CN103480339B - Hydrated alumina forming matter and preparation method thereof and aluminium oxide article shaped and their application - Google Patents
Hydrated alumina forming matter and preparation method thereof and aluminium oxide article shaped and their application Download PDFInfo
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- CN103480339B CN103480339B CN201210193378.9A CN201210193378A CN103480339B CN 103480339 B CN103480339 B CN 103480339B CN 201210193378 A CN201210193378 A CN 201210193378A CN 103480339 B CN103480339 B CN 103480339B
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Abstract
The invention provides a kind of hydrated alumina forming matter and its preparation method and application, this article shaped is made containing the compound of rare earth element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one, the water absorption rate of this article shaped is 0.4-1.5, δ value is less than 10%, Q
1for more than 12N/mm.Present invention also offers a kind of aluminium oxide article shaped and application thereof, hydrated alumina forming matter of the present invention is carried out roasting and makes by this aluminium oxide article shaped.Article shaped of the present invention has high intensity and good strength retention.According to method of the present invention, in forming process, do not use peptizing agent.
Description
Technical field
The present invention relates to a kind of hydrated alumina forming matter and its preparation method and application, the invention still further relates to a kind of aluminium oxide article shaped and application thereof.
Background technology
Aluminium oxide, particularly gama-alumina, because it has good pore structure and heat-resistant stability, and higher specific area, therefore aluminium oxide article shaped is commonly used for the carrier of drier or loaded catalyst.Modulation can be carried out to the character of aluminium oxide, with the requirement making it meet specific occasion by introducing metallic element in aluminium oxide article shaped.Such as, adopt the aluminium oxide article shaped containing rare earth element to prepare Hydrobon catalyst as carrier, modulation can be carried out to the hydrofinishing performance of catalyst.
Aluminium oxide article shaped containing rare earth element can by mixing hydrated alumina with water, peptizing agent and optional extrusion aid, and mixture is successively carried out shaping, dry and high-temperature roasting and obtains aluminium oxide article shaped, then with containing rare earth element compound dip forming thing and then carry out drying and roasting and obtain; Can also by mix by hydrated alumina with containing the compound of rare earth element with water, peptizing agent and optional extrusion aid, mixture priority carried out shaping, drying and high-temperature roasting and obtain.
Drying and without high-temperature roasting article shaped (namely, hydrated alumina forming matter) when the carrier being used as loaded catalyst is had the active component of catalytic action by the method load of dipping or is used as drier, be easy to dissolve, phenomenon that efflorescence and duct cave in, thus make article shaped lose shape, therefore only drying and article shaped without high-temperature roasting can not directly as drier or as dipping carrier, the process that must experience a high-temperature roasting just can as drier or as dipping carrier.
And; usual use acid (such as: nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid) is as peptizing agent; the existence of acid is easy to corrode former on the one hand; a large amount of sour gas is discharged on the other hand in drying and roasting process; both unfavorable to the health of operating personnel, be also unfavorable for environmental protection.
Summary of the invention
The object of the invention is to overcome prior art and must use peptizing agent when preparing aluminium oxide article shaped, and the technical problem that unfired hydrated alumina forming matter strength retention is low.The invention provides a kind of hydrated alumina forming matter, this hydrated alumina forming matter has good strength retention, even if carry out the phenomenon that long-time immersion also can not or there will not be dissolving, efflorescence and duct to cave in substantially in the solution; Present invention also offers a kind of method preparing aluminium oxide article shaped, the method does not use peptizing agent.
The present inventor finds in research process, hydrated alumina forming matter without high-temperature roasting is easy to occur dissolving in adsorption process and in dipping process, efflorescence and duct cave in, and then the reason losing shape may be: the hydrated alumina forming matter without high-temperature roasting contains peptizing agent, the Main Function of described peptizing agent be make as raw material various powder adhesion together, but in absorption and dipping process, because peptizing agent dissolves, run off in a large number from article shaped, and then make article shaped occur dissolving, efflorescence and duct cave in phenomenon, final forfeiture shape.
The present inventor is through further investigation, find: in the forming process of hydrated alumina, do not use peptizing agent, introduce cellulose ether simultaneously, even if the article shaped of preparation like this does not carry out high-temperature roasting, also have good strength retention, even if carry out the phenomenon that long-time dipping also can not or there will not be dissolving, efflorescence and hole to cave in substantially in maceration extract, and this article shaped also has good absorbent properties.This completes the present invention.
A first aspect of the present invention provides a kind of hydrated alumina forming matter, this article shaped is made containing the compound of rare earth element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one, the water absorption rate of this 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 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.
A second aspect of the present invention provides a kind of method preparing hydrated alumina forming matter, the method comprises to be prepared formed body containing the compound of rare earth element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one, and described formed body is carried out drying.
A third aspect of the present invention provides a kind of hydrated alumina forming matter prepared by method of the present invention.
A fourth aspect of the present invention provides a kind of according to the application as drier or the carrier as loaded catalyst of hydrated alumina forming matter of the present invention or aluminium oxide article shaped.
