CN103480327A - Iron-containing hydrated alumina molded matter and preparation method thereof, and iron-containing alumina molded matter and applications of iron-containing hydrated alumina molded matter and iron-containing alumina molded matter - Google Patents
Iron-containing hydrated alumina molded matter and preparation method thereof, and iron-containing alumina molded matter and applications of iron-containing hydrated alumina molded matter and iron-containing alumina molded matter Download PDFInfo
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- CN103480327A CN103480327A CN201210193937.6A CN201210193937A CN103480327A CN 103480327 A CN103480327 A CN 103480327A CN 201210193937 A CN201210193937 A CN 201210193937A CN 103480327 A CN103480327 A CN 103480327A
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Abstract
The invention provides an iron-containing hydrated alumina molded matter, and a preparation method and an application thereof. The iron-containing hydrated alumina molded matter is prepared from raw materials comprising at least one hydrated alumina, at least one iron-containing compound and at least one cellulose ether. The water absorption rate of the iron-containing hydrated alumina molded matter is 0.4-1.5, the delta value is 10% or less, and the Q1 is 12 N/mm or more. The invention also provides an iron-containing alumina molded matter prepared by calcination of the iron-containing hydrated alumina molded matter. The invention also provides an application of the molded matters as a drying agent or as a carrier of a supported catalyst. The iron-containing hydrated alumina molded matter contains no peptizing agent, has good strength retention rate, and cannot or basically cannot generate phenomena of dissolving, powdering or pore collapsing even being immersed in an impregnating solution for a long time. The method of the invention does not adopt the peptizing agent.
Description
Technical field
The present invention relates to a kind of iron content hydrated alumina forming matter and its preparation method and application, the invention still further relates to a kind of iron content 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 ferro element in the aluminium oxide article shaped, so that it meets the requirement of specific occasion.For example, adopt iron content aluminium oxide article shaped to prepare hydrogenation catalyst as carrier, can carry out modulation to the hydrofinishing performance of catalyst.
Iron content aluminium oxide article shaped can be by mixing hydrated alumina and water, peptizing agent and optional extrusion aid, and mixture is successively carried out to moulding, drying and high-temperature roasting obtain the aluminium oxide article shaped, then by the solution impregnation article shaped that contains iron containing compounds and then carry out drying and roasting and make; Can also, by hydrated alumina and iron containing compounds and water, peptizing agent and optional extrusion aid are mixed, mixture successively be carried out to moulding, drying and high-temperature roasting and make.
Drying and without the article shaped of high-temperature roasting (, the iron content hydrated alumina forming matter) 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 be directly as drier or as the dipping carrier without the article shaped of high-temperature roasting only, the process that must experience a high-temperature roasting could be 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 iron content aluminium oxide article shaped, and the low technical problem of unfired iron content hydrated alumina forming matter strength retention.The invention provides a kind of iron content hydrated alumina forming matter and its preparation method and application, this iron content hydrated alumina forming matter has 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 present invention also provides a kind of iron content aluminium oxide article shaped, and this iron content aluminium oxide article shaped is formed by iron content hydration aluminium oxide calcining provided by the invention, does not use peptizing agent in forming process.
The present inventor finds in research process, iron content 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 of losing shape may be: the iron content hydrated alumina forming matter 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 is through further investigation, surprisingly find: in the forming process of iron content hydrated alumina, 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 has good absorbent properties.Completed thus the present invention.
A first aspect of the present invention provides a kind of iron content hydrated alumina forming matter, this article shaped is made by the raw material that contains at least one hydrated alumina, at least one iron containing compounds and 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.
A second aspect of the present invention provides a kind of method for preparing the iron content hydrated alumina forming matter, the method comprises by the raw material that contains at least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether and prepares formed body, and described formed body is carried out to drying.
A third aspect of the present invention provides a kind of iron content hydrated alumina forming matter prepared by method of the present invention.
A fourth aspect of the present invention provides a kind of iron content aluminium oxide article shaped, and this article shaped is carried out iron content hydrated alumina forming matter of the present invention roasting and makes.
A fifth aspect of the present invention provide a kind of according to iron content hydrated alumina forming matter of the present invention or iron content 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 iron content 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, also can be as drier or as the carrier of loaded catalyst even do not carry out high-temperature roasting according to iron content hydrated alumina forming matter of the present invention.Iron content aluminium oxide article shaped according to the present invention is formed by iron content hydrated alumina forming matter provided by the invention roasting, not only has good absorbent properties, and has high intensity and strength retention.
