CN103480327B - Iron content hydrated alumina forming matter and preparation method and iron content aluminium oxide article shaped and application - Google Patents
Iron content hydrated alumina forming matter and preparation method and iron content aluminium oxide article shaped and application Download PDFInfo
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Abstract
The invention provides a kind of iron content hydrated alumina forming matter and its preparation method and application, this article shaped is made up of the raw material containing 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, δ value is less than 10%, Q
1for more than 12N/mm.Present invention also offers a kind of iron content aluminium oxide article shaped, iron content hydrated alumina forming matter of the present invention is carried out roasting and makes by this article shaped.Present invention also offers the application of article shaped according to the present invention as drier or the carrier as loaded catalyst.Iron content hydrated alumina forming matter of the present invention, not containing peptizing agent, has good strength retention, even if carry out the phenomenon that long-time dipping also can not or there will not be dissolving, efflorescence and duct to cave in substantially in maceration extract.Method of the present invention does not use 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 good pore structure and heat-resistant stability, and higher specific area, therefore aluminium oxide article shaped is commonly used for the carrier of drier or loaded catalyst.Modulation can be carried out to the character of aluminium oxide, with the requirement making it meet specific occasion by introducing ferro element in aluminium oxide article shaped.Such as, adopt iron content aluminium oxide article shaped to prepare hydrogenation catalyst as carrier, modulation can be carried out to the hydrofinishing performance of catalyst.
Iron content aluminium oxide article shaped can by mixing hydrated alumina with water, peptizing agent and optional extrusion aid, and mixture is successively carried out shaping, dry and high-temperature roasting and obtain aluminium oxide article shaped, then then carry out drying and roasting by the solution impregnation article shaped containing iron containing compounds and obtain; Can also by hydrated alumina and iron containing compounds mixs with water, peptizing agent and optional extrusion aid, mixture priority carried out shaping, drying and high-temperature roasting and obtain.
Drying and without high-temperature roasting article shaped (namely, iron content hydrated alumina forming matter) when the carrier being used as loaded catalyst is had the active component of catalytic action by the method load of dipping or is used as drier, be easy to dissolve, phenomenon that efflorescence and duct cave in, thus make article shaped lose shape, therefore only drying and article shaped without high-temperature roasting can not directly as drier or as dipping carrier, the process that must experience a high-temperature roasting could as drier or as dipping carrier.
And; usual use acid (such as: nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid) is as peptizing agent; the existence of acid is easy to corrode former on the one hand; a large amount of sour gas is discharged on the other hand in drying and roasting process; both unfavorable to the health of operating personnel, be also unfavorable for environmental protection.
Summary of the invention
The object of the invention is to overcome prior art and must use peptizing agent when preparing iron content aluminium oxide article shaped, and the technical problem that unfired iron content hydrated alumina forming matter strength retention is low.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 if carry out the phenomenon that long-time immersion also can not or there will not be dissolving, efflorescence and duct to cave in substantially in the solution; Present invention also offers a kind of iron content aluminium oxide article shaped, this iron content aluminium oxide article shaped is formed by iron content hydration aluminium oxide calcining provided by the invention, in forming process, do not use peptizing agent.
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 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 be make as raw material various powder adhesion together, but in absorption and dipping process, because peptizing agent dissolves, run off in a large number from article shaped, and then make article shaped occur dissolving, efflorescence and duct cave in phenomenon, final forfeiture shape.
The present inventor is through further investigation, surprisingly find: in the forming process of iron content hydrated alumina, do not use peptizing agent, introduce cellulose ether simultaneously, even if the article shaped of preparation like this does not carry out high-temperature roasting, also there is good strength retention, in maceration extract, carry out the phenomenon that long-time dipping also can not or there will not be dissolving, efflorescence and duct to cave in substantially, and this article shaped also has good absorbent properties.This completes the present invention.
A first aspect of the present invention provides a kind of iron content hydrated alumina forming matter, this article shaped is made up of the raw material containing 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, δ value is less than 10%, Q
1for more than 12N/mm, wherein,
Q
1for the radial crushing strength of the article shaped without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radial crushing strength of the article shaped of 120 DEG C of dryings after 4 hours, in N/mm.
