CN103480428A - Hydrated alumina molded matter and preparation method thereof, alumina molded matter and applications of hydrated alumina molded matter and alumina molded matter - Google Patents
Hydrated alumina molded matter and preparation method thereof, alumina molded matter and applications of hydrated alumina molded matter and alumina molded matter Download PDFInfo
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- CN103480428A CN103480428A CN201210193376.XA CN201210193376A CN103480428A CN 103480428 A CN103480428 A CN 103480428A CN 201210193376 A CN201210193376 A CN 201210193376A CN 103480428 A CN103480428 A CN 103480428A
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Abstract
The invention provides a hydrated alumina molded matter, and a preparation method and an application thereof. The hydrated alumina molded matter is prepared from raw materials comprising at least one hydrated alumina, at least one group IVB metal element-containing compound and at least one cellulose ether. The water absorption rate of the hydrated alumina molded matter is 0.4-1.5, the delta value is below 10%, and the Q1 is more than 12 N/mm. The invention also provides an alumina molded matter and an application thereof. The alumina molded matter is prepared by calcination of the hydrated alumina molded matter. The molded matters provided by the invention have high strength and good strength retention rate. According to the method of the invention, a peptizing agent is not used during the molding process.
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 pore structure and heat-resistant stability preferably, and higher specific area, therefore the aluminium oxide article shaped is commonly used for the carrier of drier or loaded catalyst.Can carry out modulation to the character of aluminium oxide by introduce metallic element in the aluminium oxide article shaped, so that it meets the requirement of specific occasion.For example, adopt the aluminium oxide article shaped that contains IVB family metallic element as the carrier loaded active component with hydrogenation catalyst effect, the hydrogenation catalyst performance of the catalyst of preparation can be carried out modulation.
Can be by hydrated alumina and water, peptizing agent and optional extrusion aid be mixed containing the aluminium oxide article shaped of IVB family metallic element, and mixture is successively carried out to moulding, drying and high-temperature roasting obtain the aluminium oxide article shaped, then with the compound dip forming thing containing IVB family metallic element and then carry out drying and roasting and make; Can also, by mixing by hydrated alumina with containing the compound of IVB family metallic element and water, peptizing agent and optional extrusion aid, mixture successively be carried out to moulding, drying and high-temperature roasting and make.
Drying and without the article shaped of high-temperature roasting (, hydrated alumina forming matter containing IVB family metallic element) when the carrier as loaded catalyst has the active component of catalytic action or is used as drier by the method load of flooding, the phenomenon of be easy to dissolve, efflorescence and duct caving in, thereby make article shaped lose shape, therefore drying and can not directly as drier or as dipping, use carrier without the article shaped of high-temperature roasting only, the process that must experience a high-temperature roasting just can be used as drier or as the dipping carrier.
And; usually use acid (for example: nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid) as peptizing agent; the existence of acid is easy to corrode former on the one hand; discharge on the other hand a large amount of sour gas in dry and roasting process; both unfavorable to operating personnel's health, also be unfavorable for environmental protection.
Summary of the invention
The object of the invention is to overcome prior art and must use peptizing agent when preparation contains the aluminium oxide article shaped of IVB family metallic element, and the unfired low technical problem of hydrated alumina forming matter strength retention that contains IVB family metallic element.The invention provides a kind of hydrated alumina forming matter that contains IVB family metallic element and preparation method thereof, should not use peptizing agent in forming process containing the hydrated alumina forming matter of IVB family metallic element, there is good strength retention, even carry out the long-time phenomenon that also can or substantially not there will be dissolving, efflorescence and duct to cave in of soaking in solution.The method according to this invention, do not used peptizing agent in forming process.
The present inventor finds in research process, the hydrated alumina forming matter containing IVB family metallic element without high-temperature roasting is easy in adsorption process and in dipping process occur dissolving, efflorescence and duct cave in, and then the reason of losing shape may be: the hydrated alumina forming matter containing IVB family metallic element without high-temperature roasting contains peptizing agent, the Main Function of described peptizing agent is to make as the various powder adhesion of raw material together, yet in absorption and dipping process, because peptizing agent dissolves, from article shaped, run off in a large number, and then make article shaped occur dissolving, efflorescence and the duct phenomenon of caving in, the final shape of losing.
The present inventor finds through further investigation: in the forming process containing the hydrated alumina of IVB family metallic element, do not use peptizing agent, introduce cellulose ether simultaneously, even so the article shaped of preparation is not carried out high-temperature roasting, also there is good strength retention, carry out the phenomenon that long-time dipping can or not there will be dissolving, efflorescence and duct to cave in substantially yet in maceration extract, and this article shaped also have good absorbent properties.Completed thus the present invention.
A first aspect of the present invention provides a kind of hydrated alumina forming matter, this article shaped is made by containing at least one hydrated alumina, at least one compound containing IVB family metallic element and the raw material of at least one cellulose ether, the water absorption rate of this article shaped is 0.4-1.5, the δ value is below 10%, Q
1more than 12N/mm,
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.
A second aspect of the present invention provides a kind of method for preparing hydrated alumina forming matter, the method comprises by containing at least one hydrated alumina, at least one prepares formed body containing compound of IVB family metallic element and the raw material of at least one cellulose ether, and described formed body is carried out to 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 aluminium oxide article shaped, and this aluminium oxide article shaped is carried out hydrated alumina forming matter of the present invention roasting and makes.
A fifth aspect of the present invention provide a kind of according to hydrated alumina forming matter of the present invention or aluminium oxide article shaped as drier or as the application of the carrier of loaded catalyst.
