CN103480427A - Lithium containing hydrated alumina forming material and its application, eggshell type catalyst and its preparation method and application and method for preparing vinyl carboxylates - Google Patents
Lithium containing hydrated alumina forming material and its application, eggshell type catalyst and its preparation method and application and method for preparing vinyl carboxylates Download PDFInfo
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- CN103480427A CN103480427A CN201210191977.7A CN201210191977A CN103480427A CN 103480427 A CN103480427 A CN 103480427A CN 201210191977 A CN201210191977 A CN 201210191977A CN 103480427 A CN103480427 A CN 103480427A
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Abstract
The invention provides a lithium containing hydrated alumina forming material and its application, and the lithium containing hydrated alumina forming material is prepared as follows: a forming body is prepared from raw materials comprising at least one hydrated alumina, at least one lithium containing compound and at least one cellulose ether, and then the forming body is dried at 80-180 DEG C. The invention also provides a preparation method of an eggshell type catalyst, and the lithium containing hydrated alumina forming material of the present invention is used as a carrier in the method. The invention also provides the eggshell type catalyst and its application, and the lithium containing hydrated alumina forming material of the present invention is used as the carrier of the catalyst. The invention further provides a method for preparing vinyl carboxylates. The lithium containing hydrated alumina forming material can obtain high strength and strength retention without calcination, the eggshell type catalyst carrier using the lithium containing hydrated alumina forming material as the carrier can be prepared by a routine method, and the prepared catalyst shows a higher catalytic activity in preparing the 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 Pd of usining and Au as the egg-shell catalyst of active component and the application in preparing vinyl carboxylates thereof, the invention further relates to a kind of method for preparing vinyl carboxylates.
Background technology
The catalyst (that is, lamella catalyst or egg-shell catalyst) that the active metal component shell distributes can be for multiple heterogeneous catalytic reaction.For example, hydrogenation, oxidation reaction and be subject to chemical reaction (as Fischer-Tropsch synthesis) of DIFFUSION CONTROLLED etc.
In prior art, lamella catalyst mainly loads on slaine on carrier and prepares by methods such as dipping, spraying, vapor deposition, dip-coating or precipitations.
For example, CN1306459A discloses a kind of technique for preparing the noble metal lamella catalyst with definite shell thickness on cellular ceramic substrate, this technique be by with chemical vapor deposition (CVD) method by suitable noble metal precursor with vapor phase deposition on porous carrier, become metal and noble metal be fixed on carrier by chemistry or thermal reduction afterwards.The catalyst activity metal component of this explained hereafter has the feature that shell distributes.
US4048096 discloses a kind of method for preparing lamella catalyst, the solution impregnating catalyst carrier of the compound of the compound that contains water-soluble Pd and water-soluble Au for the method, by by impregnated catalyst carrier with can form water-fast Pd with the compound reaction of the compound of described water-soluble Pd and water-soluble Au and contact (preferred sodium metasilicate) with the compound solution of Au compound, by the compound precipitation of the compound of water-insoluble Pd and water-insoluble Au to the catalyst carrier surface, then with reducing agent, the reduction of the compound of described water-insoluble Pd compound and water-insoluble Au is become to metal Pd and Au, thereby prepare and using Pd and the Au lamella catalyst as reactive metal.
CN101462079B discloses a kind of preparation method of shell distribution catalyst, the method comprises with the solution impregnating carrier containing the 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 forms, the total amount of solution of take is benchmark, the content of described surfactant is the 0.01-10 % by weight, and described dipping meets: V
l: V
c=0.01-0.99, wherein V
lfor maceration extract volume, V
cpore volume for carrier.The method adopts spray drying, and the distribution of catalyst activity metal component in carrier of preparation presents obvious shell and distribute.
CN101143325B discloses a kind of method of Kaolinite Preparation of Catalyst, the method comprises and at first preparing a kind of containing by the solution of the soluble compound of load component, afterwards by the solution spraying for preparing to the carrier rolled or load in advance on the carrier of active metal component, in the time of spraying process, carrier is heated, product drying or the roasting of making.The catalyst that adopts the method to prepare, can obtain the catalyst that obvious shell distributes.
Summary of the invention
One object of the present invention is to provide a kind of new method for preparing egg-shell catalyst, and the method is simple and easy to do; Another object of the present invention is to provide a kind of Pd of usining and the Au egg-shell catalyst as active component, and this catalyst has higher catalytic activity.
The present inventor finds in research process, prepare formed body with the raw material by containing at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether, and using described formed body the 80-180 ℃ of article shaped of carrying out drying and making as carrier, for example, will there is the active constituent loading of catalytic activity on carrier by conventional carrying method (: dipping or spraying), the catalyst of preparation has eggshell type structure (that is the active component that, has a catalytic action mainly concentrates on the surface of catalyst) thus.Completed on this basis the present invention.
It is a kind of containing the lithium hydrated alumina forming matter that a first aspect of the present invention provides, this article shaped prepares formed body by the raw material that contains at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether, and described formed body is carried out to drying and makes at 80-180 ℃.
A second aspect of the present invention provides the application of article shaped according to the present invention in preparing 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 on carrier load, and at least one has the active component of catalytic action, and wherein, described carrier is containing the 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 loads on the active component with catalytic action on described carrier, the described active component with catalytic action is Pd and Au, wherein, described carrier is provided by the invention containing the 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 with the application in preparing vinyl carboxylates.
A sixth aspect of the present invention provides a kind of method for preparing vinyl carboxylates, the method is included under the catalyst existence, ethene is contacted with oxygen with carboxylic acid, to obtain the mixture that contains vinyl carboxylates, wherein, described catalyst is catalyst provided by the invention.
Prepare formed body containing the lithium hydrated alumina forming matter with the raw material that contains at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether (described raw material is containing peptizing agent) according to according to the present invention, and described formed body is carried out to drying and makes at 80-180 ℃.Should there are good absorbent properties containing the lithium hydrated alumina forming matter; And, according to of the present invention, containing the lithium hydrated alumina forming matter, without carrying out roasting, can obtain high intensity and strength retention.