A second aspect of the present invention provides a kind of method preparing iron content hydrated alumina forming matter, the method comprises prepares formed body by the raw material containing at least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether, and described formed body is carried out 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 iron content hydrated alumina forming matter of the present invention is carried out roasting and makes by this article shaped.
A fifth aspect of the present invention provides a kind of according to the application as drier or the carrier as loaded catalyst of iron content hydrated alumina forming matter of the present invention or iron content aluminium oxide article shaped.
According to iron content hydrated alumina forming matter of the present invention not containing peptizing agent (such as: Alumina gel, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid), there is good strength retention, even if carry out the phenomenon that long-time dipping also can not or there will not be dissolving, efflorescence and duct to cave in substantially in maceration extract.Thus, even if do not carry out high-temperature roasting according to iron content hydrated alumina forming matter of the present invention also can be used as drier or the carrier as loaded catalyst.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, radial crushing strength according to iron content hydrated alumina forming matter of the present invention and iron content aluminium oxide article shaped can reach more than 12N/mm respectively, water absorption rate can reach 0.4-1.5 respectively, and δ value (that is, the radial crushing strength loss late after immersion) can be less than 10% respectively.
According to method of the present invention, do not use peptizing agent (that is, described raw material is not containing peptizing agent) in forming process, decrease the corrosion to former on the one hand, extend the service life of former, reduce production cost; Greatly reduce the amount of the sour gas discharged in dry and roasting process on the other hand, reduce the impact on operator ' s health, also help environmental protection simultaneously.
Detailed description of the invention
A first aspect of the present invention provides a kind of iron content hydrated alumina forming matter, and described article shaped is made up of the raw material containing 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 not containing peptizing agent, the iron content hydrated alumina forming matter made has good absorbent properties, after steeping still there is good strength retention simultaneously.
According to iron content hydrated alumina forming matter of the present invention, the composition for the formation of the raw material of described article shaped can carry out suitable selection according to the expection application scenario of article shaped.Usually, with the total amount of described raw material for benchmark, the total content of described cellulose ether can be 0.5-10 % by weight, is preferably 1-9 % by weight, is more preferably 3-8 % by weight; With Fe
2o
3the total content of the described iron containing compounds of meter can be 0.5-8 % by weight, is preferably 1-7 % by weight, is more preferably 1.5-6 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be 82-98 % by weight, is preferably 84-96 % by weight, is more preferably 86-95 % by weight.In the present invention, when 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 introduced in forming process.
In the present invention, described cellulose ether refers to the ether system derivative formed after the hydrogen atom at least part of hydroxyl in cellulosic molecule is replaced by one or more alkyl, and wherein, multiple described alkyl can be identical, also can be different.Described alkyl is selected from the alkyl of replacement and unsubstituted alkyl.Described unsubstituted alkyl is preferably alkyl (such as: C
1-C
5alkyl).In the present invention, C
1-C
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 can be such as by the alkyl of hydroxyl or carboxyl substituted (such as: C
1-C
5the alkyl be optionally substituted by a hydroxyl group, C
1-C
5by the alkyl of carboxyl substituted), its instantiation can include but not limited to: methylol, ethoxy, hydroxypropyl, hydroxyl butyl, carboxymethyl, carboxyethyl and carboxylic propyl group.
The present invention is not particularly limited for the substituent quantity of the kind of described cellulose ether and the hydrogen atom in substituted cellulose molecule on 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, the compound containing iron atom in the various molecular structures that described iron containing compounds can be commonly used for this area can be such as the water soluble compound containing 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 be that the routine of this area is selected.Preferably, described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.More preferably, described hydrated alumina is boehmite.
According to iron content hydrated alumina forming matter of the present invention, described article shaped is made up of described raw material.The mode being prepared described article shaped by described raw material can be selected for the routine of this area.Preferably, described article shaped prepares formed body by described raw material, and described formed body is carried out drying make.
The various methods that this area can be adopted conventional, to prepare described formed body, are not particularly limited.Such as: directly by hydrated alumina, cellulose ether and iron containing compounds mixed-forming, thus described formed body can be obtained; Also can first by hydrated alumina and cellulose ether mixed-forming, obtained preform, then load iron containing compounds on this preform, thus obtain described formed body.
One of the present invention preferred embodiment in, described formed body is mixed with water at least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether, obtains the first mixture, and make shaping for described first mixture.