Do not contain peptizing agent (for example: aluminium colloidal sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid) according to hydrated alumina forming matter of the present invention, there is good strength retention, even carry out the phenomenon that long-time dipping can or not there will be dissolving, efflorescence and duct to cave in substantially yet in maceration extract.Thereby hydrated alumina forming matter according to the present invention can be used as drier without high-temperature roasting or as the carrier of loaded catalyst.Aluminium oxide article shaped according to the present invention is made by hydrated alumina forming matter of the present invention is carried out to roasting, has high intensity and strength retention, also has good absorbent properties simultaneously.
Particularly, more than can reaching 12N/mm respectively according to the radially crushing strength of hydrated alumina forming matter of the present invention and aluminium oxide article shaped, water absorption rate can reach 0.4-1.5 respectively, and δ value (that is, the crushing strength loss late after immersion) respectively can be for below 10%.
The method according to this invention, do not used peptizing agent (that is, described raw material does not contain peptizing agent) in forming process, reduced the corrosion to former on the one hand, extended the service life of former, reduced production cost; Greatly reduce on the other hand the amount of the sour gas discharged in dry and roasting process, reduced the impact on operator ' s health, also helped environmental protection simultaneously.
The specific embodiment
A first aspect of the present invention provides a kind of hydrated alumina forming matter, and described article shaped is made by containing at least one hydrated alumina, at least one compound containing IVB family metallic element and the raw material of at least one cellulose ether.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, contains compound and the cellulose ether of IVB family metallic element, but do not contain peptizing agent, the hydrated alumina forming matter of making has good strength retention, also there are good absorbent properties simultaneously.
According to hydrated alumina forming matter of 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 0.5-10 % by weight, is preferably the 1-8 % by weight, more preferably the 2-7 % by weight; The described total content that contains the compound of IVB family metallic element of oxide of take can be the 0.5-55 % by weight, is preferably the 1-50 % by weight, more preferably the 1.5-45 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be the 35-98 % by weight, is preferably the 42-96 % by weight, more preferably the 48-95 % by weight.In the present invention, while calculating the total amount of described raw material, the described compound that contains IVB family metallic element is in oxide, and described hydrated alumina is with Al
2o
3meter, described raw material does not comprise the water of introducing in the process of described material forming.
According to 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
5alkyl comprise C
1-C
5straight chained alkyl and C
3-C
5branched alkyl, its instantiation can include but 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 amount 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 IVB family metallic element can for example can be selected from titanium, zirconium and hafnium for this area various IVB family metallic element commonly used, is preferably selected from titanium and zirconium, more preferably titanium.
According to the present invention, the described compound that contains IVB family metallic element can be the compound that contains IVB family metallic element in the various molecular structures commonly used of this area.For example, when described IVB family metallic element is selected from titanium and zirconium, the described compound that contains IVB family metallic element can be selected from basic zirconium chloride (as ZrOCl
28H
2o), zirconium acetate, zirconium sulfate, zirconium nitrate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium are (as (NH
4)
2zrO (CO
3)
2nH
2o), zirconium dioxide, metatitanic acid, metatitanic acid (H
2tiO
3), the compound shown in titanium dioxide, titanium sulfate and formula I,
TiX
n(OR)
4-n （I），
In formula I, X is halogen (for example: can, for chlorine, bromine and iodine, be preferably chlorine), and R is C
1-C
5alkyl, the integer that n is 0-4 (can be for example 0,1,2,3 or 4, be preferably 0 or 4).
Preferably, the described compound that contains IVB family metallic element is selected from zirconium acetate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium, zirconium dioxide, metatitanic acid, metatitanic acid, titanium dioxide, titanium sulfate, titanium tetrachloride, tetra-n-butyl titanate, tetrabutyl titanate and tetraisopropyl titanate.More preferably, the described compound that contains IVB family metallic element is selected from metatitanic acid and titanium dioxide.
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, 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 be by containing at least one hydrated alumina, at least one prepares formed body containing compound of IVB family metallic element and the raw material of at least one cellulose ether, and described formed body carried out to drying make.
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 with containing the compound moulding of IVB family metallic element, thereby obtain described formed body; Also can make preform first by hydrated alumina and cellulose ether mixed-forming, then on this preform, load contains the compound of IVB family metallic element, thereby obtains described formed body.
Of the present invention a kind of preferred embodiment in, described formed body is that at least one hydrated alumina, at least one compound and at least one cellulose ether containing IVB family metallic element are mixed with water, obtain the first mixture, and described the first mixture moulding is made.
In another preferred embodiment of the present invention, described formed body is that 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, on described preform load at least one containing the compound of IVB family metallic element, make.
In this embodiment, on described preform, at least one mode containing the compound of IVB family metallic element of load can be selected for the routine of this area, for example: can be by described preform is contacted with containing at least one solution containing the compound of IVB family metallic element, thus contain the compound loaded on described preform of IVB family metallic element by described.By described preform, with containing the mode that at least one solution containing the compound of IVB family metallic element contact, can be the routine selection of this area, for example: can by dipping or spray by described preform with contain at least one solution that contains the compound of IVB family metallic element and contact, thereby contain the compound loaded on described preform of IVB family metallic element by described.In the mode that adopts dipping, by described contain IVB family metallic element compound loaded on described preform the time, described dipping can be saturated dipping, also can flood for supersaturation.Described at least one solvent containing the solution of the compound of IVB family metallic element that contains can be selected for the routine of this area, is preferably water.Describedly contain at least one concentration containing the solution of the compound of IVB family metallic element and the number of times of described contact is not particularly limited so that load on the amount of the compound containing IVB family metallic element 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 carried out more than 60 ℃ and at lower than the temperature of 350 ℃, preferably at the temperature of 80-300 ℃, carries out, and more preferably at the temperature of 120-250 ℃, 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 1-48 hour, is preferably 2-24 hour, more preferably 2-12 hour.
