CN103480427B - Containing lithium hydrated alumina forming matter and application and egg-shell catalyst and preparation method and application and the method preparing vinyl carboxylates - Google Patents
Containing lithium hydrated alumina forming matter and application and egg-shell catalyst and preparation method and application and the method preparing vinyl carboxylates Download PDFInfo
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- CN103480427B CN103480427B CN201210191977.7A CN201210191977A CN103480427B CN 103480427 B CN103480427 B CN 103480427B CN 201210191977 A CN201210191977 A CN 201210191977A CN 103480427 B CN103480427 B CN 103480427B
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Abstract
The invention provides a kind of containing lithium hydrated alumina forming matter and application thereof, this article shaped prepares formed body by the raw material containing at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether, and described formed body is carried out drying at 80-180 DEG C and makes.Present invention also offers a kind of preparation method of egg-shell catalyst, the method is using the lithium hydrated alumina forming matter that contains of the present invention as carrier.Invention further provides a kind of egg-shell catalyst and application thereof, this catalyst is using the lithium hydrated alumina forming matter that contains provided by the invention as carrier.Invention further provides a kind of method preparing vinyl carboxylates.High intensity and strength retention can be obtained containing lithium hydrated alumina forming matter without the need to carrying out roasting according to of the present invention, adopt conventional method to prepare egg-shell catalyst using this article shaped as carrier, and the catalyst of preparation demonstrate higher catalytic activity preparing in vinyl carboxylates.
Description
Technical field
The present invention relates to a kind of containing lithium hydrated alumina forming matter and application thereof, the invention still further relates to a kind of preparation method of egg-shell catalyst, the present invention relates to again a kind of egg-shell catalyst using Pd and Au as active component and is preparing the application in vinyl carboxylates, the invention further relates to a kind of method preparing vinyl carboxylates.
Background technology
The catalyst (that is, lamella catalyst or egg-shell catalyst) of active metal component shell distribution may be used for multiple heterogeneous catalytic reaction.Such as, hydrogenation, oxidation reaction and the chemical reaction (as Fischer-Tropsch synthesis) etc. by diffusion control.
In prior art, slaine is mainly prepared on carrier by method loads such as dipping, spraying, vapor deposition, dip-coating or precipitations by lamella catalyst.
Such as, CN1306459A disclose a kind of on cellular ceramic substrate preparation there is the technique of the noble metal lamella catalyst determining shell thickness, this technique is by with chemical vapor deposition (CVD) method by suitable noble metal precursor with vapor phase deposition on porous support, is become metal and is fixed on carrier by noble metal afterwards by chemistry or thermal reduction.The catalyst activity metal component of this explained hereafter has the feature of shell distribution.
US4048096 discloses a kind of method preparing lamella catalyst, the solution impregnating catalyst carrier of the method containing the compound of water-soluble Pd and the compound of water-soluble Au, by by impregnated catalyst carrier with can react with the compound of described water-soluble Pd and the compound of water-soluble Au the compound solution forming water-fast Pd with Au compound and contact (preferred sodium metasilicate), by the compound precipitation of the compound of water-insoluble Pd and water-insoluble Au on catalyst support surface, then with reducing agent, the compound reduction of described water-insoluble Pd compound and water-insoluble Au is become metal Pd and Au, thus the lamella catalyst prepared using Pd and Au as active metal.
CN101462079B discloses a kind of preparation method of shell distribute catalyst, the method comprises with the solution impregnating carrier containing effective dose active metal component, wherein, solvent in solution used is the mixture that one or more and at least one surfactant in water, alcohol, ether, aldehyde, ketone form, with the total amount of solution for benchmark, the content of described surfactant is 0.01-10 % by weight, and described dipping meets: V
l: V
c=0.01-0.99, wherein V
lfor maceration extract volume, V
cfor the pore volume of carrier.The method adopts spray drying, and the catalyst activity metal component distribution in the carrier of preparation presents the distribution of obvious shell.
CN101143325B discloses a kind of method of Kaolinite Preparation of Catalyst, first the method comprises prepares a kind of containing by the solution of the soluble compound of load component, afterwards by the solution spraying for preparing on the carrier rolled or the load in advance carrier of active metal component, while spraying process, carrier is heated, the product drying of making or roasting.The catalyst adopting the method to prepare, can obtain the catalyst of obvious shell distribution.
Summary of the invention
One object of the present invention is to provide a kind of method preparing egg-shell catalyst newly, and the method is simple and easy to do; Another object of the present invention is to provide a kind of egg-shell catalyst using Pd and Au as active component, and this catalyst has higher catalytic activity.
The present inventor finds in research process, to prepare formed body by the raw material containing at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether, and using described formed body 80-180 DEG C carry out drying and the article shaped made as carrier, to there is the active constituent loading of catalytic activity on carrier by the carrying method (such as: dipping or spraying) of routine, the catalyst prepared thus has eggshell type structure (that is, the active component with catalytic action mainly concentrates on the surface of catalyst).Complete the present invention on this basis.
A first aspect of the present invention provides a kind of containing lithium hydrated alumina forming matter, this article shaped prepares formed body by the raw material containing at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether, and described formed body is carried out drying at 80-180 DEG C and makes.
A second aspect of the present invention provides article shaped according to the present invention and is preparing the application in egg-shell catalyst.
A third aspect of the present invention provides a kind of preparation method of egg-shell catalyst, and the method is included in the active component that supported on carriers at least one has catalytic action, and wherein, described carrier is containing lithium hydrated alumina forming matter according to of the present invention.
A fourth aspect of the present invention provides a kind of egg-shell catalyst, this catalyst contains carrier and the load active component with catalytic action on the carrier, the described active component with catalytic action is Pd and Au, wherein, described carrier is provided by the invention containing lithium hydrated alumina forming matter.
A fifth aspect of the present invention provide a kind of catalyst according to the invention by ethene and carboxylic acid oxidative to prepare the application in vinyl carboxylates.
A sixth aspect of the present invention provides a kind of method preparing vinyl carboxylates, the method comprises in the presence of a catalyst, is contacted by ethene with carboxylic acid with oxygen, to obtain the mixture containing vinyl carboxylates, wherein, described catalyst is catalyst provided by the invention.
Prepare formed body containing lithium hydrated alumina forming matter with the raw material (described raw material do not contain peptizing agent) containing at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether according to according to the present invention, and described formed body is carried out drying at 80-180 DEG C and makes.Good absorbent properties should be had containing lithium hydrated alumina forming matter; Further, high intensity and strength retention can be obtained containing lithium hydrated alumina forming matter without the need to carrying out roasting according to of the present invention.
Method according to the present invention is using the lithium hydrated alumina forming matter that contains provided by the invention as carrier, and the carrying method adopting this area to commonly use can prepare the catalyst with eggshell type structure.