Particularly, more than can reaching 12N/mm respectively according to the radially crushing strength of iron content hydrated alumina forming matter of the present invention and iron content aluminium oxide article shaped, water absorption rate can reach 0.4-1.5 respectively, and δ value (that is, the radially 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 iron content hydrated alumina forming matter, and described article shaped is made by the raw material that contains at least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether.Term " at least one " refers to one or more.
According to iron content hydrated alumina forming matter of the present invention, described raw material contains hydrated alumina, iron containing compounds and cellulose ether, but, containing peptizing agent, the iron content hydrated alumina forming matter of making does not have good absorbent properties, still there is good strength retention simultaneously after immersion.
According to iron content 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 expection application scenario of article shaped.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 1-9 % by weight, more preferably the 3-8 % by weight; With Fe
2o
3the total content of the described iron containing compounds of meter can be the 0.5-8 % by weight, is preferably the 1-7 % by weight, more preferably the 1.5-6 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be the 82-98 % by weight, is preferably the 84-96 % by weight, more preferably the 86-95 % by weight.In the present invention, while calculating the total amount of described raw material, iron containing compounds is with Fe
2o
3meter, hydrated alumina is with Al
2o
3meter, and described raw material does not comprise the water of introducing in forming process.
In the present invention, described cellulose ether refers to after the hydrogen atom at least part of hydroxyl in cellulosic molecule is replaced by one or more alkyl that the ether formed is derivative, and wherein, a plurality of described alkyl can, for identical, can be also difference.Described alkyl is selected from alkyl and the unsubstituted alkyl of replacement.Described unsubstituted alkyl (for example: C is preferably alkyl
1-C
5alkyl).In the present invention, C
1-C
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 quantity of the hydrogen atom on substituted cellulose molecule hydroxyl, 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 iron containing compounds can be the compound that contains iron atom in the commonly used various molecular structures in this area, for example can be for containing the water soluble compound of iron atom in molecular structure.Preferably, described iron containing compounds is selected from iron chloride, ferric nitrate and ironic citrate.More preferably, described iron containing compounds is selected from iron chloride and ferric nitrate.
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 iron content hydrated alumina forming matter of the present invention, described article shaped is made by described raw material.The mode that is prepared described article shaped by described raw material can be selected for the routine of this area.Preferably, described article shaped is to prepare formed body by described raw material, and described formed body is carried out to drying and 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 and iron containing compounds mixed-forming, thus obtain described formed body; Also can make preform first by hydrated alumina and cellulose ether mixed-forming, load iron containing compounds on this preform then, thus obtain 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 iron containing compounds and at least one cellulose ether are mixed with water, obtains 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, at least one iron containing compounds of load is made.
In this embodiment, on described preform, the mode of at least one iron containing compounds of load can be selected for the routine of this area, for example: can be by described preform is contacted with the solution that contains at least one iron containing compounds, thus described iron containing compounds is loaded on described preform.The mode that described preform is contacted with described solution can be selected for the routine of this area, for example: can described preform be contacted with the solution that contains at least one iron containing compounds by dipping or spray, thereby described iron containing compounds is loaded on described preform.When the mode that adopts dipping loads on described preform by described iron containing compounds, described dipping can be saturated dipping, also can flood for supersaturation.The solvent of the described solution that contains at least one iron containing compounds can be selected for the routine of this area, is preferably water.The concentration of the described solution that contains at least one iron containing compounds is not particularly limited so that load on the amount of the iron containing compounds 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 80-300 ℃, carries out, and more preferably at 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 iron content 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 iron content 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 iron content 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 iron content 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 component 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 iron content 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 iron content 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 iron content 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%, to be generally below 5%.
In the present invention, the δ value, for estimating the strength retention of article shaped, is defined by following formula:
Wherein, Q
1for the radially crushing strength of the article shaped without water soaking, in N/mm, Q
2for through water soaking 30 minutes and in the radially crushing strength of the article shaped of 120 ℃ of dryings after 4 hours, in N/mm.
According to iron content hydrated alumina forming matter of the present invention, without radially crushing strength (that is, the Q of the article shaped of water soaking
1) can, for more than 12N/mm, be even more than 15N/mm.Particularly, can be for 15-30N/mm(as 15-25N/mm according to the radially crushing strength of the article shaped without water soaking of the present invention).