According to hydrated alumina forming matter of 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 hydrated alumina forming matter of 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 hydrated alumina forming matter of 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 hydrated alumina forming matter of the present invention, the temperature of described formed body drying can be selected for the routine of this area.Usually, the temperature of described drying can, for more than 60 ℃ and lower than 350 ℃, be preferably 80-300 ℃, more preferably 120-250 ℃.The time of described drying can be carried out suitable selection according to dry temperature, can make in the article shaped finally obtained volatile matter content meet instructions for use, is as the criterion.Usually, the time of described drying can be 1-48 hour, is preferably 2-24 hour, 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 selected for the routine of this area.Usually, 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.According to hydrated alumina forming matter of the present invention, described extrusion aid is preferably 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.Described extrusion aid can adopt this area the whole bag of tricks 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.
According to hydrated alumina forming matter of the present invention, the radially crushing strength loss late (that is, δ value) of described article shaped after immersion is below 10%, is generally below 5%; Radially crushing strength (that is, Q without the article shaped of water soaking
1) can, 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 15-30N/mm.The water absorption rate of described article shaped is 0.4-1.5, is generally 0.6-1.
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.
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.
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 hydrated alumina forming matter of the present invention, and there is excellent strength retention, even 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 or loaded catalyst.
A second aspect of the present invention provides a kind of method for preparing hydrated alumina forming matter, the method comprises by containing at least one hydrated alumina, at least one prepares formed body containing compound of IVB family metallic element and the raw material of at least one cellulose ether, and described formed body is carried out to drying.
The method according to this invention, contain at least one hydrated alumina, at least one compound containing IVB family metallic element and the raw material of at least one cellulose ether by use, do not use peptizing agent, also can prepare article shaped, and the article shaped of preparation not only has good absorbent properties, and has high strength retention.
The method according to this invention, the composition of described raw material can carry out suitable selection according to the concrete application scenario of the article shaped of final preparation.Usually, the total amount of described raw material of take is benchmark, and the total content of described cellulose ether can be the 0.5-10 % by weight, is preferably the 1-8 % by weight, more preferably the 2-7 % by weight; The described total content that contains the compound of IVB family metallic element of oxide of take can be the 0.5-55 % by weight, is preferably the 1-50 % by weight, more preferably the 1.5-45 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be the 35-98 % by weight, is preferably the 42-96 % by weight, more preferably the 48-95 % by weight.
The method according to this invention, the kind of described cellulose ether, the compound that contains IVB family metallic element and hydrated alumina, with described identical above, does not repeat them here.
The method according to this invention, can adopt this area the whole bag of tricks commonly used to prepare described formed body, is not particularly limited.For example: can be directly by hydrated alumina, cellulose ether with containing the compound aftershaping of IVB family metallic element, thereby obtain described formed body; Also can first hydrated alumina and cellulose ether be mixed and moulding, make preform, then on this preform, load contains the compound of IVB family metallic element, thereby obtains 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 compound and at least one cellulose ether containing IVB family metallic element 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 compound containing IVB family metallic element of load on described preform.
In this embodiment, on described preform, at least one mode containing the compound of IVB family metallic element of load can be selected for the routine of this area, for example: can be by described preform is contacted with containing at least one solution containing the compound of IVB family metallic element, thus contain the compound loaded on described preform of IVB family metallic element by described.By described preform, with containing the mode that at least one solution containing the compound of IVB family metallic element contact, can be the routine selection of this area, for example: can by dipping or spray by described preform with contain at least one solution that contains the compound of IVB family metallic element and contact, thereby contain the compound loaded on described preform of IVB family metallic element by described.In the mode that adopts dipping, by described contain IVB family metallic element compound loaded on described preform the time, described dipping can be saturated dipping, also can flood for supersaturation.Described at least one solvent containing the solution of the compound of IVB family metallic element that contains can be selected for the routine of this area, is preferably water.Describedly contain at least one concentration containing the solution of the compound of IVB family metallic element and the number of times of described contact is not particularly limited so that load on the amount of the compound containing IVB family metallic element on described preform can meet the demands (for example previously described content) be as the criterion.
The method according to this invention, be not particularly limited for the preparation of the consumption of the water of described the first mixture or described the second mixture, as long as the consumption of water can be guaranteed various components are mixed.
The method according to this 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.
The method according to this 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.
The method according to this invention, the temperature of described drying can be selected for the routine of this area.Usually, the temperature of described drying can, for more than 60 ℃ and lower than 350 ℃, be preferably 80-300 ℃, more preferably 120-250 ℃.The time of described drying can be carried out suitable selection according to dry temperature, can make in the article shaped finally obtained volatile matter content meet instructions for use, is as the criterion.Usually, the time of described drying can be 1-48 hour, is preferably 2-24 hour, more preferably 2-12 hour.
The method according to this invention, described raw material can also contain at least one extrusion aid.The consumption of described extrusion aid and kind can be selected for the routine of this area.Usually, 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.The method according to this invention, described extrusion aid is preferably 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.Described extrusion aid can adopt this area the whole bag of tricks 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.
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, radially crushing strength can be even more than 15N/mm for more than 12N/mm, can be for example 15-30N/mm; The δ value can, for below 10%, be generally below 5%; Water absorption rate can be 0.4-1.5, can be for example 0.6-1.Therefore, the method according to this invention in forming process without using peptizing agent, and the hydrated alumina forming matter of preparation has good strength retention and absorbent properties, be suitable for coming load to there is the active component of catalytic action as drier or as the carrier of loaded catalyst.
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 this aluminium oxide article shaped is carried out hydrated alumina forming matter of the present invention roasting and makes.