Egg-shell catalyst using Pd and Au as active component according to the present invention for by ethene and carboxylic acid oxidative to prepare in the reaction of vinyl carboxylates, demonstrate higher catalytic activity.
Detailed description of the invention
A first aspect of the present invention provides a kind of containing lithium hydrated alumina forming matter, this article shaped prepares formed body by the raw material containing at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether, and described formed body is carried out drying at 80-180 DEG C and makes.Term " at least one " refers to one or more.
According to article shaped of the present invention, by using the raw material containing hydrated alumina, lithium-containing compound and cellulose ether, do not use peptizing agent, even if do not carry out high-temperature roasting also can obtain higher intensity and good strength retention, also there are good absorbent properties simultaneously.In the present invention, the composition for the formation of the raw material of described article shaped can carry out suitable selection according to the embody rule occasion of the article shaped of expection.Usually, with the total amount of described raw material for benchmark, the total content of described cellulose ether can be 0.5-12 % by weight, is preferably 1-10 % by weight, is more preferably 2-8 % by weight; With Li
2the total content of the described lithium-containing compound of O meter can be 0.5-10 % by weight, is preferably 0.5-8 % by weight, is more preferably 0.5-5 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be 78-98 % by weight, is preferably 82-98 % by weight, is more preferably 87-97 % by weight.In the present invention, when calculating the total amount of described raw material, lithium-containing compound is with Li
2o counts, and hydrated alumina is with Al
2o
3meter, and do not comprise the water introduced in described material forming process.
In the present invention, described cellulose ether refers to the ether system derivative formed after the hydrogen atom at least part of hydroxyl in cellulosic molecule is replaced by one or more alkyl, and wherein, multiple described alkyl can be identical, also can be different.Described alkyl is selected from the alkyl of replacement and unsubstituted alkyl.Described unsubstituted alkyl is preferably alkyl (such as: C
1-C
5alkyl).In the present invention, C
1-C
5the instantiation of alkyl comprise C
1-C
5straight chained alkyl and C
3-C
5branched alkyl, can for but be not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl and tertiary pentyl.The alkyl of described replacement can be such as by the alkyl of hydroxyl or carboxyl substituted (such as: C
1-C
5the alkyl be optionally substituted by a hydroxyl group, C
1-C
5by the alkyl of carboxyl substituted), its instantiation can include but not limited to: methylol, ethoxy, hydroxypropyl, hydroxyl butyl, carboxymethyl, carboxyethyl and carboxylic propyl group.
The present invention is not particularly limited for the substituent quantity of the hydrogen atom in the kind of described cellulose ether and the hydroxyl in substituted cellulose molecule, can be common various cellulose ethers.Particularly, described cellulose ether can be selected from but be not limited to: methylcellulose, ethyl cellulose, hydroxyethylcellulose, HEMC, hydroxypropyl cellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose, carboxyethyl cellulose and carboxymethyl hydroxyethyl cellulose.Preferably, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
According to the present invention, the compound containing lithium atom in the various molecular structures that described lithium-containing compound can be commonly used for this area.Such as, described lithium-containing compound can be selected from lithium salts and the organic acid lithium salts of inorganic acid, is preferably selected from water-soluble lithium salts and the water-soluble lithium salts of organic acid of inorganic acid.Particularly, described lithium-containing compound can be selected from lithium nitrate, lithium sulfate, lithium chloride, lithium oxalate and lithium acetate.Preferably, described lithium-containing compound is selected from lithium nitrate, lithium oxalate and lithium acetate.
The present invention is not particularly limited for the kind of described hydrated alumina, can be that the routine of this area is selected.Preferably, described hydrated alumina is selected from boehmite, gibbsite, unformed hydrated alumina and boehmite.More preferably, described hydrated alumina is boehmite.
According to the present invention, described article shaped is by preparing formed body by the raw material containing at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether, and described formed body is obtained 80-180 DEG C of drying.
According to the present invention, described formed body preferably carries out drying at 100-150 DEG C.The time of described drying can carry out suitable selection according to the temperature of drying, and usually, the time of described drying can be 0.5-24 hour, is preferably 1-5 hour.
The various methods that this area can be adopted conventional, to prepare described formed body, are not particularly limited.Such as: directly by hydrated alumina, cellulose ether and lithium-containing compound mixed-forming, thus described formed body can be obtained; Also can first by hydrated alumina and cellulose ether mixed-forming, obtained preform, then load lithium-containing compound on this preform, thus obtain described formed body.
One of the present invention preferred embodiment in, the method being prepared described formed body by described raw material comprises: at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether are mixed with water, obtain the first mixture, and by shaping for described first mixture.
In another preferred embodiment of the present invention, the method being prepared described formed body by described raw material comprises: at least one hydrated alumina and at least one cellulose ether are mixed with water, obtain the second mixture, and described second mixture is successively carried out shaping and dehydration, obtain preform, load at least one lithium-containing compound on described preform.
In this embodiment, on described preform, the mode of load at least one lithium-containing compound can be the routine selection of this area, such as: can by described preform is contacted with the solution containing at least one lithium-containing compound, thus by described lithium-containing compound load on described preform.The mode contacted with described solution by described preform can be selected for the routine of this area, such as: by flooding or spraying, described preform can be contacted with the solution containing at least one lithium-containing compound, thus by described lithium-containing compound load on described preform.Adopt dipping mode by described lithium-containing compound load on described preform time, described dipping can be saturated dipping, also can flood for supersaturation.The solvent of the described solution containing at least one lithium-containing compound can be the routine selection of this area, is preferably water.The concentration of the described solution containing at least one lithium-containing compound is not particularly limited, with enable the amount of the lithium-containing compound of load on described preform meet the demands (such as previously described content) be as the criterion.
In this embodiment, the condition of described dehydration is not particularly limited, and can be that the routine of this area is selected, be as the criterion can remove water.Usually, described dehydration can be carried out at the temperature of 80-180 DEG C, preferably carries out at the temperature of 100-150 DEG C.The time of described dehydration can carry out suitable selection according to the temperature of dehydration, is not particularly limited.Usually, the time of described dehydration can be 0.5-24 hour, is preferably 1-5 hour.
According to the present invention, the consumption for the preparation of the water of described first mixture or described second mixture is not particularly limited, as long as the consumption of water can guarantee various component to mix.
According to the present invention, described shaping mode is not particularly limited, and can adopt the various molding modes that this area is conventional, such as: extrusion, spraying, round as a ball, compressing tablet or their combination.One of the present invention preferred embodiment in, come shaping by the mode of extrusion.
According to the present invention, described article shaped can have various shape according to concrete instructions for use, such as: spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.