According to hydrated alumina forming matter of the present invention not containing peptizing agent (such as: Alumina gel, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid), there is good strength retention, even if carry out the phenomenon that long-time dipping also can not or there will not be dissolving, efflorescence and duct to cave in substantially in maceration extract.Thus, namely hydrated alumina forming matter according to the present invention can be used as drier or the carrier as loaded catalyst without the need to high-temperature roasting.Aluminium oxide article shaped of the present invention is made by hydrated alumina forming matter of the present invention is carried out roasting, not only has good absorbent properties, but also has high intensity and strength retention.
Particularly, radial crushing strength according to hydrated alumina forming matter of the present invention and aluminium oxide article shaped can reach more than 12N/mm respectively, water absorption rate can reach 0.4-1.5 % by weight, δ value (that is, the crushing strength loss late after immersion) respectively can be respectively less than 10%.
According to method of the present invention, do not use peptizing agent (that is, described raw material is not containing peptizing agent) in forming process, decrease the corrosion to former on the one hand, extend the service life of former, reduce production cost; Greatly reduce the amount of the sour gas discharged in dry and roasting process on the other hand, reduce the impact on operator ' s health, also help environmental protection simultaneously.
Detailed description of the invention
A first aspect of the present invention provides a kind of hydrated alumina forming matter, and described article shaped is made containing the compound of rare earth element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one.Term " at least one " refers to one or more.
According to hydrated alumina forming matter of the present invention, described raw material contains hydrated alumina, containing the compound of rare earth element and cellulose ether, not containing peptizing agent (such as: Alumina gel, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid), the hydrated alumina forming matter made has good strength retention, also has good absorbent properties simultaneously.
According to hydrated alumina forming matter of 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 0.5-10 % by weight, is preferably 1-8 % by weight, is more preferably 3-7 % by weight; Can be 0.5-12 % by weight with the total content of compound containing rare earth element described in oxide basis, preferably 1-10 % by weight, be more preferably 1-9 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be 78-98 % by weight, is preferably 82-97 % by weight, is more preferably 84-95 % by weight.In the present invention, when calculating the total amount of described raw material, containing the compound of rare earth element with oxide basis, hydrated alumina is with Al
2o
3meter, and do not comprise the water introduced in described material forming process.
According to 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 various rare earth elements that described rare earth element can be commonly used for this area.In article shaped according to the present invention as when having the carrier of catalyst of hydrogenation catalyst effect, described rare earth element is preferably selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm; More preferably La and Ce is selected from.
According to the present invention, the compound containing rare earth element in the various molecular structures that the described compound containing rare earth element can be commonly used for this area.Preferably, the described compound containing rare earth element is selected from rare earth chloride (that is, RECl
3), nitric acid rare earth (that is, RE (NO
3)
3), nitric acid rare earth ammonium (that is, (NH
4)
2rE (NO
3)
6) and rare earth acetate (that is, RE (Ac)
3, Ac is acetate).Particularly, the described compound containing rare earth element can be selected from RECl
3, La (NO
3)
36H
2o and (NH
4)
2ce (NO
3)
6, wherein RE is selected from rare earth element.
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, amorphous hydrated aluminium oxide and boehmite.More preferably, described hydrated alumina is boehmite.
According to hydrated alumina forming matter of the present invention, described article shaped is made containing the compound of rare earth element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one.Particularly, described article shaped prepares formed body by described raw material, and described formed body is carried out drying make.
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 the compound mixed-forming containing rare earth element, thus described formed body can be obtained; Also can first by hydrated alumina and cellulose ether mixed-forming, obtained preform, then on this preform, load contains the compound of rare earth element, thus obtains 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 are mixed with water containing the compound of rare earth element and at least one cellulose ether, 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, on described preform, load at least one is containing the compound of rare earth element.
In this embodiment, the various methods that this area can be adopted to commonly use load at least one on described preform contains the compound of rare earth element, such as described preform can be contacted with containing the solution of at least one containing the compound of rare earth element, thus at least one is contained the compound loaded on described preform of rare earth element.Particularly, by flooding or spraying, described preform can be contacted with containing the solution of at least one containing the compound of rare earth element, thus contain the compound loaded on described preform of rare earth element by described.Adopting the method for dipping by described containing when rare earth element compound loaded is on described preform, described dipping can be saturated dipping, also can flood for supersaturation.The described solvent containing the solution of the compound of rare earth element containing at least one can be that the routine of this area is selected, and is preferably water.Describedly to be not particularly limited containing the concentration of solution of compound of rare earth element and the number of times of described contact containing at least one, with enable the amount of the compound containing rare earth element 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 lower than at the temperature of 350 DEG C more than 60 DEG C, preferably at the temperature of 80-300 DEG C, more preferably carries out at the temperature of 120-250 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 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
According to hydrated alumina forming matter of 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 hydrated alumina forming matter of 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 hydrated alumina forming matter of 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 hydrated alumina forming matter of the present invention, can be that the routine of this area is selected by the temperature of described formed body drying.Usually, the temperature of described drying can be more than 60 DEG C and lower than 350 DEG C, be preferably 80-300 DEG C, be more preferably 120-250 DEG C.The time of described drying can carry out suitable selection according to the temperature of drying, meets instructions for use be as the criterion can make volatile matter content in the article shaped that finally obtains.Usually, the time of described drying can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
According to hydrated alumina forming matter of the present invention, described raw material can also contain at least one extrusion aid.The consumption of described extrusion aid and kind can be that the routine of this area is selected.Usually, 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.Described extrusion aid is preferably 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.Described extrusion aid can adopt the conventional various methods 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.