The present invention is not particularly limited for the condition of roasting, can select for the routine of this area.Particularly, the temperature of described roasting can be 450-950 ℃, is preferably 500-900 ℃; 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, the radially crushing strength of described aluminium oxide article shaped can be even more than 15N/mm for more than 12N/mm, can be for example 15-30N/mm; The δ value is below 10%, is generally below 5%; Water absorption rate is 0.4-1.5, can be for example 0.6-1.
A fifth aspect of the present invention provides according to hydrated alumina forming matter of the present invention or aluminium oxide article shaped as drier or as the application of the carrier of loaded catalyst.
In the present invention, described loaded catalyst can be usingd hydrated alumina or the aluminium oxide article shaped catalyst as carrier for commonly used various in this area.Preferably, described catalyst is the catalyst with hydrogenation catalyst effect, according to hydrated alumina forming matter of the present invention and aluminium oxide article shaped, is particularly suitable for as the carrier with catalyst of hydrogenation catalyst effect.
In hydrated alumina forming matter according to the present invention or aluminium oxide article shaped during as the carrier of the catalyst with hydrogenation catalyst effect, can adopt this area the whole bag of tricks commonly used (for example: dipping) will there is the active constituent loading of hydrogenation catalyst effect on hydrated alumina forming matter according to the present invention or aluminium oxide article shaped, for example: the aqueous solution that can contain described active component by use floods article shaped of the present invention, then load there is is the article shaped of described active component to carry out drying and optional roasting, thereby obtain having the catalyst of hydrogenation catalyst effect.
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 the article shaped of preparation.
In following examples and Comparative Examples, adopt following methods to measure the δ value of the article shaped of preparation: the radially crushing strength that the method for stipulating in employing RIPP 25-90 is measured without the article shaped of water soaking (is designated as Q
1); The article shaped of preparation is placed in to the 50g deionized water, soaks 30 minutes, then filter, by the solid that obtains, 120 ℃ of dryings 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 the article shaped of preparation: 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 was measured testing sample 600 ℃ of roastings 4 hours.
Embodiment 1-16 is for illustrating according to hydrated alumina forming matter of 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 sea, Zhejiang Shen chemical industry Co., Ltd), 3.0g sesbania powder, 20.2g metatitanic acid slurries (with TiO
2the meter, Ti content is 40 % by weight) and the 80g deionized water mix.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 hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Comparative Examples 1
Adopt the method identical with embodiment 1 to prepare hydrated alumina forming matter, different, do not use methylcellulose, but use the 2.5mL red fuming nitric acid (RFNA), thereby obtain hydrated alumina forming matter, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Comparative Examples 2
Adopt the method identical with Comparative Examples 1 to prepare article shaped, different, the wet bar drying of extruding to be followed afterwards 600 ℃ of roastings 4 hours, thereby obtained article shaped, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Comparative Examples 3
Adopt the method identical with embodiment 1 to prepare article shaped, different, do not use methylcellulose, result can't make article shaped.
Embodiment 2
(1) in the retort of a 2L, take and the stream mode add aluminum sulfate solution and the sodium aluminate solution (Al that 2000mL concentration is 48g/L
2o
3content is 200g/L, and 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, Al
2o
3content is 63 % by weight, through XRD analysis, is defined as amorphous state.
(2) the amorphous hydrated aluminium oxide prepared by 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), 2.0g methylcellulose (purchased from sea, Zhejiang Shen chemical industry Co., Ltd), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 5.0g metatitanic acid slurries are (with TiO
2the meter, Ti content is 40 % by weight) and the 90g deionized water mix.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 220 ℃ of dryings 6 hours, thereby obtains according to hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 3
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, 30.0g titanium dioxide and the 120g deionized water and stirring even.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 hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 4
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), 75.0g titanium dioxide and 150g deionized water and stirring is even.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 hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Comparative Examples 4
Adopt the method identical with embodiment 4 to prepare hydrated alumina forming matter, different, do not use HEMC, but use 20mL aluminium colloidal sol (purchased from this promise New Chemical Material science and technology Co., Ltd of Dalian, Al
2o
3content is 10 % by weight), thus hydrated alumina forming matter obtained, and radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 5
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), 20.0g titanium dioxide are mixed with the 115g deionized water.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 250 ℃ of dryings 4 hours, thereby obtains hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 6
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, 70.0g metatitanic acid slurries (with TiO
2meter, the content of titanium is 40 % by weight) with the 55g deionized 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, obtains hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Comparative Examples 5
Adopt the method identical with embodiment 6 to prepare hydrated alumina forming matter, different, do not use hydroxypropyl methylcellulose, but use 5.0mL acetic acid, thereby obtain hydrated alumina forming matter, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 7
Adopt the method identical with embodiment 2 to prepare hydrated alumina forming matter, different is, the content of methylcellulose is 2.0g, the content of HEMC is 5.0g, thereby obtain according to hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
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 Shanghai Hui Guang Fine Chemical 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.Take 50g shaping and drying bar, put into by the 12.0g tetra-n-butyl titanate and be dissolved in the 100mL solution that deionized water is prepared, flood after 4 hours and filter, 120 ℃ of dryings 6 hours, thereby obtain hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 9
Adopt the method identical with embodiment 3 to prepare article shaped, different, the wet bar obtained is placed in to baking oven, 120 ℃ of dryings 12 hours, thereby obtain hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 10
Adopt the method identical with embodiment 5 to prepare article shaped, different, the wet bar obtained is placed in to baking oven, 300 ℃ of dryings 4 hours, thereby obtain hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 11
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, 25.0g zirconium hydroxide (with ZrO
2the meter, zirconium content is 35 % by weight) and the 85g deionized water mix.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 hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Comparative Examples 6
Adopt the method identical with embodiment 11 to prepare hydrated alumina forming matter, different, do not use methylcellulose, but use the 2.5mL red fuming nitric acid (RFNA), thereby obtain hydrated alumina forming matter.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value are listed in table 1.
