726A1/en not_active Application Discontinuation
- 1997-12-03 KR KR1019990705014A patent/KR20000057428A/en not_active Application Discontinuation
- 1997-12-03 JP JP10525282A patent/JP2000505771A/en active Pending
-
1998
- 1998-02-09 TW TW086118392A patent/TW426542B/en active
-
1999
- 1999-06-04 NO NO992741A patent/NO992741L/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100540473C (en) * | 2003-09-04 | 2009-09-16 | 罗狄亚电子与催化公司 | Have high reductibility and high-ratio surface based on cerium oxide and zirconic composition, its preparation method and as the purposes of catalyzer |
| CN102463034A (en) * | 2010-11-15 | 2012-05-23 | 温州大学 | Oxygen storage material for purifying motorcycle tail gas |
| CN105263864A (en) * | 2013-03-19 | 2016-01-20 | 罗地亚经营管理公司 | Composition based on oxides of zirconium, cerium, niobium and tin, preparation processes and use in catalysis |
| CN105263864B (en) * | 2013-03-19 | 2017-07-14 | 罗地亚经营管理公司 | Composition, preparation method and the purposes in catalysis of oxide based on zirconium, cerium, niobium and tin |
Also Published As
| Publication number | Publication date |
|---|---|
| NO992741D0 (en) | 1999-06-04 |
| WO1998024726A1 (en) | 1998-06-11 |
| JP2000505771A (en) | 2000-05-16 |
| FR2756819B1 (en) | 1999-02-19 |
| CA2274013A1 (en) | 1998-06-11 |
| CA2274013C (en) | 2003-02-11 |
| NO992741L (en) | 1999-08-05 |
| FR2756819A1 (en) | 1998-06-12 |
| EP0950022A1 (en) | 1999-10-20 |
| TW426542B (en) | 2001-03-21 |
| KR20000057428A (en) | 2000-09-15 |
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