The method according to this invention is usingd the lithium hydrated alumina forming matter that contains provided by the invention as carrier, adopts this area carrying method commonly used can prepare the catalyst with eggshell type structure.
According to the Pd of usining of the present invention and Au as the egg-shell catalyst of active component for by ethene and carboxylic acid oxidative to prepare the reaction of vinyl carboxylates, demonstrate higher catalytic activity.
The specific embodiment
It is a kind of containing the lithium hydrated alumina forming matter that a first aspect of the present invention provides, this article shaped prepares formed body by the raw material that contains at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether, and described formed body is carried out to drying and makes at 80-180 ℃.Term " at least one " refers to one or more.
According to article shaped of the present invention, the raw material that contains hydrated alumina, lithium-containing compound and cellulose ether by use, do not use peptizing agent, even do not carry out high-temperature roasting, can not obtain higher intensity and good strength retention yet, also there are good absorbent properties simultaneously.In the present invention, the composition that is used to form the raw material of described article shaped can carry out suitable selection according to the concrete application scenario of the article shaped of expecting.Usually, the total amount of described raw material of take is benchmark, and the total content of described cellulose ether can be the 0.5-12 % by weight, is preferably the 1-10 % by weight, more preferably the 2-8 % by weight; With Li
2the total content of the described lithium-containing compound of O meter can be the 0.5-10 % by weight, is preferably the 0.5-8 % by weight, more preferably the 0.5-5 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be the 78-98 % by weight, is preferably the 82-98 % by weight, more preferably the 87-97 % by weight.In the present invention, while calculating the total amount of described raw material, lithium-containing compound is with Li
2the O meter, hydrated alumina is with Al
2o
3meter, and do not comprise the water of introducing in described material forming process.
In the present invention, described cellulose ether refers to after the hydrogen atom at least part of hydroxyl in cellulosic molecule is replaced by one or more alkyl that the ether formed is derivative, and wherein, a plurality of described alkyl can, for identical, can be also difference.Described alkyl is selected from alkyl and the unsubstituted alkyl of replacement.Described unsubstituted alkyl (for example: C is preferably alkyl
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 for example can for the alkyl by hydroxyl or carboxyl substituted (for example: C
1-C
5the alkyl replaced by hydroxyl, 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 kind of described cellulose ether and for the substituent quantity of the hydrogen atom on the hydroxyl of 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, described lithium-containing compound can be the compound that contains lithium atom in the commonly used various molecular structures in this area.For example, 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 select for the routine of this area.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 to prepare formed body by the raw material by containing at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether, and described formed body is made 80-180 ℃ of drying.
According to the present invention, described formed body preferably carries out drying at 100-150 ℃.The time of described drying can be carried out suitable selection according to dry temperature, and usually, the time of described drying can be 0.5-24 hour, is preferably 1-5 hour.
Can adopt this area the whole bag of tricks commonly used to prepare described formed body, be not particularly limited.For example: can be directly by hydrated alumina, cellulose ether and lithium-containing compound mixed-forming, thus obtain described formed body; Also can make preform first by hydrated alumina and cellulose ether mixed-forming, load lithium-containing compound on this preform then, thus obtain described formed body.
Of the present invention a kind of preferred embodiment in, the method that is 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 described the first mixture moulding.
In another preferred embodiment of the present invention, the method that is 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 the second mixture is successively carried out to moulding and dehydration, obtain preform, at least one lithium-containing compound of load on described preform.
In this embodiment, on described preform, the mode of at least one lithium-containing compound of load can be selected for the routine of this area, for example: can be by described preform is contacted with the solution that contains at least one lithium-containing compound, thus described lithium-containing compound is loaded on described preform.The mode that described preform is contacted with described solution can be selected for the routine of this area, for example: can described preform be contacted with the solution that contains at least one lithium-containing compound by dipping or spray, thereby described lithium-containing compound is loaded on described preform.When the mode that adopts dipping loads on described preform by described lithium-containing compound, described dipping can be saturated dipping, also can flood for supersaturation.The solvent of the described solution that contains at least one lithium-containing compound can be selected for the routine of this area, is preferably water.The concentration of the described solution that contains at least one lithium-containing compound is not particularly limited so that load on the amount of the lithium-containing compound on described preform can meet the demands (for example previously described content) be as the criterion.
In this embodiment, the condition of described dehydration is not particularly limited, and can select for the routine of this area, can remove water, is as the criterion.Usually, described dehydration can be carried out at the temperature of 80-180 ℃, preferably at the temperature of 100-150 ℃, carries out.The time of described dehydration can be carried 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, for the preparation of the consumption of the water of described the first mixture or described the second mixture, be not particularly limited, as long as the consumption of water can be guaranteed various components are mixed.
According to the present invention, the mode of described moulding is not particularly limited, and can adopt this area various molding modes commonly used, for example: extrusion, spraying, round as a ball, compressing tablet or their combination.Of the present invention a kind of preferred embodiment in, carry out moulding by the mode of extrusion.
According to the present invention, described article shaped can have various shapes according to concrete instructions for use, for example: 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 this area method commonly used to add in raw material, for example: can respectively described extrusion aid be added in above-mentioned the first mixture and the second mixture.The kind of described extrusion aid and consumption can be selected for the routine of this area.General, the total amount of described raw material of take is benchmark, and the content of described extrusion aid can be the 0.1-8 % by weight, is preferably the 0.5-5 % by weight.Preferably, described extrusion aid is starch (that is, described raw material also contains starch).Starch as extrusion aid can be the starch in various sources commonly used, this area, for example: the powder obtained through pulverizing by vegetable seeds, as the sesbania powder.
According to the present invention, the radially crushing strength loss late (that is, δ value) of described article shaped after immersion is below 10%, even can be for below 5%.