In the present invention, described radially crushing strength according to " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety front page, the volumes such as Yang Cuiding) in the RIPP 25-90 of record the method stipulated measure.
According to iron content hydrated alumina forming matter of the present invention, the water absorption rate of described article shaped is 0.4-1.5.Preferably, the water absorption rate of described article shaped is 0.6-1, is generally 0.6-0.9.
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:
Iron content hydrated alumina forming matter of the present invention not only has good absorbent properties, and has excellent strength retention, even long-time immersion still has higher intensity in water.Therefore, iron content 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 the iron content hydrated alumina forming matter, the method comprises by the raw material that contains at least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether and prepares formed body, and described formed body is carried out to drying.
The method according to this invention, the raw material that contains at least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether by use, do not used peptizing agent, can prepare article shaped yet.The composition of described raw material can carry out suitable selection according to the expection application scenario of article shaped.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 1-9 % by weight, more preferably the 3-8 % by weight; With Fe
2o
3the total content of the described iron containing compounds of meter can be the 0.5-8 % by weight, is preferably the 1-7 % by weight, more preferably the 1.5-6 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be the 82-98 % by weight, is preferably the 84-96 % by weight, more preferably the 86-95 % by weight.
The method according to this invention, the kind of described cellulose ether, iron containing compounds 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 and iron containing compounds mixing aftershaping, thus obtain described formed body; Also can be first hydrated alumina and cellulose ether be mixed and moulding, make preform, load iron containing compounds on this preform then, thus obtain described formed body.
Of the present invention a kind of preferred embodiment in, the mode that is prepared described formed body by described raw material comprises: at least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether are mixed with water, obtain the first mixture, and by described the first mixture moulding.
In another preferred embodiment of the present invention, the mode 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 iron containing compounds of load on described preform.
In this embodiment, can adopt this area variety of way commonly used that described iron containing compounds is loaded on described preform, for example: described preform can be contacted with the solution that contains at least one iron containing compounds, thereby described iron containing compounds is loaded on described preform.The mode that described preform is contacted with the solution that contains at least one iron containing compounds can be selected for the routine of this area, for example: can described preform be contacted with the solution that contains at least one iron containing compounds by dipping or spray, thereby described iron containing compounds is loaded on described preform.When the mode that adopts dipping loads on described preform by described iron containing compounds, described dipping can be saturated dipping, also can flood for supersaturation.The solvent of the described solution that contains at least one iron containing compounds can be selected for the routine of this area, is preferably water.The concentration of the described solution that contains at least one iron containing compounds is not particularly limited so that load on the amount of the iron containing compounds 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 ℃, 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.
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, can select the temperature of described formed body drying 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, meets instructions for use with volatile matter content in the article shaped that can make finally to obtain and 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 iron content hydrated alumina forming matter (that is, only drying and unfired article shaped) has good strength retention and absorbent properties.Usually, the radially crushing strength of the iron content hydrated alumina forming matter prepared by method of the present invention can be even more than 15N/mm for more than 12N/mm, for example can be for 15-30N/mm(as 15-25N/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, is generally 0.6-0.9.
Therefore, prepared according to the methods of the invention iron content hydrated alumina forming matter is suitable for use as drier or comes load to have the active component of catalytic action as the carrier of loaded catalyst.
Thus, a third aspect of the present invention provides a kind of iron content hydrated alumina forming matter prepared by method of the present invention.
A fourth aspect of the present invention provides a kind of iron content aluminium oxide article shaped, and this article shaped is carried out iron content hydrated alumina forming matter provided by the 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.
Iron content 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 iron content aluminium oxide article shaped provided by the invention 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, is generally 0.6-0.9.
A fifth aspect of the present invention provide a kind of according to iron content hydrated alumina forming matter of the present invention or iron content 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 iron content hydrated alumina or the iron content 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 iron content hydrated alumina forming matter of the present invention and iron content aluminium oxide article shaped, is particularly suitable for as the carrier with catalyst of hydrogenation catalyst effect.