In another preferred embodiment of the present invention, described formed body is mixed with water at least one hydrated alumina and at least one cellulose ether, obtain the second mixture, and described second mixture is successively carried out shaping and dehydration, obtain preform, on described preform, load at least one iron containing compounds is made.
In this embodiment, on described preform, the mode of load at least one iron containing compounds can be the routine selection of this area, such as: can by described preform is contacted with the solution containing at least one iron containing compounds, thus by described iron containing compounds load on described preform.The mode contacted with described solution by described preform can be selected for the routine of this area, such as: by flooding or spraying, described preform can be contacted with the solution containing at least one iron containing compounds, thus by described iron containing compounds load on described preform.Adopt dipping mode by described iron containing compounds load on described preform time, described dipping can be saturated dipping, also can flood for supersaturation.The solvent of the described solution containing at least one iron containing compounds can be the routine selection of this area, is preferably water.The concentration of the described solution containing at least one iron containing compounds is not particularly limited, with enable the amount of the iron containing compounds of load on described preform meet the demands (such as previously described content) be as the criterion.
In this embodiment, the condition of described dehydration is not particularly limited, and can be that the routine of this area is selected, be as the criterion can remove water.Usually, described dehydration can be carried out lower than at the temperature of 350 DEG C more than 60 DEG C, preferably carries out at 80-300 DEG C, more preferably carries out at 120-250 DEG C.The time of described dehydration can carry out suitable selection according to the temperature of dehydration, is not particularly limited.Usually, the time of described dehydration can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
According to iron content hydrated alumina forming matter of the present invention, the consumption for the preparation of the water of described first mixture or described second mixture is not particularly limited, as long as the consumption of water can guarantee various component to mix.
According to iron content hydrated alumina forming matter of the present invention, described shaping mode is not particularly limited, and can adopt the various molding modes that this area is conventional, such as: extrusion, spraying, round as a ball, compressing tablet or their combination.One of the present invention preferred embodiment in, come shaping by the mode of extrusion.
According to iron content hydrated alumina forming matter of the present invention, described article shaped can have various shape according to concrete instructions for use, such as: spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.
According to iron content hydrated alumina forming matter of the present invention, can be that the routine of this area is selected by the temperature of described formed body drying.Usually, the temperature of described drying can be more than 60 DEG C and lower than 350 DEG C, be preferably 80-300 DEG C, be more preferably 120-250 DEG C.The time of described drying can carry out suitable selection according to the temperature of drying, meets instructions for use be as the criterion can make volatile component content in the article shaped that finally obtains.Usually, the time of described drying can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
According to 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 that the routine of this area is selected.Usually, with the total amount of described raw material for benchmark, the content of described extrusion aid can be 0.1-8 % by weight, is preferably 0.5-5 % by weight.According to iron content hydrated alumina forming matter of the present invention, described extrusion aid is preferably starch (that is, described raw material is also containing starch).As the starch in the various sources that the starch of extrusion aid can be commonly used for this area, such as: by vegetable seeds through pulverizing the powder obtained, as sesbania powder.Described extrusion aid can adopt the conventional various methods in this area to add in raw material, such as: can be added in above-mentioned first mixture and the second mixture by described extrusion aid respectively.
According to iron content hydrated alumina forming matter of the present invention, described article shaped radial crushing strength loss late (that is, δ value) is after steeping less than 10%, is generally less than 5%.
In the present invention, δ value, for evaluating the strength retention of article shaped, is defined by following formula:
Wherein, Q
1for the radial crushing strength of the article shaped without water soaking, in N/mm, Q
2for through water soaking 30 minutes and in the radial crushing strength of the article shaped of 120 DEG C of dryings after 4 hours, in N/mm.
According to iron content hydrated alumina forming matter of the present invention, without radial crushing strength (that is, the Q of the article shaped of water soaking
1) can be more than 12N/mm, be even more than 15N/mm.Particularly, can be that 15-30N/mm(is as 15-25N/mm according to the radial crushing strength of the article shaped without water soaking of the present invention).
In the present invention, described radial crushing strength according to " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety the first edition, the volumes such as Yang Cuiding) in the RIPP25-90 that records the method that specifies measure.