According to the present invention, described raw material can also contain at least one extrusion aid.Described extrusion aid can adopt the conventional method in this area to add in raw material, such as: can be added in above-mentioned first mixture and the second mixture by described extrusion aid respectively.The kind of described extrusion aid and consumption can be that the routine of this area is selected.General, with the total amount of described raw material for benchmark, the content of described extrusion aid can be 0.1-8 % by weight, is preferably 0.5-5 % by weight.Preferably, described extrusion aid is starch (that is, described raw material is also containing starch).As the starch in the various sources that the starch of extrusion aid can be commonly used for this area, such as: by vegetable seeds through pulverizing the powder obtained, as sesbania powder.
According to the present invention, described article shaped radial crushing strength loss late (that is, δ value) is after steeping less than 10%, can be even less than 5%.
In the present invention, δ value, for evaluating the strength retention of article shaped, is defined by following formula:
Wherein, Q
1for the radial crushing strength of the article shaped without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radial crushing strength of the article shaped of 120 DEG C of dryings after 4 hours, in N/mm.
According to the present invention, the Q of described article shaped
1can be more than 12N/mm, be even more than 15N/mm.Particularly, according to the Q of article shaped of the present invention
1can be that 15-30N/mm(is as 15-25N/mm).
In the present invention, described radial crushing strength according to " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety the first edition, the volumes such as Yang Cuiding) in the RIPP25-90 that records the method that specifies measure.
According to the present invention, the water absorption rate of described article shaped is 0.4-1.5, is generally 0.6-1(as 0.6-0.8).
In the present invention, described water absorption rate refers to that the dry excessive deionized water of article shaped soaks the ratio of the weight of the weight change value of 30 minutes front and back and the article shaped of described drying.Concrete method of testing is: by article shaped to be measured 120 DEG C of dryings 4 hours, then sieves with 40 object standard screens, takes 20g oversize and (be designated as w as testing sample
1), testing sample 50g deionized water is soaked 30 minutes, after filtration, solid phase is drained 5 minutes, the weight then weighing the solid phase drained (is designated as w
2), with following formulae discovery water absorption rate:
Containing lithium hydrated alumina forming matter, not only there are good absorbent properties according to of the present invention, and there is higher intensity and good strength retention, be suitable for the carrier as loaded catalyst.Further, adopt that of the present invention the catalyst prepared has eggshell type structure (that is, having the active component integrated distribution of catalytic action on the surface of catalyst carrier) containing as carrier, lithium hydrated alumina forming matter comes that load has the active component of catalytic action.
Thus, a second aspect of the present invention provides and is preparing the application in egg-shell catalyst according to of the present invention containing lithium hydrated alumina forming matter.
A third aspect of the present invention provides a kind of preparation method of egg-shell catalyst, and the method is included in the active component that supported on carriers at least one has catalytic action, and wherein, described carrier is provided by the invention above-mentioned containing lithium hydrated alumina forming matter.
In the present invention, term " egg-shell catalyst " refers to the catalyst of active component integrated distribution on the surface of catalyst carrier with catalytic action.Usually, for egg-shell catalyst, shell factor sigma is 0≤σ≤0.9, wherein,
c
outwardfor there is the mean concentration of active component at the outer surface of described catalyst of catalytic action, C
infor having the mean concentration of active component in the center of described catalyst of catalytic action.Preferably, 0≤σ≤0.5; More preferably, 0≤σ≤0.1(can be such as 0.01≤σ≤0.09).
In the present invention, the shell factor adopts SEM and energy disperse spectroscopy (SEM-EDX) to measure the distribution of active component along catalyst radial section, and calculated activity component is at the ratio of the mean concentration of catalyst granules outer surface with the mean concentration of center.Wherein, the mean concentration of outer surface is the mean value of outer surface 20 numerical point counting rates; Mean value (the note: the counting rate along the radial every bit of carrier in SEM-EDX characterization result is mutually corresponding with this tenor of 20 the numerical point counting rates in some place centered by the mean concentration of center, the size of counting rate reflects this tenor height, but does not represent the real content of this metal).
Method according to the present invention is that the lithium hydrated alumina forming matter that contains that the application of the invention provides prepares egg-shell catalyst as carrier, kind for described catalyst is not particularly limited, the distribution of active component on carrier that the various needs can commonly used for this area make to have catalytic action concentrates on the catalyst of the outer surface of carrier, the catalyst such as, applied in the various chemical reaction controlling by diffusion.
Correspondingly, the kind that method according to the present invention has an active component of catalytic action for described and load capacity are also not particularly limited, and can carry out suitable selection according to the embody rule occasion of the egg-shell catalyst of preparation.
Such as, be used for making ethene and carboxylic acid carry out oxidation reaction at prepared according to the methods of the invention catalyst, during to prepare vinyl carboxylates, described in there is catalytic action active component be preferably Pd and Au.Pd and Au load capacity on the carrier can carry out suitable selection according to concrete reaction condition.Preferably, Pd and Au load capacity on the carrier makes, and with the total amount of the catalyst prepared for benchmark, the content of described carrier can be 96-99.5 % by weight, is preferably 96.8-99 % by weight; In element, the content of Pd can be 0.1-2.5 % by weight, is preferably 0.2-2 % by weight; The content of Au can be 0.1-1.5 % by weight, is preferably 0.2-1.2 % by weight.
According to method of the present invention, the various methods that this area can be adopted to commonly use by the described active constituent loading with catalytic action on the carrier.Usually, the mode in supported on carriers at least one with the active component of catalytic action comprises: the solution described in being contained with containing at least one by described carrier with the compound of the active component of catalytic action contacts, and removes load and have solvent on the carrier of described compound.The solution described in described carrier contains with containing at least one by the various modes that this area can be adopted to commonly use with the compound of the active component of catalytic action contacts, as dipping or spraying.When adopting the mode of dipping to realize described contact, described dipping can be saturated dipping, also can be excessive dipping.Described contain containing at least one described in there is the solution of the compound of the active component of catalytic action concentration can select for the routine of this area, concrete instructions for use can be met so that the content described in the catalyst finally prepared with the active component of catalytic action can be made and be as the criterion.Described contain containing at least one described in there is the solution of the compound of the active component of catalytic action solvent be not particularly limited, the various solvents can commonly used for this area.From environmental protection and cost-saving angle, described solvent is preferably water.The present invention is not particularly limited for the condition of desolvation.Usually, removing load has the condition of the solvent on the carrier of described compound to comprise: temperature can be 100-200 DEG C; Time can be 1-15 hour.
According to method of the present invention, when the described active component with catalytic action is two or more active component, can on the carrier by the described active constituent loading with catalytic action simultaneously, also can gradation by the described active constituent loading with catalytic action on the carrier.
Particularly, when the described active component with catalytic action is Pd and Au, can comprise according to method of the present invention: will can form metal Pd (namely under the reducing conditions, valence state is the Pd of 0) containing Pd compound and metal A u(can be formed namely under the reducing conditions, valence state is the Au of 0) on the carrier compound loaded containing Au.The various methods that this area can be adopted to commonly use can form containing Pd compound and can forming the on the carrier compound loaded containing Au of metal A u under the reducing conditions of metal Pd under the reducing conditions by described.