In the present invention, the δ value, for estimating the strength retention of article shaped, is defined by following formula:
Wherein, Q
1for the radially crushing strength of the article shaped without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radially crushing strength of the article shaped of 120 ℃ of dryings after 4 hours, in N/mm.
According to the present invention, the Q of described article shaped
1can, for more than 12N/mm, be even more than 15N/mm.Particularly, according to the Q of article shaped of the present invention
1can be for 15-30N/mm(as 15-25N/mm).
In the present invention, described radially crushing strength according to " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety front page, the volumes such as Yang Cuiding) in the RIPP 25-90 of record the method stipulated 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 dry article shaped soaks the ratio of weight of the article shaped of weight change value before and after 30 minutes and described drying by excessive deionized water.Concrete method of testing is: article shaped to be measured, 120 ℃ of dryings 4 hours, is then sieved with 40 purpose standard screens, take the 20g oversize and (be designated as w as testing sample
1), testing sample is soaked 30 minutes by the 50g deionized water, after filtration, solid phase is drained to 5 minutes, the weight of the solid phase that then weighing drains (is designated as w
2), calculate water absorption rate with following formula:
Not only there are good absorbent properties according to of the present invention containing the lithium hydrated alumina forming matter, and there is higher intensity and good strength retention, be suitable for the carrier as loaded catalyst.Further, adopt the catalyst prepared containing the lithium hydrated alumina forming matter comes load to have the active component of catalytic action as carrier of the present invention to there is eggshell type structure (that is the active component that, has catalytic action is concentrated the surface that is distributed in catalyst carrier).
Thus, a second aspect of the present invention provides according to of the present invention containing the application of lithium hydrated alumina forming matter in preparing 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 on carrier load, and at least one has the active component of catalytic action, and wherein, described carrier is provided by the invention above-mentioned containing the lithium hydrated alumina forming matter.
In the present invention, term " egg-shell catalyst " refers to the concentrated catalyst that is distributed in the surface of catalyst carrier of the active component with catalytic action.Usually, for egg-shell catalyst, the shell factor sigma is 0≤σ≤0.9, wherein,
c
outwardfor active component with catalytic action mean concentration at the outer surface of described catalyst, C
infor active component with catalytic action mean concentration in the center of described catalyst.Preferably, 0≤σ≤0.5; More preferably, 0≤σ≤0.1(can be for example 0.01≤σ≤0.09).
In the present invention, the shell factor is to adopt SEM and energy disperse spectroscopy (SEM-EDX) to measure the distribution of active component along the catalyst radial section, and the calculated activity component is at the ratio of mean concentration with the mean concentration of center of catalyst granules outer surface.Wherein, the mean value that the mean concentration of outer surface is 20 numerical point counting rates of outer surface; (annotate: in the SEM-EDX characterization result, along carrier, radially the counting rate of every bit is mutually corresponding with this tenor for the mean value 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).
The method according to this 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, can concentrate on for the distribution of active component on carrier that this area various needs commonly used make to have catalytic action the catalyst of the outer surface of carrier, for example various catalyst of applying in being subject to the chemical reaction of DIFFUSION CONTROLLED.
Correspondingly, the method according to this invention also is not particularly limited for described kind and load capacity with active component of catalytic action, can carry out suitable selection according to the concrete application scenario of the egg-shell catalyst prepared.
For example, at the prepared according to the methods of the invention catalyst, for making ethene and carboxylic acid carry out oxidation reaction, when preparing vinyl carboxylates, the described active component with catalytic action is preferably Pd and Au.Pd and the Au load capacity on described carrier can be carried out suitable selection according to concrete reaction condition.Preferably, Pd and the Au load capacity on described carrier makes, and the total amount of catalyst of preparation of take is benchmark, and the content of described carrier can be the 96-99.5 % by weight, is preferably the 96.8-99 % by weight; In element, the content of Pd can be the 0.1-2.5 % by weight, is preferably the 0.2-2 % by weight; The content of Au can be the 0.1-1.5 % by weight, is preferably the 0.2-1.2 % by weight.
The method according to this invention, can adopt this area the whole bag of tricks commonly used to have the active constituent loading of catalytic action on described carrier by described.Usually, on carrier, at least one mode with active component of catalytic action of load comprises: described carrier is contacted with containing at least one solution containing the compound of the described active component with catalytic action, and remove load and have the solvent on the carrier of described compound.Can adopt this area variety of way commonly used that described carrier contact with containing at least one solution containing the compound of the described active component with catalytic action, as dipping or spray.When the mode that adopts dipping realizes described contact, described dipping can be saturated dipping, can be also excessive dipping.Described at least one concentration containing the solution of the compound of the described active component with catalytic action that contains can be that the routine of this area is selected, and can meet concrete instructions for use with the content of the active component that has catalytic action described in the catalyst that can make final preparation and be as the criterion.Described at least one solvent containing the solution of the compound of the described active component with catalytic action that contains is not particularly limited, and can be this area various solvents commonly used.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, the condition that removes load and have the solvent on the carrier of described compound can comprise: temperature can be 100-200 ℃; Time can be 1-15 hour.
The method according to this invention, during the active component that is two or more in the described active component with catalytic action, can be simultaneously by the described active constituent loading with catalytic action on described carrier, also can gradation there is the active constituent loading of catalytic action on described carrier by described.
Particularly, when the described active component with catalytic action is Pd and Au, the method according to this invention can comprise: will under reducing condition, can form metal Pd (, the Pd that valence state is 0) containing the Pd compound and can form metal A u(under reducing condition, the Au that valence state is 0) containing Au compound loaded on described carrier.Can adopt this area the whole bag of tricks commonly used by described under reducing condition, can form metal Pd containing the Pd compound and under reducing condition, can form metal A u containing Au compound loaded on described carrier.
The method according to this invention a kind of preferred embodiment in, by described under reducing condition, can form metal Pd containing the Pd compound and can form metal A u under reducing condition containing the compound loaded mode on described carrier of Au be: on described carrier, load contains at least one containing water soluble compound of Pd and at least one water soluble compound containing Au, there is the described water soluble compound containing Pd to contact with precipitating reagent with the carrier of the water soluble compound that contains Au load, and remove the solvent on carrier.