According to 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 the dry excessive deionized water of article shaped soaks the ratio of the weight of the weight change value of 30 minutes front and back and the article shaped of described drying.Concrete method of testing is: by article shaped to be measured 120 DEG C of dryings 4 hours, then sieves with 40 object standard screens, takes 20g oversize and (be designated as w as testing sample
1), testing sample 50g deionized water is soaked 30 minutes, after filtration, solid phase is drained 5 minutes, the weight then weighing the solid phase drained (is designated as w
2), with following formulae discovery water absorption rate:
Iron content hydrated alumina forming matter of the present invention not only has good absorbent properties, and has excellent strength retention, even if 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 preparing iron content hydrated alumina forming matter, the method comprises prepares formed body by the raw material containing at least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether, and described formed body is carried out drying.
According to method of the present invention, by using the raw material containing at least one hydrated alumina, at least one iron containing compounds and at least one cellulose ether, not using peptizing agent, also can prepare article shaped.The composition of described raw material can carry out suitable selection according to the expection application scenario of article shaped.Usually, with the total amount of described raw material for benchmark, the total content of described cellulose ether can be 0.5-10 % by weight, is preferably 1-9 % by weight, is more preferably 3-8 % by weight; With Fe
2o
3the total content of the described iron containing compounds of meter can be 0.5-8 % by weight, is preferably 1-7 % by weight, is more preferably 1.5-6 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be 82-98 % by weight, is preferably 84-96 % by weight, is more preferably 86-95 % by weight.
According to method of the present invention, the kind of described cellulose ether, iron containing compounds and hydrated alumina, with described identical above, does not repeat them here.
According to method of the present invention, the various methods that this area can be adopted conventional, to prepare described formed body, are not particularly limited.Such as: directly by hydrated alumina, cellulose ether and iron containing compounds mixing aftershaping, thus described formed body can be obtained; Also can be first shaping by hydrated alumina and cellulose ether mixing, obtained preform, then load iron containing compounds on this preform, thus obtain described formed body.
One of the present invention preferred embodiment in, the mode being 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 shaping for described first mixture.
In another preferred embodiment of the present invention, the mode being prepared described formed body by described raw material comprises: at least one hydrated alumina and at least one cellulose ether are mixed with water, obtain the second mixture, and described second mixture is successively carried out shaping and dehydration, obtain preform, load at least one iron containing compounds on described preform.
In this embodiment, the various modes that this area can be adopted conventional by described iron containing compounds load on described preform, such as: described preform can be contacted with the solution containing at least one iron containing compounds, thus by described iron containing compounds load on described preform.The mode contacted with the solution containing at least one iron containing compounds by described preform can be selected for the routine of this area, such as: by flooding or spraying, described preform can be contacted with the solution containing at least one iron containing compounds, thus by described iron containing compounds load on described preform.Adopt dipping mode by described iron containing compounds load on described preform time, described dipping can be saturated dipping, also can flood for supersaturation.The solvent of the described solution containing at least one iron containing compounds can be the routine selection of this area, is preferably water.The concentration of the described solution containing at least one iron containing compounds is not particularly limited, with enable the amount of the iron containing compounds of load on described preform meet the demands (such as previously described content) be as the criterion.
In this embodiment, the condition of described dehydration is not particularly limited, and can be that the routine of this area is selected, be as the criterion can remove water.Usually, described dehydration can be carried out lower than at the temperature of 350 DEG C more than 60 DEG C, preferably at the temperature of 80-300 DEG C, more preferably carries out at the temperature of 120-250 DEG C.The time of described dehydration can carry out suitable selection according to the temperature of dehydration, is not particularly limited.Usually, the time of described dehydration can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
According to method of the present invention, the consumption for the preparation of the water of described first mixture or described second mixture is not particularly limited, as long as the consumption of water can guarantee various component to mix.
According to method of the present invention, described shaping mode is not particularly limited, and can adopt the various molding modes that this area is conventional, such as: extrusion, spraying, round as a ball, compressing tablet or their combination.One of the present invention preferred embodiment in, come shaping by the mode of extrusion.
According to method of the present invention, described article shaped can have various shape according to concrete instructions for use, such as: spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.