Method according to the present invention one preferred embodiment in, by described can be formed under the reducing conditions metal Pd containing Pd compound and metal A u can be formed under the reducing conditions containing the compound loaded mode on the carrier of Au be: load contains at least one containing the water soluble compound of Pd and at least one water soluble compound containing Au on the carrier, load there is the described water soluble compound containing Pd to contact with precipitating reagent with the carrier of the water soluble compound containing Au, and remove the solvent on carrier.
The described water soluble compound containing Pd and the water soluble compound containing Au can be that the routine of this area is selected separately, such as: the described water soluble compound containing Pd can be selected from the acid of palladium bichloride, palladium, palladium nitrate and chlorine palladium and water soluble salt (as alkali metal salt) thereof; The described water soluble compound containing Au can be selected from chlorauride and tetra chlorauric acid and water soluble salt (as alkali metal salt) thereof.
The various methods that this area can be adopted to commonly use by described water soluble compound containing Pd and containing Au water soluble compound load on the carrier, such as: can by described carrier is contacted containing the aqueous solution of the water soluble compound of Au with containing water soluble compound and at least one of at least one containing Pd, thus by the water soluble compound of the described Pd of containing and contain Au water soluble compound load on the carrier.The mode that described carrier and the water soluble compound containing Pd containing at least one contact with the aqueous solution that at least one contains the water soluble compound of Au can be selected for the routine of this area, such as: dipping or spray, be preferably dipping (as saturated dipping or excessive dipping), be more preferably saturated dipping.
The various materials that the described water soluble compound containing Pd and the water soluble compound containing Au can be made to form precipitation that described precipitating reagent can be commonly used for this area, as alkali.Particularly, described precipitating reagent can be NaOH and/or potassium hydroxide.Preferably, described precipitating reagent is NaOH.The present invention is not particularly limited for the consumption of described precipitating reagent, forms precipitation be as the criterion can make the water soluble compound of whole or the basic all described water soluble compound containing Pd and the described Au of containing.
Load has the described water soluble compound containing Pd to contact with precipitating reagent with the carrier of the water soluble compound containing Au by the various methods that this area can be adopted to commonly use, such as: precipitating reagent can be mixed with the aqueous solution, and with this aqueous impregnation (be preferably saturated dipping) or spray the carrier that described load has the described water soluble compound containing Pd and the water soluble compound containing Au.The temperature and time of described contact can be the routine selection of this area, forms precipitation be as the criterion can make the whole or basic water soluble compound of all described Pd of containing and the water soluble compound of the described Au of containing.
In this embodiment, described solvent is preferably water.The present invention is not particularly limited for the condition of the solvent removed on carrier, being as the criterion by desolvation.Usually, the condition removing described solvent comprises: temperature can be 100-200 DEG C; Time can be 1-15 hour.
In addition, the active component with catalytic action be the Pd(of reduction-state such as, valence state is the Pd of 0) and reduction-state Au(such as, valence state is the Au of 0) time, method according to the present invention also comprises: under reductive condition, is contacted by the carrier being stripped of solvent with reducing agent.
According to the present invention, can under the conventional reductive condition in this area, by load contact with reducing agent with containing Au compound containing Pd compound on the carrier, with by described contain Pd compound and contain Au compound reduce separately and become metal Pd and metal A u.Described reducing agent can for this area commonly use various can by described containing Pd compound and containing Au compound reduction reducing agent, such as: hydrogen, carbon monoxide or hydrogen sulfide.Described reductive condition can carry out suitable selection according to the kind of described reducing agent, such as: when using hydrogen as reducibility gas, described reductive condition can comprise: temperature can be 300-500 DEG C; Time can be 1-8 hour.
According to method of the present invention, as the case may be, can also comprise and introduce at least one auxiliary element on the carrier.
Such as, when the described active component with catalytic action is Pd and Au, preferably introduce the following auxiliary element of at least one on the carrier according to method of the present invention: K, La, Ce, Cr, V, B, Mn, Re, Pt, Ru, Ba and Ca.Above-mentioned auxiliary element introduction volume on the carrier can carry out suitable selection according to the embody rule occasion of the catalyst of final preparation.Usually, described auxiliary element introduction volume on the carrier makes, and with the total amount of the catalyst prepared for benchmark, in element, the total content of described auxiliary element can be 0.1-5 % by weight, is preferably 0.3-1 % by weight.
The conventional various methods in this area can be adopted to introduce auxiliary element on the carrier.Such as, by introducing described auxiliary element in the process of the described carrier of preparation, also by being contacted with containing the solution of at least one containing the compound of described auxiliary element by described carrier, thus auxiliary element can be introduced on the carrier.
The mode introducing described auxiliary element in the process of the described carrier of preparation can comprise: mixed with at least one hydrated alumina, at least one cellulose ether and optional at least one lithium-containing compound by the compound of at least one containing described auxiliary element, by shaping for the mixture obtained, and carry out drying at 80-180 DEG C (preferred 100-150 DEG C), prepare the carrier containing described auxiliary element.
By described carrier is contacted with containing the solution of at least one containing the compound of described auxiliary element, thus when introducing auxiliary element on the carrier, described auxiliary element can be loaded on described carrier while load P d and Au, also can gradation by Pd, Au and described auxiliary element load on the carrier.
The various water soluble compounds containing described auxiliary element that the described compound containing auxiliary element can be commonly used for this area.Such as, when described auxiliary element is K, the described compound containing auxiliary element can be KOAc and/or KNO
3.
A fourth aspect of the present invention provides a kind of egg-shell catalyst, this catalyst contains carrier and the load active component with catalytic action on the carrier, the described active component with catalytic action is Pd and Au, wherein, described carrier is provided by the invention containing lithium hydrated alumina forming matter.
According to egg-shell catalyst of the present invention, can be loaded on carrier with the form of oxidation state as the active component Pd and Au with catalytic action, also can be loaded on carrier with the form of reduction-state (that is, valence state is for 0).When being loaded on carrier with the form of oxidation state, by contacting with reducing agent under reductive condition, described active component can be reduced before use according to egg-shell catalyst of the present invention.
According to egg-shell catalyst of the present invention, Pd and Au load capacity on the carrier can carry out suitable selection according to the embody rule occasion of described catalyst.Usually, with the total amount of described catalyst for benchmark, the content of described carrier can be 96-99.5 % by weight, is preferably 96.8-99 % by weight; In element, the content of Pd can be 0.1-2.5 % by weight, is preferably 0.2-2 % by weight; The content of Au can be 0.1-1.5 % by weight, is preferably 0.2-1.2 % by weight.
According to egg-shell catalyst of the present invention, the shell factor sigma of Pd and Au can be 0≤σ≤0.9 separately, and be preferably 0≤σ≤0.5, being more preferably 0≤σ≤0.1(can be such as 0.01≤σ≤0.09).