Described water soluble compound containing Pd and the routine that can be this area separately containing the water soluble compound of Au are selected, and for example: the described water soluble compound containing Pd can be selected from palladium bichloride, palladium, palladium nitrate and the acid of 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.
Can adopt this area the whole bag of tricks commonly used to load on described carrier by described water soluble compound containing Pd with containing the water soluble compound of Au, for example: can be by described carrier contact containing water soluble compound of Pd and at least one aqueous solution containing the water soluble compound of Au with containing at least one, thus the water soluble compound of the described Pd of containing and the water soluble compound that contains Au are loaded on described carrier.By described carrier, with containing at least one water soluble compound containing Pd, with at least one mode contacted containing the aqueous solution of the water soluble compound of Au, can be the routine selection of this area, for example: dipping or spray, be preferably dipping (as saturated dipping or excessive dipping), more preferably saturated dipping.
Described precipitating reagent can be for this area various materials that can make the described water soluble compound containing Pd and form precipitation containing the water soluble compound of Au commonly used, 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, can make whole or basic all described water soluble compounds containing Pd and the described water soluble compound containing Au formation precipitation, is as the criterion.
Can adopt this area the whole bag of tricks commonly used to have the described water soluble compound containing Pd to contact with precipitating reagent with the carrier of the water soluble compound that contains Au load, for example: precipitating reagent can be mixed with to the aqueous solution, and flood (being preferably saturated dipping) or spray the carrier that described load has the described water soluble compound containing Pd and contains the water soluble compound of Au with this aqueous solution.The temperature and time of described contact can be selected for the routine of this area, can make whole or basic all described water soluble compounds containing Pd and the described water soluble compound containing Au formation precipitation, is as the criterion.
In this embodiment, described solvent is preferably water.The present invention is not particularly limited for the condition that removes the solvent on carrier, being as the criterion by desolvation.Usually, the condition that removes described solvent comprises: temperature can be 100-200 ℃; Time can be 1-15 hour.
In addition, the Pd(that is reduction-state in the active component with catalytic action for example, the Pd that valence state is 0) and the Au(of reduction-state for example, the Au that valence state is 0) time, the method according to this invention also comprises: under reductive condition, the carrier that has removed solvent is contacted with reducing agent.
According to the present invention, can the reductive condition commonly used in this area under, will load on contact with reducing agent containing the Pd compound with containing the Au compound on described carrier, with by described contain the Pd compound and contain the Au compound reduce separately and become metal Pd and metal A u.Described reducing agent can for commonly used various in this area can be described for example, containing Pd compound and the reducing agent that reduces containing the Au compound: hydrogen, carbon monoxide or hydrogen sulfide.Described reductive condition can carry out suitable selection according to the kind of described reducing agent, and for example: when using hydrogen as reducibility gas, described reductive condition can comprise: temperature can be 300-500 ℃; Time can be 1-8 hour.
The method according to this invention, as the case may be, can also be included on described carrier and introduce at least one auxiliary element.
For example, when the described active component with catalytic action is Pd and Au, the method according to this invention is preferably introduced at least one following auxiliary element: K, La, Ce, Cr, V, B, Mn, Re, Pt, Ru, Ba and Ca on described carrier.The introduction volume of above-mentioned auxiliary element on described carrier can be carried out suitable selection according to the concrete application scenario of the catalyst of final preparation.Usually, the introduction volume of described auxiliary element on described carrier makes, and the total amount of catalyst of preparation of take is benchmark, and in element, the total content of described auxiliary element can be the 0.1-5 % by weight, is preferably the 0.3-1 % by weight.
Can adopt this area the whole bag of tricks commonly used to introduce auxiliary element on described carrier.For example, can be by introducing described auxiliary element in the process at the described carrier of preparation, also can be by described carrier is contacted with containing at least one solution that contains the compound of described auxiliary element, thus introduce auxiliary element on described carrier.
The mode of introducing described auxiliary element in the process of the described carrier of preparation can comprise: at least one compound containing described auxiliary element and at least one hydrated alumina, at least one cellulose ether and at least one optional lithium-containing compound are mixed, by the mixture moulding obtained, and carry out drying at 80-180 ℃ (preferably 100-150 ℃), prepare the carrier that contains described auxiliary element.
By by described carrier with contain at least one solution containing the compound of described auxiliary element and contact, thereby while on described carrier, introducing auxiliary element, described auxiliary element can be loaded on described carrier in load P d and Au, also can Pd, Au and described auxiliary element be loaded on described carrier gradation.
The described compound containing auxiliary element can be this area various water soluble compounds containing described auxiliary element commonly used.For example, 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 loads on the active component with catalytic action on described carrier, the described active component with catalytic action is Pd and Au, wherein, described carrier is provided by the invention containing the lithium hydrated alumina forming matter.
According to egg-shell catalyst of the present invention, as the active component Pd with catalytic action and Au, can with the form of oxidation state, be loaded on carrier, also can be loaded on carrier with the form of reduction-state (that is, valence state is for 0).When the form with oxidation state is loaded on carrier, before use can be by contacting with reducing agent under reductive condition and by described active component reduction according to egg-shell catalyst of the present invention.
According to egg-shell catalyst of the present invention, Pd and the Au load capacity on described carrier can be carried out suitable selection according to the concrete application scenario of described catalyst.Usually, the total amount of described catalyst of take is benchmark, and the content of described carrier can be the 96-99.5 % by weight, is preferably the 96.8-99 % by weight; In element, the content of Pd can be the 0.1-2.5 % by weight, is preferably the 0.2-2 % by weight; The content of Au can be the 0.1-1.5 % by weight, is preferably the 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, is preferably 0≤σ≤0.5, and more preferably 0≤σ≤0.1(can be for example 0.01≤σ≤0.09).