In iron content hydrated alumina forming matter according to the present invention or iron content 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 will there is the active constituent loading of hydrogenation catalyst effect on iron content hydrated alumina forming matter according to the present invention or iron content 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 at the temperature of 120 ℃ dry 4 hours, the radially crushing strength of measuring dry solid according to the method for stipulating in RIPP 25-90 (was designated as Q
2), adopt following formula to calculate the δ value,
In following examples and Comparative Examples, adopt following methods to measure the water absorption rate of 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 is by measuring testing sample in 4 hours 600 ℃ of roastings.
Embodiment 1-10 is for illustrating iron content hydrated alumina forming matter of the present invention and preparation method thereof.
Embodiment 1
Follow stirring, by 10.0g iron chloride (FeCl
36H
2o) be dissolved in the 90mL deionized water, obtain ferric chloride solution.100.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 4.0g methylcellulose (purchased from sea, Zhejiang Shen chemical industry Co., Ltd), 3.0g sesbania powder and above-mentioned ferric chloride solution 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, thereby obtains according to iron content hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Comparative Examples 1
Follow stirring, by 10.0g iron chloride (FeCl
36H
2o) be dissolved in the 90mL deionized water, obtain ferric chloride solution.100.0g boehmite powder (with embodiment 1), 2.5mL red fuming nitric acid (RFNA), 3.0g sesbania powder and above-mentioned ferric chloride solution 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, obtains article shaped.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Comparative Examples 2
Adopt the method identical with Comparative Examples 1 to prepare article shaped, different, the wet bar drying of extruding is followed afterwards 600 ℃ of roastings 4 hours, thereby obtained article shaped.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Comparative Examples 3
Adopt the method identical with embodiment 1 to prepare article shaped, different, 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 in 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) follow stirring, by 6.0g iron chloride (FeCl
36H
2o) be dissolved in the 95mL deionized water, obtain ferric chloride solution.Amorphous hydrated aluminium oxide prepared by 50.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 50.0g step (1), 2.0g methylcellulose (purchased from sea, Zhejiang Shen chemical industry Co., Ltd), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd) and above-mentioned ferric chloride solution stir.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 iron content hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 3
At the temperature of 60 ℃, follow stirring, by 16.0g iron chloride (FeCl
36H
2o) be dissolved in the 95mL deionized water, obtain ferric chloride solution.By the 60.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 40.0g gibbsite (purchased from Pingguo Aluminium Industry Co., Guangxi, contents on dry basis is 64.5 % by weight), 1.0g methylcellulose (purchased from sea, Zhejiang Shen chemical industry Co., Ltd), 2.0g hydroxypropyl methylcellulose (purchased from sea, Zhejiang Shen chemical industry Co., Ltd), 3.0g sesbania powder and above-mentioned ferric chloride solution stir.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 80 ℃ of dryings 12 hours, thereby obtains according to iron content hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 4
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 5.0g iron chloride (FeCl
36H
2o) mix, then in above-mentioned solid mixture, add the 95mL deionized water, stir.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 according to iron content hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Comparative Examples 4
By 100.0g boehmite SB powder (with embodiment 4), 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) and 5.0g iron chloride (FeCl
36H
2o) mix, then in above-mentioned solid mixture, add the 95mL 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, 150 ℃ of dryings 12 hours, thereby obtains article shaped.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 5
At the temperature of 40 ℃, follow stirring, by 12.0g iron chloride (FeCl
36H
2o) be dissolved in the 90mL deionized water, obtain ferric chloride solution.100.0g boehmite SB powder (purchased from Sasol company, contents on dry basis is 75.0 % by weight), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 2.0g hydroxypropyl methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder and above-mentioned ferric chloride solution are mixed.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 according to iron content hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 6
At the temperature of 50 ℃, follow stirring, by 14.0g iron chloride (FeCl
36H