According to egg-shell catalyst of the present invention, from the further angle improving the catalytic activity of catalyst according to the invention, this catalyst is preferably also containing load at least one auxiliary element on the carrier, described auxiliary element is selected from K, La, Ce, Cr, V, B, Mn, Re, Pt, Ru, Ba and Ca, is preferably selected from K and Ba.With the total amount of described catalyst for benchmark, in element, the total content of described auxiliary element can be 0.1-5 % by weight, is preferably 0.3-1 % by weight.
According to egg-shell catalyst of the present invention, described carrier and preparation method thereof, with described identical above, does not repeat them here.The previously described method preparing egg-shell catalyst such as can be adopted to obtain according to egg-shell catalyst of the present invention, be not described in detail in this.
Egg-shell catalyst using Pd and Au as active component according to the present invention is particularly suitable for as catalyst when preparing vinyl carboxylates by ethene and carboxylic acid by oxidation reaction.
Thus, a fifth aspect of the present invention provide a kind of egg-shell catalyst according to the present invention by ethene and carboxylic acid oxidative to prepare the application in vinyl carboxylates.
A sixth aspect of the present invention provides a kind of method preparing vinyl carboxylates, the method comprises in the presence of a catalyst, is contacted by ethene with carboxylic acid with oxygen, to obtain the mixture containing vinyl carboxylates, wherein, described catalyst is catalyst provided by the invention.
The method preparing vinyl carboxylates according to the present invention is that the egg-shell catalyst that the application of the invention provides obtains higher catalytic activity, is not particularly limited for other condition preparing vinyl carboxylates, can be that the routine of this area is selected.
Usually, what described carboxylic acid can be commonly used for this area can to form the various organic acids of vinyl carboxylates with ethene by oxidation reaction, such as: carbon number is the various straight or branched organic carboxyl acids of 2-10.Particularly, described carboxylic acid can be but be not limited to: acetic acid, n Propanoic acid, n-butyric acie, isobutyric acid, positive valeric acid, n-caproic acid and positive enanthic acid.Method according to the present invention is specially adapted to prepare vinyl acetate by ethene and acetic acid and oxygen reaction.
According to method of the present invention, ethene, ratio between described carboxylic acid and oxygen can be that the routine of this area is selected.Preferably, the mol ratio of ethene, described carboxylic acid and oxygen is 1:0.1-0.2:0.05-0.1.More preferably, the mol ratio of ethene, described carboxylic acid and oxygen is 1:0.12-0.18:0.06-0.08.
According to method of the present invention, the consumption of described catalyst can carry out suitable selection according to concrete reaction condition, is as the criterion can realize catalysis.
The condition that ethene and carboxylic acid contact with oxygen is not particularly limited by method according to the present invention, is as the criterion with the mixture that can obtain containing vinyl carboxylates.Such as, described condition comprises: temperature can be 100-200 DEG C, is preferably 120-180 DEG C; In gauge pressure, pressure can be 0.5-1.5MPa, is preferably 0.8-1.2MPa.
Can also comprise according to method of the present invention and isolate vinyl carboxylates from described mixture.The present invention is not particularly limited for the method be separated, and can be that the routine of this area is selected, repeat no more herein.
The present invention is described in detail below in conjunction with embodiment and comparative example.
In following examples and comparative example, the method specified in RIPP25-90 is adopted to measure the radial crushing strength of article shaped.
In following examples and comparative example, following methods is adopted to measure the δ value of article shaped: to adopt the method mensuration that specifies in RIPP25-90 (to be designated as Q without the radial crushing strength of the article shaped of water soaking
1); Article shaped is placed in 50g deionized water, soaks 30 minutes, then filter, by the solid that obtains at the temperature of 120 DEG C dry 4 hours, the radial crushing strength measuring dry solid according to the method specified in RIPP25-90 (was designated as Q
2), adopt following formulae discovery δ value,
In following examples and comparative example, following methods is adopted to measure the water absorption rate of article shaped: by article shaped to be measured 120 DEG C of dryings 4 hours, then to sieve with 40 object standard screens, take 20g oversize and (be designated as w as testing sample
1), testing sample 50g deionized water is soaked 30 minutes, after filtration, solid phase is drained 5 minutes, the weight then weighing the solid phase drained (is designated as w
2), with following formulae discovery water absorption rate:
In following examples and comparative example, contents on dry basis is by measuring testing sample 600 DEG C of roastings 4 hours.
In following examples and comparative example, measured the content of active component in catalyst by x-ray fluorescent spectrometry (that is, XRF).
In following examples and comparative example, adopt SEM-EDX to measure the distribution of active component along catalyst radial section, calculated activity component is at the ratio of the mean concentration of catalyst granules outer surface with the mean concentration of center.Wherein, the mean concentration of outer surface is the mean value of outer surface 20 numerical point counting rates; Mean value (the note: the counting rate along the radial every bit of carrier in SEM-EDX characterization result is mutually corresponding with this tenor of 20 the numerical point counting rates in some place centered by the mean concentration of center, the size of counting rate reflects this tenor height, but does not represent the real content of this metal).
Embodiment 1-9 contains lithium hydrated alumina forming matter for illustration of according to of the present invention.
Embodiment 1
With stirring 5.0gLiNO
3be dissolved in 95mL deionized water, obtain containing the lithium aqueous solution.By 100.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 4.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder and above-mentioned containing lithium aqueous solution even.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven, 150 DEG C of dryings 12 hours, thus obtains according to of the present invention containing lithium hydrated alumina forming matter.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Comparative example 1
With stirring 5.0gLiNO
3be dissolved in 95mL deionized water, obtain containing the lithium aqueous solution.By 100.0g boehmite powder (with embodiment 1), 2.5mL red fuming nitric acid (RFNA), 3.0g sesbania powder and above-mentioned containing lithium aqueous solution even.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven, 150 DEG C of dryings 12 hours, then 600 DEG C of roastings 4 hours, thus obtains article shaped.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Comparative example 2
The method identical with comparative example 1 is adopted to prepare article shaped, unlike, do not carry out roasting at 600 DEG C, thus obtain article shaped.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Comparative example 3
The method identical with embodiment 1 is adopted to prepare article shaped, unlike, in step (1), the wet bar extruded is placed in baking oven, 150 DEG C of dryings 1 hour, then 500 DEG C of roastings 3 hours, thus obtains article shaped.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 2
(1) in the retort of a 2L with and the mode of flowing adds aluminum sulfate solution that 2000mL concentration is 48g/L and sodium aluminate solution that (alumina content is for 200g/L, causticity coefficient is 1.58) carry out precipitation reaction, reaction temperature is 50 DEG C, and pH value is 6.0, and reaction time is 15 minutes; The slurries vacuum filter obtained is filtered, to be filtered complete after, on filter cake supplement add 20L deionized water (temperature is 40 ± 5 DEG C) flush cake about 60 minutes.Filter cake after washing is joined 1.5L deionized water for stirring and becomes slurries, slurries are carried out drying with being pumped into spray dryer, control the outlet temperature of spray dryer within the scope of 100-110 DEG C, the dry materials time is 2 minutes, obtain hydrated alumina, wherein, alumina content is 63 % by weight, is defined as amorphous state through XRD analysis.