According to egg-shell catalyst of the present invention, angle from the catalytic activity of further raising catalyst according to the invention, this catalyst preferably also contains at least one auxiliary element loaded on described 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.The total amount of described catalyst of take is benchmark, and in element, the total content of described auxiliary element can be the 0.1-5 % by weight, is preferably the 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.According to egg-shell catalyst of the present invention, for example can adopt the previously described method for preparing egg-shell catalyst to make, be not described in detail in this.
Be particularly suitable for the catalyst when by ethene and carboxylic acid, by oxidation reaction, preparing vinyl carboxylates according to the Pd of usining of the present invention and Au as the egg-shell catalyst of active component.
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 with the application in preparing vinyl carboxylates.
A sixth aspect of the present invention provides a kind of method for preparing vinyl carboxylates, the method is included under the catalyst existence, ethene is contacted with oxygen with carboxylic acid, to obtain the mixture that contains vinyl carboxylates, wherein, described catalyst is catalyst provided by the invention.
The method for 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, for other condition for preparing vinyl carboxylates, is not particularly limited, and can select for the routine of this area.
Usually, described carboxylic acid can form the various organic acids of vinyl carboxylates for what this area was commonly used by oxidation reaction with ethene, for example: the various straight or branched organic carboxyl acids that carbon number is 2-10.Particularly, described carboxylic acid can for 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.The method according to this invention is specially adapted to prepare vinyl acetate by ethene and acetic acid and oxygen reaction.
The method according to this invention, the ratio between ethene, described carboxylic acid and oxygen can be selected for the routine of this area.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.
The method according to this invention, the consumption of described catalyst can carry out suitable selection according to concrete reaction condition, can realize that catalysis is as the criterion.
The method according to this invention is not particularly limited ethene with the condition that carboxylic acid contacts with oxygen, can access the mixture that contains vinyl carboxylates, be as the criterion.For example, described condition comprises: temperature can be 100-200 ℃, is preferably 120-180 ℃; In gauge pressure, pressure can be 0.5-1.5MPa, is preferably 0.8-1.2MPa.
The method according to this invention can also comprise from described mixture isolates vinyl carboxylates.The present invention is not particularly limited for the method for separating, and can select for the routine of this area, and this paper repeats no more.
Describe the present invention in detail below in conjunction with embodiment and Comparative Examples.
In following examples and Comparative Examples, adopt the method for stipulating in RIPP 25-90 to measure the radially crushing strength of article shaped.
In following examples and Comparative Examples, adopt following methods to measure the δ value of article shaped: the radially crushing strength that the method for stipulating in employing RIPP25-90 is measured without the article shaped of water soaking (is designated as Q
1); Article shaped is placed in to the 50g deionized water, soaks 30 minutes, then filter, by the solid that obtains at the temperature of 120 ℃ dry 4 hours, the radially crushing strength of measuring dry solid according to the method for stipulating in RIPP 25-90 (was designated as Q
2), adopt following formula to calculate the δ value,
In following examples and Comparative Examples, adopt following methods to measure the water absorption rate of article shaped: article shaped to be measured, 120 ℃ of dryings 4 hours, then to be sieved with 40 purpose standard screens, take the 20g oversize and (be designated as w as testing sample
1), testing sample is soaked 30 minutes by the 50g deionized water, after filtration, solid phase is drained to 5 minutes, the weight of the solid phase that then weighing drains (is designated as w
2), calculate water absorption rate with following formula:
In following examples and Comparative Examples, contents on dry basis is by measuring testing sample in 4 hours 600 ℃ of roastings.
In following examples and Comparative Examples, by the x ray fluorescence spectrometry, (that is, XRF) measure the content of active component in catalyst.
In following examples and Comparative Examples, adopt SEM-EDX to measure the distribution of active component along the catalyst radial section, the calculated activity component is at the ratio of mean concentration with the mean concentration of center of catalyst granules outer surface.Wherein, the mean value that the mean concentration of outer surface is 20 numerical point counting rates of outer surface; (annotate: in the SEM-EDX characterization result, along carrier, radially the counting rate of every bit is mutually corresponding with this tenor for the mean value 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 is for illustrating according to of the present invention containing the lithium hydrated alumina forming matter.
Embodiment 1
Follow and stir 5.0g LiNO
3be dissolved in the 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 sea, Zhejiang Shen chemical industry Co., Ltd), 3.0g sesbania powder and above-mentioned even containing the lithium aqueous solution.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar of extruding is placed in to baking oven, 150 ℃ of dryings 12 hours, thereby obtains according to of the present invention containing the lithium hydrated alumina forming matter.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Comparative Examples 1
Follow and stir 5.0g LiNO
3be dissolved in the 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 even containing the lithium aqueous solution.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar of extruding is placed in to baking oven, 150 ℃ of dryings 12 hours, then 600 ℃ of roastings 4 hours, thereby obtains article shaped.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Comparative Examples 2
Adopt the method identical with Comparative Examples 1 to prepare article shaped, different, at 600 ℃, do not carry out roasting, thereby obtain article shaped.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Comparative Examples 3
Adopt the method identical with embodiment 1 to prepare article shaped, different, in step (1), the wet bar of extruding is placed in to baking oven, 150 ℃ of dryings 1 hour, then 500 ℃ of roastings 3 hours, thereby obtain article shaped.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 2
(1) in the retort of a 2L, take and the stream mode adds aluminum sulfate solution that 2000mL concentration is 48g/L and sodium aluminate solution (alumina content is 200g/L, the causticity coefficient is 1.58) carry out precipitation reaction, reaction temperature is 50 ℃, and the pH value is 6.0, and reaction time is 15 minutes; The slurries that obtain are filtered with vacuum filter, after to be filtered completing, on filter cake, supplement and add 20L deionized water (temperature is 40 ± 5 ℃) flush cake approximately 60 minutes.Filter cake after washing is joined to the 1.5L deionized water for stirring and become slurries, slurries are carried out to drying with being pumped into spray dryer, control the outlet temperature of spray dryer within the scope of 100-110 ℃, the dry materials time is 2 minutes, obtain hydrated alumina, wherein, alumina content is 63 % by weight, through XRD analysis, is defined as amorphous state.