According to method of the present invention, can be that the routine of this area is selected by the temperature of described formed body drying.Usually, the temperature of described drying can be more than 60 DEG C and lower than 350 DEG C, be preferably 80-300 DEG C, be more preferably 120-250 DEG C.The time of described drying can carry out suitable selection according to the temperature of drying, meets instructions for use be as the criterion can make volatile matter content in the article shaped that finally obtains.Usually, the time of described drying can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
According to method of the present invention, described raw material can also contain at least one extrusion aid.The consumption of described extrusion aid and kind can be that the routine of this area is selected.Usually, with the total amount of described raw material for benchmark, the content of described extrusion aid can be 0.1-8 % by weight, is preferably 0.5-5 % by weight.According to method of the present invention, described extrusion aid is preferably starch (that is, described raw material is also containing starch).As the starch in the various sources that the starch of extrusion aid can be commonly used for this area, such as: by vegetable seeds through pulverizing the powder obtained, as sesbania powder.Described extrusion aid can adopt the conventional various methods in this area to add in raw material, such as: can be added in above-mentioned first mixture and the second mixture by described extrusion aid respectively.
Prepared according to the methods of the invention iron content hydrated alumina forming matter (that is, only drying and unfired article shaped) has good strength retention and absorbent properties.Usually, the radial crushing strength of the iron content hydrated alumina forming matter prepared by method of the present invention can be more than 12N/mm, and being even more than 15N/mm, such as, can be that 15-30N/mm(is as 15-25N/mm); δ value is less than 10%, is generally less than 5%; Water absorption rate is 0.4-1.5, such as, can be 0.6-1, be 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 carrys out as the carrier of loaded catalyst the active component that load has catalytic action.
Thus, a third aspect of the present invention provides a kind of 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 iron content hydrated alumina forming matter provided by the invention is carried out roasting and makes by this article shaped.
The present invention is not particularly limited for the condition of roasting, can be that the routine of this area is selected.Particularly, the temperature of described roasting can be 450-950 DEG C, is preferably 500-900 DEG C; The time of described roasting can be 2-8 hour, is preferably 3-6 hour.
Iron content aluminium oxide article shaped according to the present invention has high intensity and strength retention and good absorbent properties.Usually, the radial crushing strength of iron content aluminium oxide article shaped provided by the invention can be more than 12N/mm, is even more than 15N/mm, such as, can be 15-30N/mm; δ value is less than 10%, is generally less than 5%; Water absorption rate is 0.4-1.5, such as, can be 0.6-1, be generally 0.6-0.9.
A fifth aspect of the present invention provides a kind of according to the application as drier or the carrier as loaded catalyst of iron content hydrated alumina forming matter of the present invention or iron content aluminium oxide article shaped.
In the present invention, described loaded catalyst can for this area commonly use various can using iron content hydrated alumina or iron content aluminium oxide article shaped as the catalyst of carrier.Preferably, described catalyst is the catalyst with hydrogenation catalyst effect, is namely particularly suitable for the carrier as 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.
In iron content hydrated alumina forming matter according to the present invention or iron content aluminium oxide article shaped as when there is the carrier of catalyst of hydrogenation catalyst effect, the various methods that this area can be adopted to commonly use will have 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, such as: can by using the aqueous impregnation article shaped of the present invention containing described active component, then the article shaped of described active component load is had to carry out drying and optional roasting, thus obtain the catalyst with hydrogenation catalyst effect.
The present invention is described in detail below in conjunction with embodiment and comparative example.
In following examples and comparative example, the method specified in RIPP25-90 is adopted to measure the radial crushing strength of the article shaped of preparation.
In following examples and comparative example, following methods is adopted to measure the δ value of the article shaped of preparation: to adopt the method mensuration that specifies in RIPP25-90 (to be designated as Q without the radial crushing strength of the article shaped of water soaking
1); The article shaped of preparation is placed in 50g deionized water, soaks 30 minutes, then filter, by the solid that obtains at the temperature of 120 DEG C dry 4 hours, the radial crushing strength measuring dry solid according to the method specified in RIPP25-90 (was designated as Q
2), adopt following formulae discovery δ value,
In following examples and comparative example, following methods is adopted to measure the water absorption rate of the article shaped of preparation: by article shaped to be measured 120 DEG C of dryings 4 hours, then to sieve with 40 object standard screens, take 20g oversize and (be designated as w as testing sample
1), testing sample 50g deionized water is soaked 30 minutes, after filtration, solid phase is drained 5 minutes, the weight then weighing the solid phase drained (is designated as w
2), with following formulae discovery water absorption rate:
In following examples and comparative example, contents on dry basis is by measuring testing sample 600 DEG C of roastings 4 hours.