Comparative Examples 7
Adopt the method identical with Comparative Examples 6 to prepare article shaped, different, the wet bar drying of extruding to be followed afterwards 600 ℃ of roastings 4 hours, thereby obtained article shaped, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Comparative Examples 8
Adopt the method identical with embodiment 11 to prepare article shaped, different, do not use methylcellulose, result can't make article shaped.
Embodiment 12
(1) adopt the method identical with embodiment 2 to prepare amorphous hydrated aluminium oxide.
(2) the amorphous hydrated aluminium oxide prepared by 50.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, butt 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), 5.0g zirconium hydroxide are (with ZrO
2the meter, zirconium content is 35 % by weight) and the 90g deionized water mix.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 220 ℃ of dryings 6 hours, obtains hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 13
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, 32.0g zirconium dioxide and the 122g deionized water and stirring even.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 hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 14
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), 67.0g zirconium dioxide and 150g deionized water and stirring is even.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, obtains hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 15
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, 18.0g zirconium dioxide are mixed with the 115g deionized water.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 250 ℃ of dryings 4 hours, obtains hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Comparative Examples 9
Adopt the method identical with embodiment 15 to prepare hydrated alumina forming matter, different, do not use HEMC and hydroxypropyl methylcellulose, but use 20mL aluminium colloidal sol (purchased from this promise New Chemical Material science and technology Co., Ltd of Dalian, Al
2o
3content is 10 % by weight), thus hydrated alumina forming matter obtained, and radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Embodiment 16
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, 70.0g zirconium hydroxide (with ZrO
2meter, the content of zirconium is 35 % by weight) with the 55g deionized 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, obtains hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Comparative Examples 10
Adopt the method identical with embodiment 16 to prepare hydrated alumina forming matter, different, do not use hydroxypropyl methyl fiber, but use 5.0mL acetic acid, thereby obtain hydrated alumina forming matter, radially crushing strength, water absorption rate and δ value are listed in table 1 for they.
Table 1
| Numbering | Crushing strength (N/mm) | Water absorption rate | δ value (%) |
| Embodiment 1 | 22.2 | 0.85 | 3.4 |
| Comparative Examples 1 | 16.5 | 0.64 | 64.2 |
| Comparative Examples 2 | 25.8 | 0.85 | 3.1 |
| Embodiment 2 | 19.8 | 0.71 | 2.8 |
| Embodiment 3 | 15.1 | 0.68 | 3.9 |
| Embodiment 4 | 19.7 | 0.70 | 3.1 |
| Comparative Examples 4 | 19.1 | 0.68 | 76.1 |
| Embodiment 5 | 22.8 | 0.67 | 2.5 |
| Embodiment 6 | 19.7 | 0.78 | 2.8 |
| Comparative Examples 5 | 15.2 | 0.78 | 59.4 |
| Embodiment 7 | 19.9 | 0.70 | 2.9 |
| Embodiment 8 | 20.5 | 0.73 | 3.1 |
| Embodiment 9 | 16.8 | 0.88 | 3.0 |
| Embodiment 10 | 20.6 | 0.73 | 2.8 |
| Embodiment 11 | 23.1 | 0.83 | 3.3 |
| Comparative Examples 6 | 17.1 | 0.63 | 63.6 |
| Comparative Examples 7 | 24.3 | 0.83 | 4.2 |
| Embodiment 12 | 18.9 | 0.71 | 2.7 |
| Embodiment 13 | 16.2 | 0.84 | 3.7 |
| Embodiment 14 | 19.4 | 0.71 | 3.2 |
| Embodiment 15 | 19.5 | 0.68 | 2.7 |
| Comparative Examples 9 | 18.2 | 0.65 | 75.4 |
| Embodiment 16 | 18.6 | 0.76 | 2.6 |
| Comparative Examples 10 | 16.1 | 0.77 | 60.3 |
Embodiment 17-27 is for illustrating according to aluminium oxide article shaped of the present invention.
Embodiment 17-27
Carry out roasting under the condition that hydrated alumina forming matter prepared by embodiment 1-11 is listed at table 2 respectively, thereby obtain according to aluminium oxide article shaped of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 2 for they.
Table 2
The result of table 1 and table 2 shows, according to the present invention, article shaped has good radially crushing strength and crushing strength conservation rate radially, also has good absorbent properties simultaneously.
Embodiment 28-59 is for illustrating the application of article shaped of the present invention as drier.
Embodiment 28-43
Hydrated alumina forming matter prepared by embodiment 1-16 (is designated as N after weighing
1) be placed in respectively atmospheric dryer as drier, then in drier, place a beaker that fills 250mL water, close drier, and place 10 days in room temperature (25 ℃).Then, the taking-up article shaped is weighed and (is designated as N
2), calculate hygroscopic capacity with following formula, result is listed in table 3,
Embodiment 44-54
Adopt the method identical with embodiment 28-43 to measure hygroscopic capacity, different, the article shaped of using embodiment 17-27 to prepare is as drier.Test result is listed in table 3.
Embodiment 55-59
Adopt the method identical with embodiment 28-43 to measure hygroscopic capacity, different is, hydrated alumina forming matter prepared by embodiment 12-16 is 600 ℃ of roastings 4 hours, thereby obtains aluminium oxide article shaped of the present invention, and by the aluminium oxide article shaped effect drier obtained.Test result is shown in table 3.