(2) follow and stir 3.0g LiNO
3be dissolved in the 95mL deionized water and obtain containing the lithium aqueous solution.Unformed hydrated alumina prepared by 50.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 50.0g step (1), 2.0g methylcellulose (purchased from sea, Zhejiang Shen chemical industry 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 extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 100 ℃ of dryings 12 hours, thereby obtains according to of the present invention containing the lithium hydrated alumina forming matter.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 3
Follow at the temperature that is stirred in 60 ℃, the 9.8g lithium oxalate is dissolved in the 95mL deionized water, prepare containing the lithium aqueous solution.By the 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 sea, Zhejiang Shen chemical industry Co., Ltd), 2.0g hydroxypropyl methylcellulose (purchased from sea, Zhejiang Shen chemical industry Co., Ltd), 3.0g sesbania powder and above-mentionedly containing the lithium aqueous solution, stir.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 80 ℃ of dryings 12 hours, thereby obtains according to of the present invention containing the lithium hydrated alumina forming matter.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Comparative Examples 4
Adopt the method identical with embodiment 3 to prepare article shaped, different, in step (1), the wet bar obtained is placed in to baking oven, 60 ℃ of dryings 12 hours, thereby obtain article shaped.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 4
Follow to stir the 2.0g lithium acetate is dissolved in the 90mL deionized water, prepare 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 extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 150 ℃ of dryings 12 hours, thereby obtains according to of the present invention containing the lithium hydrated alumina forming matter.The radially crushing strength of the article shaped that mensuration obtains, 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, 6.0g LiNO
3with 90mL water, mix.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 180 ℃ of dryings 4 hours, thereby obtains according to of the present invention containing the lithium hydrated alumina forming matter.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Comparative Examples 5
Adopt the method identical with embodiment 5 preparation containing the lithium hydrated alumina forming matter, different, the bar that will wet is 200 ℃ of dryings 4 hours, thereby obtains containing the lithium hydrated alumina forming matter.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 6
At the temperature of 50 ℃, follow and stir 8.0g LiNO
3be dissolved in the 90mL deionized water, prepare containing the lithium aqueous solution.By 100.0g boehmite (purchased from Yantai, Shandong permanent brightness chemical industry 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 even containing the lithium aqueous solution.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 120 ℃ of dryings 4 hours, thereby obtains according to of the present invention containing the lithium hydrated alumina forming matter.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 7
Adopt the method preparation identical with embodiment 2 containing the lithium hydrated alumina forming matter, different, the content of methylcellulose is 4.0g, thereby obtains according to of the present invention containing the lithium hydrated alumina forming matter.The radially crushing strength of the article shaped that mensuration obtains, 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 sea, Zhejiang Shen chemical industry Co., Ltd) and 3.0g sesbania powder are mixed.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar of extruding is placed in to baking oven, 150 ℃ of dryings 12 hours.At the temperature of 50 ℃, follow and stir 8.0g LiNO
3be dissolved in the 90mL deionized water, prepare containing the lithium aqueous solution.Take 50.0g shaping and drying bar, put into above-mentionedly containing the lithium aqueous solution, soak after 4 hours and filter, 120 ℃ of dryings 6 hours, thereby obtain according to of the present invention containing the lithium hydrated alumina forming matter.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 9
Adopt the method identical with embodiment 5 to prepare article shaped, different, the wet bar obtained is placed in to baking oven, 150 ℃ of dryings 4 hours, thereby obtain according to of the present invention containing the lithium hydrated alumina forming matter.The radially crushing strength of the article shaped that mensuration obtains, 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 Examples 1 | 26.1 | 0.84 | 1.9 |
| Comparative Examples 2 | 21.6 | 0.64 | 64.6 |
| Comparative Examples 3 | 24.2 | 0.76 | 3.3 |
| Embodiment 2 | 22.3 | 0.63 | 3.1 |
| Embodiment 3 | 16.7 | 0.68 | 4.8 |
| Comparative Examples 4 | 13.4 | 0.55 | 24.6 |
| Embodiment 4 | 22.1 | 0.66 | 2.3 |
| Embodiment 5 | 23.0 | 0.57 | 3.2 |
| Comparative Examples 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 presentation of results of table 1, have good absorbent properties, higher intensity and strength retention according to of the present invention containing the lithium hydrated alumina forming matter, is suitable for the carrier as loaded catalyst.
Embodiment 10-18 is for illustrating according to the preparation method of lithium hydrated alumina forming matter at the application for preparing egg-shell catalyst and egg-shell catalyst that contain of the present invention.
Embodiment 10
By 1.19g Na
2pdCl
4with 0.37g HAuCl
4mix with water, be mixed with the 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 is obtained is placed in the aqueous solution that 20mL contains 1.5g NaOH, at room temperature standing 8 hours, uses deionized water rinsing after filtering, until do not contain Cl in washing lotion
-till.Then by the solid phase that obtains in 120 ℃ of dryings 2 hours, then at 500 ℃ with hydrogen reducing 3 hours.After being cooled to room temperature, the solid phase obtained containing the aqueous solution of 0.22g KOAc dipping with 31.5mL 30 minutes, after filtration, by the solid phase that obtains in 80 ℃ of dryings 4 hours, thereby obtain catalyst according to the invention C1, characterization result is shown in table 2.
Comparative Examples 6
By 1.19g Na
2pdCl
4with 0.37g HAuCl
4mix with water, be mixed with the 29.5mL dipping solution, with the carrier (diameter is 1.1mm, and particle length is 2-5mm) of this solution impregnation 35.1g Comparative Examples 1 preparation, dip time is 5 minutes.The carrier obtained is placed in to the solution that 20mL contains 1.5g NaOH, under room temperature standing 8 hours, uses deionized water rinsing after filtering, until do not contain Cl in washing lotion
-till.Then by the solid phase that obtains in 120 ℃ of dryings 2 hours, then at 500 ℃ with hydrogen reducing 3 hours.After being cooled to room temperature, the solid phase obtained containing the aqueous solution of 0.22g KOAc dipping with 29.5mL 30 minutes, after filtration, by the solid phase that obtains in 80 ℃ of dryings 4 hours, thereby obtain catalyst A 1, characterization result is in Table 2.