2o) be dissolved in the 90mL deionized water, obtain ferric chloride solution.100.0g boehmite (purchased from Yantai, Shandong permanent brightness chemical industry Co., Ltd, contents on dry basis is 71.0 % by weight), 5.0g hydroxypropyl methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder and above-mentioned ferric chloride solution are mixed.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 120 ℃ of dryings 4 hours, thereby obtains according to iron content hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Comparative Examples 5
At the temperature of 50 ℃, follow stirring, by 14.0g iron chloride (FeCl
36H
2o) be dissolved in the 90mL deionized water, obtain ferric chloride solution.100.0g boehmite (with embodiment 6), 5.0mL acetic acid, 3.0g sesbania powder and above-mentioned ferric chloride solution are mixed.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 120 ℃ of dryings 4 hours, thereby obtains article shaped.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 7
Adopt the method identical with embodiment 6 to prepare the iron content hydrated alumina forming matter, different, the content of hydroxypropyl methylcellulose is 6.8g, thereby obtains according to iron content hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 8
Follow stirring, by 10.0g ferric nitrate (Fe (NO
3)
39H
2o) be dissolved in the 85mL deionized water, obtain iron nitrate solution.100.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 4.0g methylcellulose (purchased from sea, Zhejiang Shen chemical industry Co., Ltd), 3.0g sesbania powder and 90mL deionized water 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, obtains dry bar.Above-mentioned dry bar dipping is placed in to above-mentioned iron nitrate solution and floods 30min, the bar that will wet is placed in baking oven 150 ℃ of dryings 12 hours, thereby obtains according to iron content hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 9
Adopt the method identical with embodiment 3 to prepare article shaped, different is, the wet bar obtained is placed in to baking oven, 120 ℃ of dryings 12 hours, thereby obtain according to iron content hydrated alumina forming matter of the present invention, the radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Embodiment 10
Adopt the method identical with embodiment 5 to prepare article shaped, different is, the wet bar obtained is placed in to baking oven, 300 ℃ of dryings 4 hours, thereby obtain according to iron content hydrated alumina forming matter of the present invention, the radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
Table 1
| Numbering | Crushing strength (N/mm) | Water absorption rate | δ value (%) |
| Embodiment 1 | 21.0 | 0.80 | 3.0 |
| Comparative Examples 1 | 19.0 | 0.84 | 64.9 |
| Comparative Examples 2 | 25.3 | 0.79 | 2.2 |
| Embodiment 2 | 18.1 | 0.67 | 2.2 |
| Embodiment 3 | 15.0 | 0.82 | 4.3 |
| Embodiment 4 | 19.4 | 0.70 | 2.2 |
| Comparative Examples 4 | 17.8 | 0.69 | 76.7 |
| Embodiment 5 | 20.6 | 0.72 | 3.0 |
| Embodiment 6 | 16.8 | 0.83 | 3.9 |
| Comparative Examples 5 | 15.5 | 0.77 | 53.0 |
| Embodiment 7 | 18.2 | 0.80 | 3.5 |
| Embodiment 8 | 21.5 | 0.77 | 2.9 |
| Embodiment 9 | 15.7 | 0.88 | 4.1 |
| Embodiment 10 | 20.5 | 0.74 | 3.1 |
The result demonstration of table 1, iron content hydrated alumina forming matter according to the present invention has good strength retention, even still have higher crushing strength after soaking in water.
Embodiment 11-20 is for illustrating iron content aluminium oxide article shaped of the present invention and preparation method thereof.
Embodiment 11
Carry out roasting under the condition that the iron content hydrated alumina forming matter that will prepare according to the method identical with embodiment 1 is listed at table 2, thereby obtain iron content aluminium oxide article shaped of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 2.
Embodiment 12
Carry out roasting under the condition that the iron content hydrated alumina forming matter that will prepare according to the method identical with embodiment 3 is listed at table 2, thereby obtain iron content aluminium oxide article shaped of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 2.
Embodiment 13
Carry out roasting under the condition that the iron content hydrated alumina forming matter that will prepare according to the method identical with embodiment 8 is listed at table 2, thereby obtain iron content aluminium oxide article shaped of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 2.
Table 2
Result in table 2 shows, iron content aluminium oxide article shaped according to the present invention not only has good absorbent properties, also has high radially crushing strength and crushing strength conservation rate radially.
Embodiment 14-23 is for illustrating the application of iron content hydrated alumina forming matter of the present invention as drier.
Embodiment 14-23
Iron content hydrated alumina forming matter prepared by embodiment 1-10 (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,
Test result is listed in table 3.
Embodiment 24-26 is for illustrating the application of iron content aluminium oxide article shaped of the present invention as drier.