(2) with stirring 3.0gLiNO
3be dissolved in 95mL deionized water and obtain containing the lithium aqueous solution.Unformed hydrated alumina 50.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 50.0g step (1) prepared, 2.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd) and the above-mentioned lithium aqueous solution that contains stir.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 100 DEG C of dryings 12 hours, thus obtains according to of the present invention containing lithium hydrated alumina forming matter.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 3
With at the temperature being stirred in 60 DEG C, 9.8g lithium oxalate is dissolved in 95mL deionized water, prepares containing the lithium aqueous solution.By 60.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 40.0g gibbsite (purchased from Pingguo Aluminium Industry Co., Guangxi, contents on dry basis is 64.5 % by weight), 1.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 2.0g hydroxypropyl methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder and above-mentionedly to stir containing the lithium aqueous solution.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 80 DEG C of dryings 12 hours, thus obtains according to of the present invention containing lithium hydrated alumina forming matter.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Comparative example 4
The method identical with embodiment 3 is adopted to prepare article shaped, unlike, in step (1), the wet bar obtained is placed in baking oven, 60 DEG C of dryings 12 hours, thus obtains article shaped.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 4
With stirring, 2.0g lithium acetate being dissolved in 90mL deionized water, preparing containing the lithium aqueous solution.100.0g boehmite SB powder (purchased from Sasol company, contents on dry basis is 75.0 % by weight), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd) and the above-mentioned lithium aqueous solution that contains are stirred.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 150 DEG C of dryings 12 hours, thus obtains according to of the present invention containing lithium hydrated alumina forming matter.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 5
By 100.0g boehmite SB powder (purchased from Sasol company, contents on dry basis is 75.0 % by weight), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 2.0g hydroxypropyl methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder, 6.0gLiNO
3mix with 90mL water.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 180 DEG C of dryings 4 hours, thus obtains according to of the present invention containing lithium hydrated alumina forming matter.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Comparative example 5
The method identical with embodiment 5 is adopted to prepare containing lithium hydrated alumina forming matter, unlike, the bar that will wet 200 DEG C of dryings 4 hours, thus obtains containing lithium hydrated alumina forming matter.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 6
At the temperature of 50 DEG C, with stirring 8.0gLiNO
3be dissolved in 90mL deionized water, prepare containing the lithium aqueous solution.By 100.0g boehmite (purchased from Yantai, Shandong Heng Hui Chemical Co., Ltd., contents on dry basis is 71.0 % by weight), 5.0g hydroxypropyl methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder and above-mentioned containing lithium aqueous solution even.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 120 DEG C of dryings 4 hours, thus obtains according to of the present invention containing lithium hydrated alumina forming matter.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 7
The method identical with embodiment 2 is adopted to prepare containing lithium hydrated alumina forming matter, unlike, the content of methylcellulose is 4.0g, thus obtains according to of the present invention containing lithium hydrated alumina forming matter.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 8
100.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 4.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.) and 3.0g sesbania powder are mixed.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven, 150 DEG C of dryings 12 hours.At the temperature of 50 DEG C, with stirring 8.0gLiNO
3be dissolved in 90mL deionized water, prepare containing the lithium aqueous solution.Take 50.0g shaping and drying bar, put into above-mentioned containing the lithium aqueous solution, soak after 4 hours and filter, 120 DEG C of dryings 6 hours, thus obtain according to of the present invention containing lithium hydrated alumina forming matter.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 9
The method identical with embodiment 5 is adopted to prepare article shaped, unlike, the wet bar obtained is placed in baking oven, 150 DEG C of dryings 4 hours, thus obtains according to of the present invention containing lithium hydrated alumina forming matter.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Table 1
| Numbering | Crushing strength (N/mm) | Water absorption rate | δ value (%) |
| Embodiment 1 | 24.0 | 0.67 | 3.1 |
| Comparative example 1 | 26.1 | 0.84 | 1.9 |
| Comparative example 2 | 21.6 | 0.64 | 64.6 |
| Comparative example 3 | 24.2 | 0.76 | 3.3 |
| Embodiment 2 | 22.3 | 0.63 | 3.1 |
| Embodiment 3 | 16.7 | 0.68 | 4.8 |
| Comparative example 4 | 13.4 | 0.55 | 24.6 |
| Embodiment 4 | 22.1 | 0.66 | 2.3 |
| Embodiment 5 | 23.0 | 0.57 | 3.2 |
| Comparative example 5 | 21.8 | 0.58 | 3.1 |
| Embodiment 6 | 19.3 | 0.67 | 4.0 |
| Embodiment 7 | 23.4 | 0.68 | 3.2 |
| Embodiment 8 | 23.9 | 0.63 | 3.3 |
| Embodiment 9 | 24.6 | 0.57 | 3.8 |
The result of table 1 illustrates, has good absorbent properties, higher intensity and strength retention, be suitable for the carrier as loaded catalyst according to of the present invention containing lithium hydrated alumina forming matter.
Embodiment 10-18 for illustration of according to of the present invention containing the preparation method of lithium hydrated alumina forming matter at the application prepared in egg-shell catalyst and egg-shell catalyst.
Embodiment 10
By 1.19gNa
2pdCl
4and 0.37gHAuCl
4mix with water, be mixed with 39.5mL dipping solution, with the carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 71.0 % by weight) of this solution impregnation 50.0g embodiment 1 preparation, dip time is 5 minutes.The carrier that dipping obtains is placed in the aqueous solution that 20mL contains 1.5gNaOH, at room temperature leaves standstill 8 hours, filter rear deionized water rinsing, until not containing Cl in washing lotion
-till.Then by the solid phase that obtains in 120 DEG C of dryings 2 hours, then at 500 DEG C with hydrogen reducing 3 hours.After being cooled to room temperature, the solid phase obtained containing the aqueous impregnation of 0.22gKOAc with 31.5mL 30 minutes, after filtration, by the solid phase that obtains in 80 DEG C of dryings 4 hours, thus obtain catalyst according to the invention C1, characterization result illustrates in table 2.
Comparative example 6
By 1.19gNa
2pdCl
4and 0.37gHAuCl
4mix with water, be mixed with 29.5mL dipping solution, with the carrier (diameter is 1.1mm, and particle length is 2-5mm) of this solution impregnation 35.1g comparative example 1 preparation, dip time is 5 minutes.The carrier obtained is placed in the solution that 20mL contains 1.5gNaOH, left at room temperature 8 hours, filters rear deionized water rinsing, until not containing Cl in washing lotion
-till.Then by the solid phase that obtains in 120 DEG C of dryings 2 hours, then at 500 DEG C with hydrogen reducing 3 hours.After being cooled to room temperature, the solid phase obtained containing the aqueous impregnation of 0.22gKOAc with 29.5mL 30 minutes, after filtration, by the solid phase that obtains in 80 DEG C of dryings 4 hours, thus obtain catalyst A 1, characterization result is in table 2.