Table 3
| Numbering | Article shaped | N 1（g） | Contents on dry basis (% by weight) | Hygroscopic capacity (%) |
| Embodiment 28 | Embodiment 1 | 20.0 | 71.3 | 68.2 |
| Embodiment 29 | Embodiment 2 | 20.0 | 70.5 | 62.5 |
| Embodiment 30 | Embodiment 3 | 20.0 | 70.2 | 77.3 |
| Embodiment 31 | Embodiment 4 | 20.0 | 78.2 | 60.3 |
| Embodiment 32 | Embodiment 5 | 20.0 | 73.4 | 56.6 |
| Embodiment 33 | Embodiment 6 | 20.0 | 74.1 | 69.2 |
| Embodiment 34 | Embodiment 7 | 20.0 | 70.9 | 68.5 |
| Embodiment 35 | Embodiment 8 | 20.0 | 67.3 | 66.8 |
| Embodiment 36 | Embodiment 9 | 20.0 | 74.8 | 78.6 |
| Embodiment 37 | Embodiment 10 | 20.0 | 78.6 | 63.6 |
| Embodiment 38 | Embodiment 11 | 20.0 | 70.6 | 67.3 |
| Embodiment 39 | Embodiment 12 | 20.0 | 71.2 | 61.6 |
| Embodiment 40 | Embodiment 13 | 20.0 | 73.7 | 78.2 |
| Embodiment 41 | Embodiment 14 | 20.0 | 77.6 | 61.2 |
| Embodiment 42 | Embodiment 15 | 20.0 | 72.8 | 57.8 |
| Embodiment 43 | Embodiment 16 | 20.0 | 73.4 | 68.6 |
| Embodiment 44 | Embodiment 17 | 20.0 | 100.0 | 67.3 |
| Embodiment 45 | Embodiment 18 | 20.0 | 100.0 | 60.6 |
| Embodiment 46 | Embodiment 19 | 20.0 | 100.0 | 75.8 |
| Embodiment 47 | Embodiment 20 | 20.0 | 100.0 | 58.3 |
| Embodiment 48 | Embodiment 21 | 20.0 | 100.0 | 55.1 |
| Embodiment 49 | Embodiment 22 | 20.0 | 100.0 | 66.4 |
| Embodiment 50 | Embodiment 23 | 20.0 | 100.0 | 67.4 |
| Embodiment 51 | Embodiment 24 | 20.0 | 100.0 | 68.5 |
| Embodiment 52 | Embodiment 25 | 20.0 | 100.0 | 79.8 |
| Embodiment 53 | Embodiment 26 | 20.0 | 100.0 | 65.9 |
| Embodiment 54 | Embodiment 27 | 20.0 | 100.0 | 66.9 |
| Embodiment 55 | Embodiment 12 * | 20.0 | 100.0 | 61.2 |
| Embodiment 56 | Embodiment 13 * | 20.0 | 100.0 | 76.3 |
| Embodiment 57 | Embodiment 14 * | 20.0 | 100.0 | 59.3 |
| Embodiment 58 | Embodiment 15 * | 20.0 | 100.0 | 56.9 |
| Embodiment 59 | Embodiment 16 * | 20.0 | 100.0 | 67.5 |
*: the aluminium oxide article shaped that hydrated alumina forming matter prepared by embodiment 12-16 obtains 600 ℃ of roastings in 4 hours.
The result demonstration of table 3, article shaped according to the present invention has good absorbent properties, is suitable for as drier.
Embodiment 60-77 is for illustrating the application of article shaped of the present invention as the carrier of loaded catalyst.
Embodiment 60
(1) 4.71g basic nickel carbonate (NiO content is 51 % by weight), 12.0g molybdenum oxide and 2.24g phosphoric acid are dissolved in the water, are mixed with 60mL solution; Article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 71.3 % by weight) prepared by the solution impregnation 20.1g embodiment 1 obtained, dip time is 4 hours.After filtration, the solid product that obtains, in 150 ℃ of dryings 3 hours, is obtained to catalyst B 1.Adopt XRF to be analyzed catalyst, result is shown in table 4.
(2) with 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) as model compound, the activity of catalyst prepared by evaluation procedure on the high-pressure hydrogenation micro-reactor (1), 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 ℃, and pressure is 4.2MPa, H
2flow velocity is 400mL/min, and sulfurized oil adopts CS
2the cyclohexane solution that mass fraction is 5 % by weight, the sulfurized oil feed rate is 0.4mL/min, sulfuration is carried out 3 hours altogether.
The hydrodesulfurization reaction condition: reaction temperature is 280 ℃, and pressure is 4.2MPa, H
2flow velocity is 400mL/min, and the feed rate of reaction raw materials is 0.2mL/min, and stable reaction sampled and analyzed by gas-chromatography after 3 hours.
Calculate desulfurization degree according to following formula, result is listed in table 4.
Desulfurization degree (%)=4, the conversion ratio of 6-DMDBT * (S
dMBCH+ S
dMCHB+ S
dMBP) * 100%
Wherein, S
dMBCH, S
dMCHBand S
dMBPrespectively in the product that obtains of 4,6-DMDBT hydrodesulfurization, dimethyl connection cyclohexane, Dimethylcyclohexyl benzene and dimethyl diphenyl selective.