Comparative Examples 7
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 10, different, the carrier that carrier is Comparative Examples 2 preparations, in dipping process, the phenomenon of dissolving and structure is caved in appears in carrier, the catalyst A 2 obtained can't be used as preformed catalyst.
Comparative Examples 8
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 10, different, the carrier (diameter is 1.1mm, and particle length is 2-5mm) that carrier is Comparative Examples 3 preparations, thus obtaining catalyst A 3, characterization result is in Table 2.
Embodiment 11
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 10, different, the carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 71.3 % by weight) that carrier is embodiment 2 preparations, thus obtaining catalyst C2, characterization result is in Table 2.
Embodiment 12
By 1.80g Na
2pdCl
4with 0.56g HAuCl
4mix with water, be mixed with the 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 preparations, dip time is 5 minutes.The carrier that dipping is obtained is placed in the solution that 20mL contains 1.5g NaOH, and standing 8h under room temperature, after filtration, use deionized water rinsing, until do not contain Cl in washing lotion
-till.Then by the solid phase that obtains in 120 ℃ of dryings 2 hours, then at 500 ℃ with hydrogen reducing 3 hours.After being cooled to room temperature, the solid phase obtained containing the aqueous solution of 0.33g KOAc dipping with 37.5mL 30 minutes.After filtration, by the solid phase that obtains in 80 ℃ of dryings 4 hours, thereby obtain catalyst according to the invention C3, characterization result is in Table 2.
Comparative Examples 9
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 12, different, the carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 66.4 % by weight) that carrier is Comparative Examples 4 preparations, thus obtaining catalyst A 4, characterization result is shown in table 2.
Embodiment 13
By 1.19g Na
2pdCl
4with 0.37g HAuCl
4mix with water, be mixed with the 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 preparations, dip time is 5 minutes.After filtration, the solid phase obtained is placed in to the solution that 20mL contains 1.5g NaOH, under room temperature standing 8 hours.After filtration, by the solid phase deionized water rinsing obtained, until do not contain Cl in washing lotion
-till.By the solid phase that obtains in 150 ℃ of dryings 2 hours, then at 500 ℃ 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
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 10, different, (diameter is 1.1mm to the carrier that carrier is embodiment 5 preparations, particle length is 2-5mm, contents on dry basis is 76.8 % by weight), thus catalyst according to the invention C5 obtained, and characterization result is shown in table 2.
Comparative Examples 10
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 10, different, the carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 80.2 % by weight) that carrier is Comparative Examples 5 preparations, thus obtaining catalyst A 5, characterization result is shown in table 2.
Embodiment 15
By 0.60g Na
2pdCl
4with 0.19g HAuCl
4mix with water, be mixed with the 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 preparations, dip time is 5 minutes.After filtration, the solid phase obtained is placed in to the solution that 20mL contains 1.5g NaOH, under room temperature standing 8 hours.After filtration, by the solid phase deionized water rinsing obtained, until do not contain Cl in washing lotion
-till.By the solid phase after washing in 120 ℃ of dryings 2 hours, then at 500 ℃ with hydrogen reducing 3 hours.After being cooled to room temperature, the solid phase obtained is flooded 30 minutes containing the aqueous solution of 0.11g KOAc with 33.5mL.After filtration, by the solid phase that obtains in 80 ℃ of dryings 4 hours, thereby obtain catalyst according to the invention C6, characterization result is shown in table 2.
Embodiment 16
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 11, different, (diameter is 1.1mm to the carrier that carrier is embodiment 7 preparations, particle length is 2-5mm, contents on dry basis is 71.2 % by weight), thus catalyst according to the invention C7 obtained, and characterization result is listed in table 2.
Embodiment 17
The catalyst that adopts the method identical with embodiment 10 to prepare, different, (diameter is 1.1mm to the carrier that carrier is embodiment 8 preparations, particle length is 2-5mm, contents on dry basis is 73.4 % by weight), thus catalyst according to the invention C8 obtained, and characterization result is listed in table 2.
Embodiment 18
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 10, different, (diameter is 1.1mm to the carrier that carrier is embodiment 9 preparations, particle length is 2-5mm, contents on dry basis is 75.5 % by weight), thus catalyst according to the invention C9 obtained, and characterization result is listed in table 2.
Embodiment 19-27 is for illustrating the application of catalyst according to the invention and the method for preparing vinyl carboxylates.
Embodiment 19-27
The catalytic performance of the catalyst that respectively prepared by Evaluation operation example 10-18 on fixed bed reactors.Wherein, raw material is ethylene/acetic acid/oxygen=82/12/6(mol ratio), catalyst volume is 30mL, the volume space velocity of ethene is 2.5h
-1.
Reaction condition comprises: temperature is 140 ℃, reactor inlet pressure 1MPa.
The mixture that reaction obtains is measured it with gas chromatography and is formed, and calculates the conversion ratio of ethene by following formula, and result is listed in table 2.
Comparative Examples 11-14
Adopt the method identical with embodiment 19-27 to carry out the performance of evaluate catalysts, different, catalyst is respectively catalyst prepared by Comparative Examples 6 and 8-10, and result is listed in table 2.
Table 2
The result of table 2 shows, usings and containing the lithium hydrated alumina forming matter, as carrier, adopts conventional method load to have the active component of catalytic action according to of the present invention, can prepare active component and be the catalyst that eggshell type distributes; And, catalyst according to the invention by ethene and carboxylic acid oxidative with the reaction for preparing vinyl carboxylates in, show higher catalytic activity.