Embodiment 24-26
Adopt the method identical with embodiment 14-23 to measure hygroscopic capacity, different, the article shaped of using embodiment 11-13 to prepare 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 14 | Embodiment 1 | 20.0 | 69.3 | 69.3 |
| Embodiment 15 | Embodiment 2 | 20.0 | 70.4 | 60.2 |
| Embodiment 16 | Embodiment 3 | 20.0 | 68.8 | 78.5 |
| Embodiment 17 | Embodiment 4 | 20.0 | 67.6 | 61.3 |
| Embodiment 18 | Embodiment 5 | 20.0 | 76.4 | 62.4 |
| Embodiment 19 | Embodiment 6 | 20.0 | 67.7 | 72.5 |
| Embodiment 20 | Embodiment 7 | 20.0 | 67.0 | 71.4 |
| Embodiment 21 | Embodiment 8 | 20.0 | 69.2 | 67.9 |
| Embodiment 22 | Embodiment 9 | 20.0 | 68.5 | 79.0 |
| Embodiment 23 | Embodiment 10 | 20.0 | 75.7 | 62.3 |
| Embodiment 24 | Embodiment 11 | 20.0 | 100.0 | 60.2 |
| Embodiment 25 | Embodiment 12 | 20.0 | 100.0 | 69.6 |
| Embodiment 26 | Embodiment 13 | 20.0 | 100.0 | 59.2 |
The result of table 3 shows to have good absorbent properties according to iron content hydrated alumina forming matter of the present invention and iron content aluminium oxide article shaped, is suitable for as drier.
Embodiment 27-36 is for illustrating the application of iron content hydrated alumina forming matter of the present invention as the carrier of loaded catalyst.
Embodiment 27
(1) 4.71g basic nickel carbonate (NiO content is 51 % by weight), 12.0g molybdenum oxide and 1.12g phosphoric acid are dissolved in the water, are mixed with 60mL solution; Carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 69.3 % by weight) prepared by the solution impregnation 20.0g embodiment 1 obtained, dip time is 4 hours.After filtration, the solid product that obtains, in 120 ℃ of dryings 4 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 hydrodesulfurization activity of evaluate catalysts B1 on the 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: 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, thus the hydrodesulfurization activity of evaluate catalysts, and result is listed in table 5,
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 6
2.03g basic nickel carbonate (with embodiment 27), 5.18g molybdenum oxide and 0.48g phosphoric acid are dissolved in the water, are mixed with 13.2mL nickel-molybdenum-phosphorus solution.Carrier (diameter is 1.1mm, and particle length is 2-5mm) prepared by the solution impregnation 15.0g Comparative Examples 2 obtained, dip time is 1 hour.After filtration, the solid product that obtains, in 120 ℃ of dryings 4 hours, then, at 600 ℃ of roasting 3h, is obtained to catalyst A 1.Adopt XRF to be analyzed catalyst, result is listed in table 4.Adopt the hydrodesulfurization activity of the method evaluation catalyst A 1 identical with embodiment 27, result is listed in table 5.
Comparative Examples 7
Adopt the method Kaolinite Preparation of Catalyst identical with Comparative Examples 6, different, at 600 ℃, do not carry out roasting, thereby obtain catalyst A 2, its composition is listed in table 4, and hydrodesulfurization activity is listed in table 5.
Embodiment 28
3.43g basic cobaltous carbonate (CoO content is 70 % by weight), 12.00g molybdenum oxide and 1.12g phosphoric acid are dissolved in the water, are mixed with 60mL nickel-molybdenum-phosphorus solution.To obtain the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.4 % by weight) of solution impregnation 20.0g embodiment 2 preparations, dip time is 4 hours.After filtration, the solid that obtains, in 140 ℃ of dryings 4 hours, is obtained to catalyst B 2.Adopt XRF to be analyzed catalyst, result is listed in table 4.Adopt the method evaluation hydrodesulfurization activity identical with embodiment 27, result is listed in table 5.
Embodiment 29
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 17.8mL nickel tungsten solution.Article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 68.8 % by weight) prepared by the solution impregnation 20.0g embodiment 3 obtained, dip time is 1 hour.By the carrier that obtains in 120 ℃ of dryings 4 hours, thereby obtain catalyst B 3.Adopt XRF to be analyzed catalyst, result is listed in table 4.Adopt the method evaluation hydrodesulfurization activity identical with embodiment 27, result is listed in table 5.
Embodiment 30
2.48g basic nickel carbonate (NiO content is 51 % by weight), 6.30g molybdenum oxide and 0.58g phosphoric acid are dissolved in the water, are mixed with 60mL nickel-molybdenum-phosphorus solution.Article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 67.6 % by weight) prepared by the solution impregnation 20.0g embodiment 4 obtained, dip time is 4 hours.After filtration, by the solid product that obtains in 120 ℃ of dryings 4 hours, thereby obtain catalyst B 4.Adopt XRF to be analyzed catalyst, result is listed in table 4.Adopt the method evaluation hydrodesulfurization activity identical with embodiment 27, result is listed in table 5.