Comparative Examples 11
2.03g basic nickel carbonate (NiO content is 51 % by weight), 5.18g molybdenum oxide and 1.32g phosphoric acid are dissolved in the water, are mixed with 12.0mL solution.Article shaped (diameter is 1.1mm, and particle length is 2-5mm) prepared by the solution impregnation 14.3g Comparative Examples 2 obtained, dip time is 1 hour.The solid product that obtains, in 150 ℃ of dryings 3 hours, then, at 400 ℃ of roasting 3h, is obtained to catalyst A 1.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Comparative Examples 12
Adopt the method Kaolinite Preparation of Catalyst identical with Comparative Examples 11, different, in step (2), at 400 ℃, do not carry out roasting, thereby obtain catalyst A 2.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 61
3.43g basic cobaltous carbonate (CoO content is 70 % by weight), 12.00g molybdenum oxide and 2.24g phosphoric acid are dissolved in the water, are mixed with 60mL solution.To obtain the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.5 % by weight) of solution impregnation 20.3g embodiment 2 preparations, dip time is 4 hours.After filtration, the solid that obtains, in 160 ℃ of dryings 4 hours, is obtained to catalyst B 2.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 62
By 3.85g nickel nitrate (Ni (NO
3)
26H
2o), 5.65g ammonium metatungstate ((NH
4)
6w
7o
244H
2o) be dissolved in the water, be mixed with 17.9mL solution.Article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.2 % by weight) prepared by the solution impregnation 19.1g embodiment 3 obtained, dip time is 1 hour.The solid product that obtains, in 120 ℃ of dryings 4 hours, is obtained to catalyst B 3.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 63
1.18g basic nickel carbonate (NiO content is 51 % by weight), 3.00g molybdenum oxide and 0.68g phosphoric acid are dissolved in the water, are mixed with 60mL solution.Article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 78.2 % by weight) prepared by the solution impregnation 18.3g embodiment 4 obtained, dip time is 4 hours.After filtration, the solid product that obtains, in 120 ℃ of dryings 4 hours, is obtained to catalyst B 4.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 64
3.53g basic nickel carbonate (NiO content is 51 % by weight), 9.00g molybdenum oxide and 1.38g phosphoric acid are dissolved in the water, are mixed with 60mL solution.Article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 73.4 % by weight) prepared by the solution impregnation 19.5g embodiment 5 obtained, dip time is 4 hours.After filtration, the solid that obtains, in 120 ℃ of dryings 4 hours, is obtained to catalyst B 5.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 65
14.12g basic nickel carbonate (NiO content is 51 % by weight), 36.00g molybdenum oxide and 6.70g phosphoric acid are dissolved in the water, are mixed with 60mL solution.The article shaped that the solution impregnation 19.3g embodiment 6 obtained is obtained (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 74.1 % by weight), dip time is 4 hours.After filtration, the solid product that obtains, in 120 ℃ of dryings 4 hours, is obtained to catalyst B 6.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 66
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 61, different, use the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.4 % by weight) of embodiment 7 preparations, thereby obtain catalyst B 7.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 67
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 60, different, use the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 67.3 % by weight) of embodiment 8 preparations, thereby obtain catalyst B 8.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 68
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 62, different, use the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 74.8 % by weight) of embodiment 9 preparations, thereby obtain catalyst B 9.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 69
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 64, different, use the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 78.6 % by weight) of embodiment 10 preparations, thereby obtain catalyst B 10.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 70
4.71g basic nickel carbonate (NiO content is 51 % by weight), 12.0g molybdenum oxide and 2.24g phosphoric acid are dissolved in the water, are mixed with 60mL solution; Article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.6 % by weight) prepared by the solution impregnation 20.1g embodiment 11 obtained, dip time is 4 hours.After filtration, the solid product that obtains, in 120 ℃ of dryings 4 hours, is obtained to catalyst B 11.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Comparative Examples 13
2.03g basic nickel carbonate (NiO content is 51 % by weight), 5.18g molybdenum oxide and 1.32g phosphoric acid are dissolved in the water, are mixed with 11.9mL solution.Article shaped (diameter is 1.1mm, and particle length is 2-5mm) prepared by the solution impregnation 14.3g Comparative Examples 7 obtained, dip time is 1 hour.The solid product that obtains, in 120 ℃ of dryings 4 hours, then, at 400 ℃ of roasting 3h, is obtained to catalyst A 3.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Comparative Examples 14
Adopt the method Kaolinite Preparation of Catalyst identical with Comparative Examples 13, different, at 400 ℃, do not carry out roasting, obtain catalyst A 4.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 71
3.43g basic cobaltous carbonate (CoO content is 70 % by weight), 12.00g molybdenum oxide and 2.24g phosphoric acid are dissolved in the water, are mixed with 60mL solution.To obtain the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 71.2 % by weight) of solution impregnation 20.1g embodiment 12 preparations, dip time is 4 hours.After filtration, the solid that obtains, in 120 ℃ of dryings 4 hours, is obtained to catalyst B 12.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 72
By 3.85g nickel nitrate (Ni (NO
3)
26H
2o), 5.65g ammonium metatungstate ((NH
4)
6w
7o
244H
2o) be dissolved in the water, be mixed with 16.1mL solution.Article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 73.7 % by weight) prepared by the solution impregnation 19.4g embodiment 13 obtained, dip time is 1 hour.The carrier that obtains, in 120 ℃ of dryings 4 hours, is obtained to catalyst B 13.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 73
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 60, different, the article shaped (diameter is 1.1mm, and particle length is 2-5mm) of using embodiment 17 to prepare, obtain catalyst B 14.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 74
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 66, different, the article shaped (diameter is 1.1mm, and particle length is 2-5mm) of using embodiment 23 to prepare, obtain catalyst B 15.Adopt XRF to be analyzed catalyst, adopt the performance of the method evaluation catalyst identical with embodiment 60, result is listed in table 4.
Embodiment 75
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 67 performance of evaluate catalysts, different, the article shaped (diameter is 1.1mm, and particle length is 2-5mm) of using embodiment 24 to prepare, obtain catalyst B 16, and it forms and desulfurization degree is listed in table 4.