According to hydrated alumina forming matter of the present invention, described article shaped has good strength retention, and the radial crushing strength loss late (that is, δ value) after immersion can be less than 10%, can be even less than 5% (as less than 4%).
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 hydrated alumina forming matter of the present invention, described article shaped has higher intensity, its radial crushing strength (that is, Q
1) can be more than 12N/mm, being even more than 15N/mm, can be generally 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 hydrated alumina forming matter of the present invention, the water absorption rate of described article shaped is 0.4-1.5, is generally 0.6-1.
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:
According to hydrated alumina forming matter of the present invention, not only there are good absorbent properties, and there is excellent strength retention, even if long-time immersion still has higher intensity in water.Therefore, hydrated alumina forming matter according to the present invention is suitable for the carrier as drier and loaded catalyst.
A second aspect of the present invention provides a kind of method preparing hydrated alumina forming matter, the method comprises to be prepared formed body containing the compound of rare earth element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one, and described formed body is carried out drying.
According to method of the present invention, by using containing at least one hydrated alumina, at least one containing the compound of rare earth element and the raw material of at least one cellulose ether, do not use peptizing agent, hydrated alumina forming matter can be prepared, and the hydrated alumina forming matter of preparation have high intensity and strength retention.
According to method of the present invention, the composition of described raw material 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 0.5-10 % by weight, is preferably 1-8 % by weight, is more preferably 3-7 % by weight; Can be 0.5-12 % by weight with the total content of compound containing rare earth element described in oxide basis, preferably 1-10 % by weight, be more preferably 1-9 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be 78-98 % by weight, is preferably 82-97 % by weight, is more preferably 84-95 % by weight.
According to method of the present invention, described cellulose ether, containing the compound of rare earth element and the kind of hydrated alumina with described identical above, do not repeat them here.
According to method of the present invention, 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 the compound mixing aftershaping containing rare earth element, thus described formed body can be obtained; Also can be first shaping by hydrated alumina and cellulose ether mixing, obtained preform, then on this preform, load, containing the compound of rare earth element, thus obtains 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 are mixed with water containing the compound of rare earth element and at least one cellulose ether, 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 dry, the preform obtained, on described preform, load at least one is containing the compound of rare earth element.
In this embodiment, the various methods that this area can be adopted to commonly use load at least one on described preform contains the compound of rare earth element, such as described preform can be contacted with containing the solution of at least one containing the compound of rare earth element, thus at least one is contained the compound loaded on described preform of rare earth element.Particularly, by flooding or spraying, described preform can be contacted with containing the solution of at least one containing the compound of rare earth element, thus contain the compound loaded on described preform of rare earth element by described.Adopting the method for dipping by described containing when rare earth element compound loaded is on described preform, described dipping can be saturated dipping, also can flood for supersaturation.The described solvent containing the solution of the compound of rare earth element containing at least one can be that the routine of this area is selected, and is preferably water.Describedly to be not particularly limited containing the concentration of solution of compound of rare earth element and the number of times of described contact containing at least one, with enable the amount of the compound containing rare earth element 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 lower than at the temperature of 350 DEG C more than 60 DEG C, preferably at the temperature of 80-300 DEG C, more preferably carries out at the temperature of 120-250 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 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
According to method of 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 method of 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 method of the present invention, the article shaped of preparation can have various shape according to concrete instructions for use, such as: spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.
According to method of the present invention, can be that the routine of this area is selected by the temperature of described formed body drying.Usually, the temperature of described drying can be more than 60 DEG C and lower than 350 DEG C, within the scope being preferably in 80-300 DEG C, within the scope being more preferably in 120-250 DEG C.The time of described drying can carry out suitable selection according to the temperature of drying, meets instructions for use be as the criterion can make volatile matter content in the article shaped that finally obtains.Usually, the time of described drying can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
According to method of the present invention, described raw material can also contain at least one extrusion aid.The consumption of described extrusion aid and kind can be that the routine of this area is selected.Usually, 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.Described extrusion aid is preferably 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.Described extrusion aid can adopt the conventional various methods 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.
Prepared according to the methods of the invention hydrated alumina forming matter (that is, only drying and unfired article shaped) has good strength retention and absorbent properties.Usually, for the hydrated alumina forming matter prepared by method of the present invention, radial crushing strength can be more than 12N/mm, is even more than 15N/mm, is generally 15-30N/mm(as 15-25N/mm); δ value is less than 10%, is generally less than 5% (as less than 4%); Water absorption rate is 0.4-1.5, such as, can be 0.6-1.