Embodiment 31
3.53g basic nickel carbonate (NiO content is 51 % by weight), 9.00g molybdenum oxide and 0.84g phosphoric acid are dissolved in the water, are mixed with 60mL nickel-molybdenum-phosphorus solution.Article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 76.4 % by weight) prepared by the solution impregnation 20.0g embodiment 5 obtained, dip time is 4 hours.After filtration, by the solid that obtains in 150 ℃ of dryings 3 hours, thereby obtain catalyst B 5.Adopt XRF to be analyzed catalyst, result is listed in table 4.Adopt the method evaluation hydrodesulfurization activity identical with embodiment 27, result is listed in table 5.
Embodiment 32
9.18g basic nickel carbonate (NiO content is 51 % by weight), 20.60g molybdenum oxide and 2.18g phosphoric acid are dissolved in the water, are mixed with 60mL nickel-molybdenum-phosphorus solution.Article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 67.7 % by weight) prepared by the solution impregnation 20.0g embodiment 6 obtained, dip time is 4 hours, temperature is 60 ℃.After filtration, by the solid product that obtains in 120 ℃ of dryings 4 hours, thereby obtain catalyst B 6.Adopt XRF to be analyzed catalyst, result is listed in table 4.Adopt the method evaluation hydrodesulfurization activity identical with embodiment 27, result is listed in table 5.
Embodiment 33
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 32, different, the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 67.0 % by weight) that carrier is embodiment 7 preparations, obtain catalyst B 7.Adopt XRF to be analyzed catalyst, result is listed in table 4.Adopt the method evaluation hydrodesulfurization activity identical with embodiment 27, result is listed in table 5.
Embodiment 34
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 27, different, the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 69.2 % by weight) that carrier is embodiment 8 preparations, obtain catalyst B 8.Adopt XRF to be analyzed catalyst, result is listed in table 4.Adopt the method evaluation hydrodesulfurization activity identical with embodiment 27, result is listed in table 5.
Embodiment 35
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 29, different, the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 68.5 % by weight) that carrier is embodiment 9 preparations, obtain catalyst B 9.Adopt XRF to be analyzed catalyst, result is listed in table 4.Adopt the method evaluation hydrodesulfurization activity identical with embodiment 27, result is listed in table 5.
Embodiment 36
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 31, different, carrier is carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 75.7 % by weight) prepared by embodiment 10 steps (1), thereby obtains catalyst B 10.Adopt XRF to be analyzed catalyst, result is listed in table 4.Adopt the method evaluation hydrodesulfurization activity identical with embodiment 27, result is listed in table 5.
Table 4
Table 5
| Numbering | The catalyst numbering | Desulfurization degree (%) |
| Embodiment 27 | B1 | 77.1 |
| Comparative Examples 6 | A1 | 50.2 |
| Comparative Examples 7 | A2 | 47.1 |
| Embodiment 28 | B2 | 71.2 |
| Embodiment 29 | B3 | 68.9 |
| Embodiment 30 | B4 | 67.5 |
| Embodiment 31 | B5 | 76.9 |
| Embodiment 32 | B6 | 84.0 |
| Embodiment 33 | B7 | 83.4 |
| Embodiment 34 | B8 | 78.2 |
| Embodiment 35 | B9 | 69.1 |
| Embodiment 36 | B10 | 76.0 |
Embodiment 37-39 is for illustrating the application of iron content aluminium oxide article shaped of the present invention as the carrier of loaded catalyst.
Embodiment 37
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 27 and the hydrodesulfurization activity of catalyst is estimated, different, the iron content aluminium oxide article shaped that carrier is embodiment 11 preparations, thus obtain catalyst B 11.The composition of catalyst is listed in table 6, and the hydrodesulfurization activity of catalyst is listed in table 7.
Embodiment 38
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 29 and the hydrodesulfurization activity of catalyst is estimated, different, the iron content aluminium oxide article shaped that carrier is embodiment 12 preparations, thus obtain catalyst B 12.The composition of catalyst is listed in table 6, and the hydrodesulfurization activity of catalyst is listed in table 7.