Embodiment 76
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 70 performance of evaluate catalysts, different, the article shaped (diameter is 1.1mm, and particle length is 2-5mm) of using embodiment 27 to prepare, obtain catalyst B 17, and it forms and desulfurization degree is listed in table 4.
Table 4
As can be seen from Table 4, using the catalyst with hydrogenation catalyst effect prepared as carrier by article shaped of the present invention shows higher catalytic activity in the hydrotreatment of hydrocarbon ils.
Claims (22)
1. a hydrated alumina forming matter, this article shaped is made by containing at least one hydrated alumina, at least one compound containing IVB family metallic element and the raw material of at least one cellulose ether, the water absorption rate of this 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 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.
2. article shaped according to claim 1, wherein, described article shaped is to prepare formed body by described raw material, and described formed body is carried out to drying and make.
3. article shaped according to claim 2, wherein, described formed body is that at least one hydrated alumina, at least one compound and at least one cellulose ether containing IVB family metallic element are mixed with water, obtains the first mixture, and described the first mixture moulding is made; Perhaps
Described formed body is that 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, and on described preform load at least one containing the compound of IVB family metallic element, make.
4. according to the described article shaped of any one in claim 1-3, wherein, the total amount of described raw material of take is benchmark, and the total content of described cellulose ether is the 0.5-10 % by weight, the described total content that contains the compound of IVB family metallic element of oxide of take is the 0.5-55 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 35-98 % by weight.
5. according to the described article shaped of any one in claim 1-3, 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, wherein, described IVB family metallic element is selected from titanium and zirconium.
7. according to the described method of any one in claim 1-3, wherein, the described compound that contains IVB family metallic element is selected from the compound shown in basic zirconium chloride, zirconium acetate, zirconium sulfate, zirconium nitrate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium, zirconium dioxide, metatitanic acid, metatitanic acid, titanium dioxide, titanium sulfate and formula I
TiX
n(OR)
4-n （I），
In formula I, X is halogen, and R is C
1-C
5alkyl, the integer that n is 0-4.
8. according to the described article shaped of any one in claim 1-3, wherein, described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
9. article shaped according to claim 1 and 2, wherein, the water absorption rate of described article shaped is 0.6-1, the δ value is below 5%, Q
1for 15-30N/mm.
10. a method for preparing hydrated alumina forming matter, the method comprises by containing at least one hydrated alumina, at least one prepares formed body containing compound of IVB family metallic element and the raw material of at least one cellulose ether, and described formed body is carried out to drying.
11. method according to claim 10, wherein, the mode that is prepared described formed body by described raw material comprises:
At least one hydrated alumina, at least one compound and at least one cellulose ether containing IVB family metallic element are mixed with water, obtain the first mixture, and by described the first mixture moulding; Perhaps
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 compound containing IVB family metallic element of load on described preform.
12. according to the described method of claim 10 or 11, wherein, the total amount of described raw material of take is benchmark, and the total content of described cellulose ether is the 0.5-10 % by weight, the described total content that contains the compound of IVB family metallic element of oxide of take is the 0.5-55 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 35-98 % by weight.
13., according to the described method of claim 10 or 11, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
14., according to the described method of claim 10 or 11, wherein, described IVB family metallic element is selected from titanium and zirconium.
15. according to the described method of claim 10 or 11, wherein, the described compound that contains IVB family metallic element is selected from the compound shown in basic zirconium chloride, zirconium acetate, zirconium sulfate, zirconium nitrate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium, zirconium dioxide, metatitanic acid, metatitanic acid, titanium dioxide, titanium sulfate and formula I
TiX
n(OR)
4-n （I），
In formula I, X is halogen, and R is C
1-C
5alkyl, the integer that n is 0-4.
16., according to the described method of claim 10 or 11, wherein, described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
17. method according to claim 10, wherein, the temperature of described drying is more than 60 ℃ and lower than 350 ℃.
18. method according to claim 17, wherein, the temperature of described drying is 80-300 ℃.
19. the hydrated alumina forming matter that in claim 10-18 prepared by the described method of any one.
20. an aluminium oxide article shaped, this aluminium oxide article shaped is carried out the described hydrated alumina forming matter of any one in claim 1-9 and 19 roasting and makes.
21. in claim 1-9 and 19, the described aluminium oxide article shaped of the described hydrated alumina forming matter of any one or claim 20 is as drier or as the application of the carrier of loaded catalyst.
22. application according to claim 21, wherein, described catalyst is the catalyst with hydrogenation catalyst effect.
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| CN105983418A (en) * | 2015-02-05 | 2016-10-05 | 中国石油天然气股份有限公司 | Macroporous residual oil hydrodemetallization catalyst containing TiO2 |
| CN107580588A (en) * | 2015-03-11 | 2018-01-12 | 塞特工业公司 | Oil-free crystal growth modifier for alumina recovery |
| CN108236940A (en) * | 2016-12-27 | 2018-07-03 | 中国石油天然气股份有限公司 | The preparation method of catalyst for hydrotreatment of residual oil carrier |
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| CN105983418A (en) * | 2015-02-05 | 2016-10-05 | 中国石油天然气股份有限公司 | Macroporous residual oil hydrodemetallization catalyst containing TiO2 |
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| CN107580588A (en) * | 2015-03-11 | 2018-01-12 | 塞特工业公司 | Oil-free crystal growth modifier for alumina recovery |
| CN107580588B (en) * | 2015-03-11 | 2020-10-30 | 塞特工业公司 | Oil-free crystal growth regulator for alumina recovery |
| CN108236940A (en) * | 2016-12-27 | 2018-07-03 | 中国石油天然气股份有限公司 | The preparation method of catalyst for hydrotreatment of residual oil carrier |
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