Therefore, prepared according to the methods of the invention hydrated alumina forming matter can directly use, such as: carry out as drier or as the carrier of loaded catalyst the active component that load has catalytic action.
Thus, a third aspect of the present invention provides a kind of hydrated alumina forming matter prepared by method of the present invention.
A fourth aspect of the present invention provides a kind of aluminium oxide article shaped, and hydrated alumina forming matter of the present invention is carried out roasting and makes by this article shaped.
The present invention is not particularly limited for the condition of roasting, can be that the routine of this area is selected, as long as described hydrated alumina can be made to form aluminium oxide.Particularly, the temperature of described roasting can be 450-950 DEG C, is preferably 500-900 DEG C; The time of described roasting can be 2-8 hour, is preferably 3-6 hour.
Aluminium oxide article shaped according to the present invention has high intensity and strength retention and good absorbent properties.Usually, for aluminium oxide article shaped of the present invention, radial crushing strength can be more than 12N/mm, is even more than 15N/mm, is generally 15-30N/mm(as 15-25N/mm); δ value is less than 10%, is generally less than 5% (as less than 4%); Water absorption rate is 0.4-1.5, such as, can be 0.9-1.2.
A fifth aspect of the present invention provides a kind of according to the application as drier or the carrier as loaded catalyst of hydrated alumina forming matter of the present invention or aluminium oxide article shaped of the present invention.
In the present invention, described loaded catalyst can for this area commonly use various can using hydrated alumina or aluminium oxide article shaped as the catalyst of carrier.Preferably, described catalyst is the catalyst with hydrogenation catalyst effect.That is, the carrier as the catalyst with hydrogenation catalyst effect is particularly suitable for according to hydrated alumina forming matter of the present invention and aluminium oxide article shaped.
In hydrated alumina forming matter according to the present invention or aluminium oxide article shaped as when there is the carrier of catalyst of hydrogenation catalyst effect, the conventional various methods in this area (such as: dipping) can be adopted to have the active constituent loading of hydrogenation catalyst effect on hydrated alumina forming matter according to the present invention or aluminium oxide article shaped, such as: can by using the aqueous impregnation article shaped of the present invention containing described active component, then the article shaped of described active component load is had to carry out drying and optional roasting, thus obtain the catalyst with hydrogenation catalyst effect.
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 the article shaped of preparation.
In following examples and comparative example, following methods is adopted to measure the δ value of the article shaped of preparation: 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); The article shaped of preparation is placed in 50g deionized water, soaks 30 minutes, then filter, by the solid that obtains 120 DEG C of dryings 4 hours, the radial crushing strength measuring dry solid according to the method specified in RIPP25-90 (is 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 the article shaped of preparation: 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 testing sample in the percent value of the weight of the weight of 600 DEG C of roastings after 4 hours and unfired sample.
Embodiment 1-10 is for illustration of hydrated alumina forming matter according to the present invention and preparation method thereof.
Embodiment 1
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, 20.0mL rare earth chloride (that is, RECl
3) aqueous solution is (with RE
2o
3meter, content of rare earth is 85.0g/L, in its total amount of rare earth: Ce
2o
363 % by weight, La
2o
325 % by weight, Pr
6o
112.1 % by weight, Nd
2o
35.0 % by weight, Sm
2o
30.5 % by weight, other rare earth 4.4 % by weight) and 80g deionized water mix.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 hydrated alumina forming matter of the present invention.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
The method identical with embodiment 1 is adopted to prepare article shaped, unlike, do not use methylcellulose, but use 2.5mL red fuming nitric acid (RFNA), 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 2
The method identical with comparative example 1 is adopted to prepare article shaped, unlike, by after the wet bar drying of extruding, then 600 DEG C of roastings 4 hours, 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, do not use methylcellulose, result cannot obtain article shaped.
Embodiment 2
(1) in the retort of a 2L with and the mode of flowing adds the aluminum sulfate solution and sodium aluminate solution (Al that 2000mL concentration is 48g/L
2o
3content is 200g/L, and 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 in 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, Al
2o
3content is 63 % by weight, is defined as amorphous state through XRD analysis.