Claims (21)
1. one kind containing the lithium hydrated alumina forming matter, and this article shaped prepares formed body by the raw material that contains at least one hydrated alumina, at least one lithium-containing compound and at least one cellulose ether, and described formed body is carried out to drying and makes at 80-180 ℃.
2. article shaped according to claim 1, wherein, the temperature of described drying is 100-150 ℃.
3. article shaped according to claim 1, wherein, the total amount of described raw material of take is benchmark, the total content of described cellulose ether is the 0.5-12 % by weight, with Li
2the total content of the described lithium-containing compound of O meter is the 0.5-10 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 78-98 % by weight.
4. article shaped according to claim 3, wherein, the total amount of described raw material of take is benchmark, the total content of described cellulose ether is the 2-8 % by weight, with Li
2the total content of the described lithium-containing compound of O meter is the 0.5-5 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 87-97 % by weight.
5. according to the described article shaped of any one in claim 1,3 and 4, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
6. according to the described article shaped of any one in claim 1,3 and 4, wherein, described lithium-containing compound is selected from lithium nitrate, lithium sulfate, lithium chloride, lithium oxalate and lithium acetate;
Described hydrated alumina is selected from boehmite, gibbsite, unformed hydrated alumina and boehmite.
7. according to the described article shaped of any one in claim 1-4, wherein, the water absorption rate of described article shaped is 0.4-1.5, and the δ value is below 10%, Q
1more than 12N/mm,
Wherein,
Q
1for the radially crushing strength of the carrier without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radially crushing strength of the carrier of 120 ℃ of dryings after 4 hours, in N/mm.
8. article shaped according to claim 7, wherein, the water absorption rate of described article shaped is 0.6-1, the δ value is below 5%, Q
1for 15-30N/mm.
9. the application of the described article shaped of any one in preparing egg-shell catalyst in claim 1-8.
10. the preparation method of an egg-shell catalyst, the method is included on carrier load, and at least one has the active component of catalytic action, it is characterized in that, and described carrier is that in claim 1-8, any one is described containing the lithium hydrated alumina forming matter.
11. method according to claim 10, wherein, on carrier, at least one mode with active component of catalytic action of load comprises: described carrier is contacted with containing at least one solution containing the compound of the described active component with catalytic action, and remove load and have the solvent on the carrier of described compound.
12. method according to claim 11, wherein, the condition that removes load and have the solvent on the carrier of described compound comprises: temperature is 100-200 ℃; Time is 1-15 hour.
13., according to the described method of claim 10 or 11, wherein, the described active component with catalytic action is Pd and Au.
14. method according to claim 13, wherein, the described load capacity of active component on described carrier with catalytic action makes, the total amount of catalyst of preparation of take is benchmark, the content of described carrier is the 96-99.5 % by weight, in element, the content of Pd is the 0.1-2.5 % by weight, and the content of Au is the 0.1-1.5 % by weight.
15. according to the described method of claim 13 or 14, wherein, the method also is included on described carrier introduces at least one auxiliary element, described auxiliary element is selected from K, La, Ce, Cr, V, B, Mn, Re, Pt, Ru, Ba and Ca, the introduction volume of described auxiliary element on described carrier makes, the total amount of catalyst of preparation of take is benchmark, and in element, the total content of described auxiliary element is the 0.1-5 % by weight.
A 16. egg-shell catalyst, this catalyst contains carrier and loads on the active component with catalytic action on described carrier, the described active component with catalytic action is Pd and Au, it is characterized in that, described carrier is that in claim 1-8, any one is described containing the lithium hydrated alumina forming matter.
17. catalyst according to claim 16, wherein, the total amount of described catalyst of take is benchmark, and the content of described carrier is the 96-99.5 % by weight, and in element, the content of Pd is the 0.1-2.5 % by weight, and the content of Au is the 0.1-1.5 % by weight.
18. according to the described catalyst of claim 16 or 17, wherein, this catalyst also contains at least one auxiliary element loaded on described carrier, described auxiliary element is selected from K, La, Ce, Cr, V, B, Mn, Re, Pt, Ru, Ba and Ca, the total amount of described catalyst of take is benchmark, in element, the total content of described auxiliary element is the 0.1-5 % by weight.
19. in claim 16-18 the described catalyst of any one by ethene and carboxylic acid oxidative with the application in preparing vinyl carboxylates.
20. a method for preparing vinyl carboxylates, the method is included under the catalyst existence, and ethene is contacted with oxygen with carboxylic acid, and to obtain the mixture that contains vinyl carboxylates, wherein, described catalyst is the described catalyst of any one in claim 16-18.
21. method according to claim 20, wherein, described carboxylic acid is acetic acid.
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| CN101722044A (en) * | 2008-10-15 | 2010-06-09 | 赢创德固赛有限责任公司 | Load catalyst used for preparing vinyl acetate monomer |
| CN101722006A (en) * | 2009-11-24 | 2010-06-09 | 山东齐鲁科力化工研究院有限公司 | Dual-functional hydrogenation catalyst |
| CN102015103A (en) * | 2007-05-31 | 2011-04-13 | 南方化学股份公司 | Doped Pd/Au shell catalyst, method for producing the same and use thereof |
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| CN1566270A (en) * | 2003-06-30 | 2005-01-19 | 中国石油化工股份有限公司 | Hydrocarbon oil cracking process for more light oil |
| CN101066530A (en) * | 2006-05-22 | 2007-11-07 | 林方 | Hydrodemetalizing catalyst and its prepn |
| CN102015103A (en) * | 2007-05-31 | 2011-04-13 | 南方化学股份公司 | Doped Pd/Au shell catalyst, method for producing the same and use thereof |
| CN101722044A (en) * | 2008-10-15 | 2010-06-09 | 赢创德固赛有限责任公司 | Load catalyst used for preparing vinyl acetate monomer |
| CN101722006A (en) * | 2009-11-24 | 2010-06-09 | 山东齐鲁科力化工研究院有限公司 | Dual-functional hydrogenation catalyst |
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