Embodiment 39
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 34 and the hydrodesulfurization activity of catalyst is estimated, different, the iron content aluminium oxide article shaped that carrier is embodiment 13 preparations, thus obtain catalyst B 13.The composition of catalyst is listed in table 6, and the hydrodesulfurization activity of catalyst is listed in table 7.
Table 6
Table 7
| Numbering | The catalyst numbering | Desulfurization degree (%) |
| Embodiment 37 | B11 | 67.5 |
| Embodiment 38 | B12 | 57.9 |
| Embodiment 39 | B13 | 68.2 |
Data in table 5 and table 7 show, the catalyst with hydrogenation catalyst effect prepared as carrier by the article shaped according to the present invention of usining demonstrates higher catalytic activity in the hydrotreatment of hydrocarbon ils.
Claims (20)
1. an iron content hydrated alumina forming matter, this article shaped is made by the raw material that contains at least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether, and 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 iron containing compounds and at least one cellulose ether 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 at least one iron containing compounds of load is made on described preform.
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, with Fe
2o
3the total content of the described iron containing compounds of meter is the 0.5-8 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 82-98 % by weight.
5. article shaped according to claim 4, wherein, the total amount of described raw material of take is benchmark, the total content of described cellulose ether is the 3-8 % by weight, with Fe
2o
3the total content of the described iron containing compounds of meter is the 1.5-6 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 86-95 % by weight.
6. 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.
7. according to the described article shaped of any one in claim 1-3, wherein, described iron containing compounds is selected from iron chloride, ferric nitrate and ironic citrate;
Described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
8. 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.
9. a method for preparing the iron content hydrated alumina forming matter, the method comprises by the raw material that contains at least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether and prepares formed body, and described formed body is carried out to drying.
10. method according to claim 9, wherein, the mode that is prepared described formed body by described raw material comprises:
At least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether 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 iron containing compounds of load on described preform.
11. method according to claim 9, wherein, the temperature of described drying is more than 60 ℃ and lower than 350 ℃.
12. method according to claim 11, wherein, the temperature of described drying is 80-300 ℃.
13., according to the described method of claim 9 or 10, wherein, the total amount of described raw material of take is benchmark, the total content of described cellulose ether is the 0.5-10 % by weight, with Fe
2o
3the total content of the described iron containing compounds of meter is the 0.5-8 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 82-98 % by weight.
14. method according to claim 13, wherein, the total amount of described raw material of take is benchmark, and the total content of described cellulose ether is the 3-8 % by weight, with Fe
2o
3the total content of the described iron containing compounds of meter is the 1.5-6 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 86-95 % by weight.
15., according to the described method of claim 9 or 10, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
16., according to the described method of claim 9 or 10, wherein, described iron containing compounds is selected from iron chloride, ferric nitrate and ironic citrate;
Described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
17. the iron content hydrated alumina forming matter that in claim 9-16 prepared by the described method of any one.
18. an iron content aluminium oxide article shaped, this article shaped is carried out the described iron content hydrated alumina forming matter of any one in claim 1-8 and 17 roasting and makes.
19. in claim 1-8 and 17, the described iron content hydrated alumina forming matter of any one or the described iron content aluminium oxide of claim 18 article shaped are as drier or as the application of the carrier of loaded catalyst.
20. application according to claim 19, wherein, described catalyst is the catalyst with hydrogenation catalyst effect.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266188A (en) * | 1991-04-22 | 1993-11-30 | Amoco Corporation | Selective hydrotreating |
| US5358633A (en) * | 1993-05-28 | 1994-10-25 | Texaco Inc. | Hydrodesulfurization of cracked naphtha with low levels of olefin saturation |
| CN101260317A (en) * | 2007-03-08 | 2008-09-10 | 北京三聚环保新材料有限公司 | Hydrorefining catalyst and its preparation method |
| CN102451743A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
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2012
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266188A (en) * | 1991-04-22 | 1993-11-30 | Amoco Corporation | Selective hydrotreating |
| US5358633A (en) * | 1993-05-28 | 1994-10-25 | Texaco Inc. | Hydrodesulfurization of cracked naphtha with low levels of olefin saturation |
| CN101260317A (en) * | 2007-03-08 | 2008-09-10 | 北京三聚环保新材料有限公司 | Hydrorefining catalyst and its preparation method |
| CN102451743A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
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