(2) amorphous hydrated aluminium oxide 50.0g boehmite powder (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), 20.0mL rare earth chloride solution are (with RE
2o
3meter, content of rare earth is 170.0g/L, in its total amount of rare earth: Ce
2o
363 % by weight, La
2o
325 % by weight, Pr
6o
112.1 % by weight, Nd
2o
35.0 % by weight, Sm
2o
30.5 % by weight, other rare earth 4.4 % by weight) and 90g deionized water mix.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 220 DEG C of dryings 6 hours, obtains according to hydrated alumina forming matter of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 3
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 be dissolved with 20gLa (NO
3)
36H
2the 90mL deionized water and stirring of O is even.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 hydrated alumina forming matter of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 4
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) and be dissolved with 9.5g (NH
4)
2ce (NO
3)
685g deionized water and stirring even.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 hydrated alumina forming matter of the present invention.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, 10gLa
2(CO
3)
38H
2o and 95g deionized water mixes.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 250 DEG C of dryings 4 hours, thus obtains according to hydrated alumina forming matter of the present invention.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 5 is adopted to prepare article shaped, unlike, do not use HEMC and hydroxypropyl methylcellulose, but use 20mL Alumina gel (purchased from this promise New Chemical Material science and technology Co., Ltd of Dalian, Al
2o
3content is 10 % by weight), thus obtain 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
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 be dissolved with 5.0gLa (Ac)
3105g deionized water mix.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 hydrated alumina forming matter of the present invention.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 6 is adopted to prepare article shaped, unlike, do not use hydroxypropyl methylcellulose, but use 5.0mL acetic acid, thus obtain 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 1 is adopted to prepare hydrated alumina forming matter, unlike, the content of methylcellulose is 5.83g, thus obtains according to hydrated alumina forming matter of the present invention.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.Take 50.0g shaping and drying bar, put into 100.0mL rare earth chloride solution (with RE
2o
3meter, content of rare earth is 85.0g/L, in total amount of rare earth: Ce
2o
363 % by weight, La
2o
325 % by weight, Pr
6o
112.1 % by weight, Nd
2o
35.0 % by weight, Sm
2o
30.5 % by weight, other rare earth 4.4 % by weight) in, soak after 4 hours and filter, 120 DEG C of dryings 6 hours, thus obtain according to hydrated alumina forming matter of the present invention.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 3 is adopted to prepare article shaped, unlike, the wet bar obtained is placed in baking oven, 120 DEG C of dryings 12 hours, thus obtains according to hydrated alumina forming matter of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 10
The method identical with embodiment 5 is adopted to prepare article shaped, unlike, the wet bar obtained is placed in baking oven, 300 DEG C of dryings 4 hours, thus obtains according to hydrated alumina forming matter of the present invention.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 | 22.2 | 0.85 | 3.4 |
| Comparative example 1 | 16.5 | 0.64 | 64.2 |
| Comparative example 2 | 19.1 | 0.86 | 3.3 |
| Embodiment 2 | 19.8 | 0.71 | 2.8 |
| Embodiment 3 | 15.1 | 0.85 | 3.9 |
| Embodiment 4 | 19.7 | 0.70 | 3.1 |
| Embodiment 5 | 20.6 | 0.67 | 2.5 |
| Comparative example 4 | 18.8 | 0.63 | 76.9 |
| Embodiment 6 | 19.7 | 0.78 | 2.8 |
| Comparative example 5 | 15.2 | 0.78 | 59.4 |
| Embodiment 7 | 21.8 | 0.83 | 2.9 |
| Embodiment 8 | 20.3 | 0.71 | 3.3 |
| Embodiment 9 | 15.5 | 0.86 | 2.7 |
| Embodiment 10 | 22.6 | 0.68 | 3.7 |
The result display of table 1, hydrated alumina forming matter according to the present invention has good strength retention, even if crushing strength still higher after soaking in water.
Embodiment 11-20 is used for according to aluminium oxide article shaped of the present invention and preparation method thereof.
Embodiment 11-20
Is carried out roasting under the condition that the hydrated alumina forming matter prepared according to the method identical with embodiment 1-10 is listed at table 2 respectively, thus obtain according to aluminium oxide article shaped of the present invention, its radial crushing strength, water absorption rate and δ value are listed in table 2.
Table 2
Embodiment 21-30 is for illustration of the application of hydrated alumina forming matter of the present invention as drier.
Embodiment 21-30
The hydrated alumina forming matter prepared by embodiment 1-10 (is designated as N after weighing
1) be placed in atmospheric dryer respectively as drier, then in drier, place the beaker that fills 250mL water, close drier, and place 10 days in room temperature (25 DEG C).Then, taking-up article shaped is weighed and (is designated as N
2), by following formulae discovery hygroscopic capacity,
Test result is listed in table 3.
Embodiment 31-40 is for illustration of the application of aluminium oxide article shaped according to the present invention as drier.
Embodiment 31-40
The method identical with embodiment 21-30 is adopted to measure hygroscopic capacity, unlike, aluminium oxide article shaped prepared by use embodiment 11-20 is as drier.Test result is listed in table 3.