Comparative example 7
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 10, unlike, carrier is carrier prepared by comparative example 2, and in dipping process, the phenomenon of dissolving and structure collapses appears in carrier, and the catalyst A 2 obtained cannot use as preformed catalyst.
Comparative example 8
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 10, unlike, carrier is carrier (diameter is 1.1mm, and particle length is 2-5mm) prepared by comparative example 3, thus obtains catalyst A 3, and characterization result is in table 2.
Embodiment 11
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 10, unlike, carrier is carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 71.3 % by weight) prepared by embodiment 2, thus obtains catalyst C2, and characterization result is in table 2.
Embodiment 12
By 1.80gNa
2pdCl
4and 0.56gHAuCl
4mix with water, be mixed with 34.5mL dipping solution, with the carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 69.4 % by weight) of this solution impregnation 50.4g embodiment 3 preparation, dip time is 5 minutes.The carrier that dipping obtains is placed in the solution that 20mL contains 1.5gNaOH, left at room temperature 8h, after filtration, with deionized water rinsing, until not containing Cl in washing lotion
-till.Then by the solid phase that obtains in 120 DEG C of dryings 2 hours, then at 500 DEG C with hydrogen reducing 3 hours.After being cooled to room temperature, the solid phase obtained with the aqueous impregnation that 37.5mL contains 0.33gKOAc 30 minutes.After filtration, by the solid phase that obtains in 80 DEG C of dryings 4 hours, thus obtain catalyst according to the invention C3, characterization result is in table 2.
Comparative example 9
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 12, unlike, carrier is carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 66.4 % by weight) prepared by comparative example 4, thus obtains catalyst A 4, and characterization result illustrates in table 2.
Embodiment 13
By 1.19gNa
2pdCl
4and 0.37gHAuCl
4mix with water, be mixed with 36.3mL dipping solution, with the carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 67.9 % by weight) of this solution impregnation 50.0g embodiment 4 preparation, dip time is 5 minutes.After filtration, the solid phase obtained is placed in the solution that 20mL contains 1.5gNaOH, left at room temperature 8 hours.After filtration, by the solid phase deionized water rinsing obtained, until not containing Cl in washing lotion
-till.By the solid phase that obtains in 150 DEG C of dryings 2 hours, then at 500 DEG C with hydrogen reducing 3 hours.After being cooled to room temperature, obtain catalyst according to the invention C4, characterization result is in table 2.
Embodiment 14
Adopting the method Kaolinite Preparation of Catalyst identical with embodiment 10, is that (diameter is 1.1mm to the carrier prepared of embodiment 5 unlike, carrier, particle length is 2-5mm, contents on dry basis is 76.8 % by weight), thus obtain catalyst according to the invention C5, characterization result illustrates in table 2.
Comparative example 10
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 10, unlike, carrier is carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 80.2 % by weight) prepared by comparative example 5, thus obtains catalyst A 5, and characterization result illustrates in table 2.
Embodiment 15
By 0.60gNa
2pdCl
4and 0.19gHAuCl
4mix with water, be mixed with 40.5mL dipping solution, with the carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 67.7 % by weight) of this solution impregnation 50.0g embodiment 6 preparation, dip time is 5 minutes.After filtration, the solid phase obtained is placed in the solution that 20mL contains 1.5gNaOH, left at room temperature 8 hours.After filtration, by the solid phase deionized water rinsing obtained, until not containing Cl in washing lotion
-till.By the solid phase after washing in 120 DEG C of dryings 2 hours, then at 500 DEG C with hydrogen reducing 3 hours.After being cooled to room temperature, by the solid phase 33.5mL that the obtains aqueous impregnation 30 minutes containing 0.11gKOAc.After filtration, by the solid phase that obtains in 80 DEG C of dryings 4 hours, thus obtain catalyst according to the invention C6, characterization result illustrates in table 2.
Embodiment 16
Adopting the method Kaolinite Preparation of Catalyst identical with embodiment 11, is that (diameter is 1.1mm to the carrier prepared of embodiment 7 unlike, carrier, particle length is 2-5mm, contents on dry basis is 71.2 % by weight), thus obtain catalyst according to the invention C7, characterization result is listed in table 2.
Embodiment 17
Adopting the catalyst prepared of the method identical with embodiment 10, is that (diameter is 1.1mm for the carrier of embodiment 8 preparation unlike, carrier, particle length is 2-5mm, contents on dry basis is 73.4 % by weight), thus obtain catalyst according to the invention C8, characterization result is listed in table 2.
Embodiment 18
Adopting the method Kaolinite Preparation of Catalyst identical with embodiment 10, is that (diameter is 1.1mm to the carrier prepared of embodiment 9 unlike, carrier, particle length is 2-5mm, contents on dry basis is 75.5 % by weight), thus obtain catalyst according to the invention C9, characterization result is listed in table 2.
Embodiment 19-27 for illustration of catalyst according to the invention application and prepare the method for vinyl carboxylates.
Embodiment 19-27
The catalytic performance of catalyst prepared of Evaluation operation example 10-18 respectively on fixed bed reactors.Wherein, raw material is ethylene/acetic acid/oxygen=82/12/6(mol ratio), catalyst volume is 30mL, and the volume space velocity of ethene is 2.5h
-1.
Reaction condition comprises: temperature is 140 DEG C, reactor inlet pressure 1MPa.
The mixture gas chromatography be obtained by reacting is to measure its composition, and by the conversion ratio of following formulae discovery ethene, result is listed in table 2.
Comparative example 11-14
Adopt the method identical with embodiment 19-27 to carry out the performance of evaluate catalysts, be respectively catalyst prepared by comparative example 6 and 8-10 unlike, catalyst, result is listed in table 2.
Table 2
The result of table 2 shows, to adopt conventional method load to have the active component of catalytic action containing lithium hydrated alumina forming matter as carrier according to of the present invention, can prepare the catalyst that active component is eggshell type distribution; Further, catalyst according to the invention by ethene and carboxylic acid oxidative to prepare in the reaction of vinyl carboxylates, show higher catalytic activity.
Claims (34)
1. the preparation method of an egg-shell catalyst, the method is included in the active component that supported on carriers at least one has catalytic action, it is characterized in that, described carrier is for containing lithium hydrated alumina forming matter, this article shaped prepares formed body by a kind of raw material, and described formed body is carried out drying at 80-180 DEG C and makes, described raw material is by least one hydrated alumina, at least one lithium-containing compound, at least one cellulose ether and at least one extrusion aid composition containing or do not contain, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-12 % by weight, with Li
2the total content of the described lithium-containing compound of O meter is 0.5-10 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 78-98 % by weight.