Table 3
| Numbering | Article shaped | N 1（g） | Contents on dry basis (% by weight) | Hygroscopic capacity (%) |
| Embodiment 21 | Embodiment 1 | 20.0 | 71.3 | 68.2 |
| Embodiment 22 | Embodiment 2 | 20.0 | 70.5 | 62.5 |
| Embodiment 23 | Embodiment 3 | 20.0 | 74.8 | 77.3 |
| Embodiment 24 | Embodiment 4 | 20.0 | 78.2 | 60.3 |
| Embodiment 25 | Embodiment 5 | 20.0 | 73.4 | 56.6 |
| Embodiment 26 | Embodiment 6 | 20.0 | 74.1 | 69.2 |
| Embodiment 27 | Embodiment 7 | 20.0 | 70.4 | 68.5 |
| Embodiment 28 | Embodiment 8 | 20.0 | 68.1 | 64.3 |
| Embodiment 29 | Embodiment 9 | 20.0 | 75.6 | 78.5 |
| Embodiment 30 | Embodiment 10 | 20.0 | 75.3 | 63.2 |
| Embodiment 31 | Embodiment 11 | 20.0 | 100.0 | 67.3 |
| Embodiment 32 | Embodiment 12 | 20.0 | 100.0 | 60.6 |
| Embodiment 33 | Embodiment 13 | 20.0 | 100.0 | 75.8 |
| Embodiment 34 | Embodiment 14 | 20.0 | 100.0 | 58.3 |
| Embodiment 35 | Embodiment 15 | 20.0 | 100.0 | 55.1 |
| Embodiment 36 | Embodiment 16 | 20.0 | 100.0 | 66.4 |
| Embodiment 37 | Embodiment 17 | 20.0 | 100.0 | 65.5 |
| Embodiment 38 | Embodiment 18 | 20.0 | 100.0 | 64.7 |
| Embodiment 39 | Embodiment 19 | 20.0 | 100.0 | 80.1 |
| Embodiment 40 | Embodiment 20 | 20.0 | 100.0 | 64.5 |
As can be seen from Table 3, the absorbent properties that article shaped of the present invention has had, are suitable for as drier.
Embodiment 41-50 is for illustration of the application of hydrated alumina forming matter of the present invention as the carrier of loaded catalyst.
Embodiment 41
(1) 4.71 grams of basic nickel carbonates (NiO content is 51 % by weight), 12.0 grams of molybdenum oxides and 2.24 grams of phosphoric acid are dissolved in the water, are mixed with 60mL solution; The article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 71.3 % by weight) the solution impregnation 20.1g embodiment 1 obtained prepared, dip time is 4 hours.After filtration, by the solid product that obtains in 120 DEG C of dryings 4 hours, obtain catalyst B 1.Adopt XRF to measure catalyst composition, result illustrates in table 4.
(2) with 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) as model compound, the catalytic activity of catalyst prepared by evaluation procedure (1) on high-pressure hydrogenation micro-reactor, actual conditions is as follows.
The n-decane solution of reaction raw materials: 4,6-DMDBT, wherein, concentration is 0.45 % by weight;
The conditions of vulcanization of catalyst: the useful load of catalyst is 0.15g, and temperature is 360 DEG C, and pressure is 4.2MPa, H
2flow velocity is 400mL/min, and sulfurized oil adopts CS
2mass fraction is the cyclohexane solution of 5 % by weight, and sulfurized oil feed rate is 0.4mL/min, and sulfuration carries out 3 hours altogether.
Hydrodesulfurization reaction condition: reaction temperature is 280 DEG C, pressure is 4.2MPa, H
2flow velocity is 400mL/min, and reaction oil feed rate is 0.2mL/min, stable reaction after 3 hours sampling gas-chromatography analyze.
According to following formulae discovery desulfurization degree, thus the catalytic activity of evaluate catalysts, result is listed in table 5.
Conversion ratio × (the S of desulfurization degree (%)=4,6-DMDBT
dMBCH+ S
dMCHB+ S
dMBP) × 100%
Wherein, S
dMBCH, S
dMCHBand S
dMBPin the product that obtains of 4,6-DMDBT hydrodesulfurization respectively, dimethyl connection cyclohexane, Dimethylcyclohexyl benzene and dimethyl diphenyl selective.
Comparative example 6
2.03 grams of basic nickel carbonates (NiO content is 51 % by weight), 5.18 grams of molybdenum oxides and 0.62 gram of phosphoric acid are dissolved in the water, are mixed with 12.3mL solution.The article shaped (diameter is 1.1mm, and particle length is 2-5mm) the solution impregnation 14.3g comparative example 2 obtained prepared, dip time is 1 hour.By the solid product that obtains in 120 DEG C of dryings 4 hours, then at 400 DEG C of roasting 3h, obtain catalyst A 1.Adopt XRF to measure the composition of catalyst, result is listed in table 4.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 5.
Comparative example 7
Adopt the method Kaolinite Preparation of Catalyst identical with comparative example 6, unlike, do not carry out roasting at 400 DEG C, obtain catalyst A 2.Adopt XRF to measure the composition of catalyst, result is listed in table 4.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 5.
Embodiment 42
3.43 grams of basic cobaltous carbonates (CoO content is 70 % by weight), 12.00 grams of molybdenum oxides and 2.24 grams of phosphoric acid are dissolved in the water, are mixed with 60mL solution.By the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.5 % by weight) obtaining solution impregnation 20.3g embodiment 2 and prepare, dip time is 4 hours.After filtration, by the solid that obtains in 150 DEG C of dryings 3 hours, obtain catalyst B 2.Adopt XRF to measure the composition of catalyst, result is listed in table 4.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 5.
Embodiment 43
By 3.85 grams of nickel nitrate (Ni (NO
3)
26H
2o), 5.65 grams of ammonium metatungstate ((NH
4)
6w
7o
244H
2o) be dissolved in the water, be mixed with 14.6mL solution.The article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 66.8 % by weight) the solution impregnation 20.3g embodiment 3 obtained prepared, dip time is 1 hour.By the solid that obtains in 120 DEG C of dryings 4 hours, thus obtain catalyst B 3.Adopt XRF to measure the composition of catalyst, result is listed in table 4.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 5.