2. method according to claim 1, wherein, the mode in supported on carriers at least one with the active component of catalytic action comprises: the solution described in being contained with containing at least one by described carrier with the compound of the active component of catalytic action contacts, and removes load and have solvent on the carrier of described compound.
3. method according to claim 2, wherein, removing load has the condition of the solvent on the carrier of described compound to comprise: temperature is 100-200 DEG C; Time is 1-15 hour.
4. method according to claim 1 and 2, wherein, described in there is catalytic action active component be Pd and Au.
5. method according to claim 1, wherein, the described active component load capacity on the carrier with catalytic action makes, with the total amount of the catalyst of preparation for benchmark, the content of described carrier is 96-99.5 % by weight, in element, the content of Pd is the content of 0.1-2.5 % by weight, Au is 0.1-1.5 % by weight.
6. method according to claim 1 and 2, wherein, the method also comprises introduces at least one auxiliary element on the carrier, described auxiliary element is selected from K, La, Ce, Cr, V, B, Mn, Re, Pt, Ru, Ba and Ca, described auxiliary element introduction volume on the carrier makes, with the total amount of the catalyst of preparation for benchmark, in element, the total content of described auxiliary element is 0.1-5 % by weight.
7. method according to claim 1, wherein, the temperature of described drying is 100-150 DEG C.
8. method according to claim 1, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 1-10 % by weight, with Li
2the total content of the described lithium-containing compound of O meter is 0.5-8 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 82-98 % by weight.
9. method according to claim 8, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 2-8 % by weight, with Li
2the total content of the described lithium-containing compound of O meter is 0.5-5 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 87-97 % by weight.
10. according to the method in claim 1,8 and 9 described in any one, wherein, described cellulose ether is be selected from least one in methylcellulose, HEMC and hydroxypropyl methylcellulose.
11. according to the method in claim 1,8 and 9 described in any one, and wherein, described lithium-containing compound is be selected from least one in lithium nitrate, lithium sulfate, lithium chloride, lithium oxalate and lithium acetate;
Described hydrated alumina is be selected from least one in boehmite, gibbsite, unformed hydrated alumina and boehmite.
12. according to the method in claim 1 and 7-9 described in any one, and wherein, the water absorption rate of described article shaped is 0.4-1.5, δ value is less than 10%, Q
1for more than 12N/mm,
Wherein,
Q
1for the radial crushing strength of the carrier without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radial crushing strength of the carrier of 120 DEG C of dryings after 4 hours, in N/mm.
13. methods according to claim 12, wherein, the water absorption rate of described article shaped is 0.6-1, δ value is less than 5%, Q
1for 15-30N/mm.
14. methods according to claim 1, wherein, with the total amount of described raw material for benchmark, the content of described extrusion aid is 0.1-8 % by weight.
15. methods according to claim 14, wherein, with the total amount of described raw material for benchmark, the content of described extrusion aid is 0.5-5 % by weight.
16. according to the method in claim 1,14 and 15 described in any one, and wherein, described extrusion aid is starch.
17. according to the method in claim 1,14 and 15 described in any one, and wherein, described extrusion aid is sesbania powder.
18. 1 kinds of egg-shell catalysts, this catalyst contains carrier and the load active component with catalytic action on the carrier, the described active component with catalytic action is Pd and Au, it is characterized in that, described carrier is for containing lithium hydrated alumina forming matter, this article shaped prepares formed body by a kind of raw material, and described formed body is carried out drying at 80-180 DEG C and makes, described raw material is by least one hydrated alumina, at least one lithium-containing compound, at least one cellulose ether and at least one extrusion aid composition containing or do not contain, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-12 % by weight, with Li
2the total content of the described lithium-containing compound of O meter is 0.5-10 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 78-98 % by weight.
19. catalyst according to claim 18, wherein, with the total amount of described catalyst for benchmark, the content of described carrier is 96-99.5 % by weight, and in element, the content of Pd is the content of 0.1-2.5 % by weight, Au is 0.1-1.5 % by weight.
20. catalyst according to claim 18 or 19, wherein, this catalyst is also containing load at least one auxiliary element on the carrier, described auxiliary element is selected from K, La, Ce, Cr, V, B, Mn, Re, Pt, Ru, Ba and Ca, with the total amount of described catalyst for benchmark, in element, the total content of described auxiliary element is 0.1-5 % by weight.
21. catalyst according to claim 18, wherein, the temperature of described drying is 100-150 DEG C.
22. catalyst according to claim 18, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 1-10 % by weight, with Li
2the total content of the described lithium-containing compound of O meter is 0.5-8 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 82-98 % by weight.
23. catalyst according to claim 22, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 2-8 % by weight, with Li
2the total content of the described lithium-containing compound of O meter is 0.5-5 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 87-97 % by weight.
24. according to the catalyst in claim 18,22 and 23 described in any one, and wherein, described cellulose ether is be selected from least one in methylcellulose, HEMC and hydroxypropyl methylcellulose.
25. according to the catalyst in claim 18,22 and 23 described in any one, and wherein, described lithium-containing compound is be selected from least one in lithium nitrate, lithium sulfate, lithium chloride, lithium oxalate and lithium acetate;
Described hydrated alumina is be selected from least one in boehmite, gibbsite, unformed hydrated alumina and boehmite.
26. according to the catalyst in claim 18 and 21-23 described in any one, and wherein, the water absorption rate of described article shaped is 0.4-1.5, δ value is less than 10%, Q
1for more than 12N/mm,
Wherein,
Q
1for the radial crushing strength of the carrier without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radial crushing strength of the carrier of 120 DEG C of dryings after 4 hours, in N/mm.
27. catalyst according to claim 26, wherein, the water absorption rate of described article shaped is 0.6-1, δ value is less than 5%, Q
1for 15-30N/mm.
28. catalyst according to claim 18, wherein, with the total amount of described raw material for benchmark, the content of described extrusion aid is 0.1-8 % by weight.
29. catalyst according to claim 28, wherein, with the total amount of described raw material for benchmark, the content of described extrusion aid is 0.5-5 % by weight.
30. according to the catalyst in claim 18,28 and 29 described in any one, and wherein, described extrusion aid is starch.
31. according to the catalyst in claim 18,28 and 29 described in any one, and wherein, described extrusion aid is sesbania powder.
Catalyst in 32. claim 18-31 described in any one by ethene and carboxylic acid oxidative to prepare the application in vinyl carboxylates.
33. 1 kinds of methods preparing vinyl carboxylates, the method comprises in the presence of a catalyst, is contacted by ethene with carboxylic acid with oxygen, and to obtain the mixture containing vinyl carboxylates, wherein, described catalyst is the catalyst in claim 18-31 described in any one.
34. methods according to claim 33, wherein, described carboxylic acid is acetic acid.
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