Embodiment 44
1.18 grams of basic nickel carbonates (NiO content is 51 % by weight), 3.00 grams of molybdenum oxides and 0.68 gram of phosphoric acid are dissolved in the water, are mixed with 60mL solution.The article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 78.2 % by weight) the solution impregnation 18.3g embodiment 4 obtained prepared, dip time is 4 hours.After filtration, by the solid product that obtains in 120 DEG C of dryings 4 hours, thus obtain catalyst B 4.Adopt XRF to measure the composition of catalyst, result is listed in table 4.Adopt the performance of the method evaluation catalyst identical with embodiment 41, result is listed in table 5.
Embodiment 45
3.53 grams of basic nickel carbonates (NiO content is 51 % by weight), 9.00 grams of molybdenum oxides and 1.38 grams of phosphoric acid are dissolved in the water, are mixed with 60mL solution.The article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 73.4 % by weight) the solution impregnation 19.5g embodiment 5 obtained prepared, dip time is 4 hours.After filtration, by the solid that obtains in 120 DEG C of dryings 4 hours, thus obtain catalyst B 5.Adopt XRF to measure the composition of catalyst, result is listed in table 4.Adopt the performance of the method evaluation catalyst identical with embodiment 41, result is listed in table 5.
Embodiment 46
14.12 grams of basic nickel carbonates (NiO content is 51 % by weight), 36.00 grams of molybdenum oxides and 3.35 grams of phosphoric acid are dissolved in the water, are mixed with 60mL solution.The article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 74.1 % by weight) the solution impregnation 19.3g embodiment 6 obtained prepared, dip time is 4 hours.After filtration, by the solid that obtains in 120 DEG C of dryings 4 hours, thus obtain catalyst B 6.Adopt XRF to measure the composition of catalyst, result is listed in table 4.Adopt the performance of the method evaluation catalyst identical with embodiment 41, result is listed in table 5.
Embodiment 47
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 41, unlike, carrier is article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.4 % by weight) prepared by embodiment 7, obtains catalyst B 7.Adopt XRF to measure the composition of catalyst, result is listed in table 4.Adopt the performance of the method evaluation catalyst identical with embodiment 41, result is listed in table 5.
Embodiment 48
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 41, unlike, carrier is article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 68.1 % by weight) prepared by embodiment 8, obtains catalyst B 8.Adopt XRF to measure the composition of catalyst, result is listed in table 4.Adopt the performance of the method evaluation catalyst identical with embodiment 41, result is listed in table 5.
Embodiment 49
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 43, unlike, carrier is article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 67.9 % by weight) prepared by embodiment 9, obtains catalyst B 9.Adopt XRF to measure the composition of catalyst, result is listed in table 4.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 5.
Embodiment 50
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 45, unlike, the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 75.3 % by weight) adopting embodiment 10 step (1) to prepare, obtains catalyst B 10.Adopt XRF to measure the composition of catalyst, result is listed in table 4.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 5.
Table 4
Table 5
| Numbering | Catalyst is numbered | Desulfurization degree (%) |
| Embodiment 41 | B1 | 96 |
| Comparative example 6 | A1 | 75 |
| Comparative example 7 | A2 | 77 |
| Embodiment 42 | B2 | 87 |
| Embodiment 43 | B3 | 85 |
| Embodiment 44 | B4 | 87 |
| Embodiment 45 | B5 | 94 |
| Embodiment 46 | B6 | 97 |
| Embodiment 47 | B7 | 94 |
| Embodiment 48 | B8 | 95 |
| Embodiment 49 | B9 | 86 |
| Embodiment 50 | B10 | 88 |
Embodiment 51-60 is for illustration of the application of aluminium oxide article shaped of the present invention as the carrier of loaded catalyst.
Embodiment 51
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 41, unlike, use the aluminium oxide article shaped of embodiment 11 preparation as carrier, thus obtain catalyst B 11.Adopt XRF to measure the composition of catalyst, result is listed in table 6.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 6.
Embodiment 52
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 42, unlike, use the aluminium oxide article shaped of embodiment 12 preparation as carrier, thus obtain catalyst B 12.Adopt XRF to measure the composition of catalyst, result is listed in table 6.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 6.
Embodiment 53
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 43, unlike, use the aluminium oxide article shaped of embodiment 13 preparation as carrier, thus obtain catalyst B 13.Adopt XRF to measure the composition of catalyst, result is listed in table 6.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 6.
Embodiment 54
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 44, unlike, use the aluminium oxide article shaped of embodiment 14 preparation as carrier, thus obtain catalyst B 14.Adopt XRF to measure the composition of catalyst, result is listed in table 6.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 6.
Embodiment 55
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 45, unlike, use the aluminium oxide article shaped of embodiment 15 preparation as carrier, thus obtain catalyst B 15.Adopt XRF to measure the composition of catalyst, result is listed in table 6.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 6.
Embodiment 56
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 46, unlike, use the aluminium oxide article shaped of embodiment 16 preparation as carrier, thus obtain catalyst B 16.Adopt XRF to measure the composition of catalyst, result is listed in table 6.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 6.
Embodiment 57
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 47, unlike, use the aluminium oxide article shaped of embodiment 17 preparation as carrier, thus obtain catalyst B 17.Adopt XRF to measure the composition of catalyst, result is listed in table 6.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 6.
Embodiment 58
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 48, unlike, use the aluminium oxide article shaped of embodiment 18 preparation as carrier, thus obtain catalyst B 18.Adopt XRF to measure the composition of catalyst, result is listed in table 6.Adopt the activity of the method evaluation catalyst identical with embodiment 41, result is listed in table 6.
Table 6
Data in table 5 and table 6 illustrate, are suitable for the carrier as loaded catalyst according to hydrated alumina forming matter of the present invention and aluminium oxide article shaped; Further, the catalyst with hydrogenation catalyst effect prepared using article shaped of the present invention as carrier demonstrates higher catalytic activity in the hydrotreatment of hydrocarbon ils.
Claims (24)
1. a hydrated alumina forming matter, this article shaped is made containing the compound of rare earth element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one, and described raw material is not containing peptizing agent, and the water absorption rate of this 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 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.
2. article shaped according to claim 1, wherein, described article shaped prepares formed body by described raw material, and described formed body is carried out drying make.
3. article shaped according to claim 2, wherein, described formed body is mixed with water containing the compound of rare earth element and at least one cellulose ether at least one hydrated alumina, at least one, obtains the first mixture, and make shaping for described first mixture; Or
Described formed body is mixed with water at least one hydrated alumina and at least one cellulose ether, obtain the second mixture, and described second mixture is successively carried out shaping and dehydration, obtain preform, and load at least one is made containing the compound of rare earth element on described preform.
4. according to the article shaped in claim 1-3 described in any one, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-10 % by weight, to contain the total content of the compound of rare earth element described in oxide basis for 0.5-12 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 78-98 % by weight.
5. article shaped according to claim 4, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 3-7 % by weight, to contain the total content of the compound of rare earth element described in oxide basis for 1-9 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 84-95 % by weight.
6. according to the article shaped in claim 1-3 described in any one, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
7. according to the article shaped in claim 1-3 described in any one, wherein, described rare earth element is selected from La, Ce, Pm, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm.
8. according to the article shaped in claim 1-3 described in any one, wherein, the described compound containing rare earth element is selected from rare earth chloride, nitric acid rare earth, nitric acid rare earth ammonium and rare earth acetate.
9. according to the article shaped in claim 1-3 described in any one, wherein, described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
10. article shaped according to claim 1 and 2, wherein, the water absorption rate of described article shaped is 0.6-1, δ value is less than 5%, Q
1for 15-30N/mm.
11. 1 kinds of methods preparing hydrated alumina forming matter, the method comprises prepares formed body by containing at least one hydrated alumina, at least one containing the compound of rare earth element and the raw material of at least one cellulose ether, and described formed body is carried out drying, described raw material is not containing peptizing agent.
12. methods according to claim 11, wherein, the mode being prepared described formed body by described raw material comprises:
At least one hydrated alumina, at least one are mixed with water containing the compound of rare earth element and at least one cellulose ether, obtains the first mixture, and by shaping for described first mixture; Or
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, on described preform, load at least one is containing the compound of rare earth element.
13. methods according to claim 11, wherein, the temperature of described drying is more than 60 DEG C and lower than 350 DEG C.
14. methods according to claim 13, wherein, the temperature of described drying is 80-300 DEG C.
15. methods according to claim 11 or 12, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-10 % by weight, with described in oxide basis containing the total content of the compound of rare earth element for 0.5-12 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 78-98 % by weight.
16. methods according to claim 15, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 3-7 % by weight, to contain the total content of the compound of rare earth element described in oxide basis for 1-9 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 84-95 % by weight.
17. methods according to claim 11 or 12, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
18. methods according to claim 11 or 12, wherein, described rare earth element is selected from La, Ce, Pm, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm.
19. methods according to claim 11 or 12, wherein, the described compound containing rare earth element is selected from rare earth chloride, nitric acid rare earth, nitric acid rare earth ammonium and rare earth acetate.
20. methods according to claim 11 or 12, wherein, described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
Hydrated alumina forming matter prepared by the method in 21. claim 11-20 described in any one.
22. 1 kinds of aluminium oxide article shaped, hydrated alumina forming matter described in any one in claim 1-10 and 21 is carried out roasting and makes by this article shaped.
Hydrated alumina forming matter in 23. claim 1-10 and 21 described in any one or aluminium oxide article shaped according to claim 22 are as the application of drier or the carrier as loaded catalyst.
24. application according to claim 23, wherein, described catalyst is the catalyst with hydrogenation catalyst effect.
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| CN201210193378.9A CN103480339B (en) | 2012-06-12 | 2012-06-12 | Hydrated alumina forming matter and preparation method thereof and aluminium oxide article shaped and their application |
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