Embodiment 1-10 is for illustration of iron content hydrated alumina forming matter of the present invention and preparation method thereof.
Embodiment 1
With stirring, by 10.0g iron chloride (FeCl
36H
2o) be dissolved in 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 Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder and above-mentioned ferric chloride solution are mixed.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven, 150 DEG C of dryings 12 hours, thus obtains according to iron content hydrated alumina forming matter of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Comparative example 1
With stirring, by 10.0g iron chloride (FeCl
36H
2o) be dissolved in 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 extrudes, obtain wet bar.The wet bar extruded is placed in baking oven 150 DEG C of dryings 12 hours, obtains article shaped.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Comparative example 2
Adopt the method identical with comparative example 1 to prepare article shaped, unlike, by after the wet bar drying of extruding then 600 DEG C of roastings 4 hours, thus obtain article shaped.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Comparative example 3
The method identical with embodiment 1 is adopted to prepare article shaped, unlike, do not use methylcellulose, result cannot obtain article shaped.
Embodiment 2
(1) in the retort of a 2L with and the mode of flowing adds the aluminum sulfate solution and sodium aluminate solution (Al that 2000mL concentration is 48g/L
2o
3content is 200g/L, and causticity coefficient is 1.58) carry out precipitation reaction, reaction temperature is 50 DEG C, and pH value is 6.0, and reaction time is 15 minutes; The slurries vacuum filter obtained is filtered, to be filtered complete after, on filter cake supplement add 20L deionized water (temperature is 40 ± 5 DEG C) flush cake about 60 minutes.Filter cake after washing is joined 1.5L deionized water for stirring and becomes slurries, slurries are carried out drying with being pumped in spray dryer, control the outlet temperature of spray dryer within the scope of 100-110 DEG C, the dry materials time is 2 minutes, obtain hydrated alumina, wherein, Al
2o
3content is 63 % by weight, is defined as amorphous state through XRD analysis.
(2) with stirring, by 6.0g iron chloride (FeCl
36H
2o) be dissolved in 95mL deionized water, obtain ferric chloride solution.Amorphous hydrated aluminium oxide, 2.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd) and the above-mentioned ferric chloride solution 50.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 50.0g step (1) prepared stir.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 220 DEG C of dryings 6 hours, thus obtains according to iron content hydrated alumina forming matter of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 3
At the temperature of 60 DEG C, with stirring, by 16.0g iron chloride (FeCl
36H
2o) be dissolved in 95mL deionized water, obtain ferric chloride solution.By 60.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 40.0g gibbsite (purchased from Pingguo Aluminium Industry Co., Guangxi, contents on dry basis is 64.5 % by weight), 1.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 2.0g hydroxypropyl methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder and above-mentioned ferric chloride solution stir.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 80 DEG C of dryings 12 hours, thus obtains according to iron content hydrated alumina forming matter of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 4
By 100.0g boehmite SB powder (purchased from Sasol company, contents on dry basis is 75.0 % by weight), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd) and 5.0g iron chloride (FeCl
36H
2o) mix, then in above-mentioned solid mixture, add 95mL deionized water, stir.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 150 DEG C of dryings 12 hours, obtains according to iron content hydrated alumina forming matter of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Comparative example 4
By 100.0g boehmite SB powder (with embodiment 4), 20mL Alumina gel (purchased from this promise New Chemical Material of Dalian science and technology Co., Ltd, Al
2o
3content is 10 % by weight) and 5.0g iron chloride (FeCl
36H
2o) mix, then in above-mentioned solid mixture, add 95mL deionized water, mix.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 150 DEG C of dryings 12 hours, thus obtains article shaped.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 5
At the temperature of 40 DEG C, with stirring, by 12.0g iron chloride (FeCl
36H
2o) be dissolved in 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 extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 250 DEG C of dryings 4 hours, thus obtains according to iron content hydrated alumina forming matter of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 6
At the temperature of 50 DEG C, with stirring, by 14.0g iron chloride (FeCl
36H
2o) be dissolved in 90mL deionized water, obtain ferric chloride solution.100.0g boehmite (purchased from Yantai, Shandong Heng Hui Chemical Co., Ltd., contents on dry basis is 71.0 % by weight), 5.0g hydroxypropyl methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder and above-mentioned ferric chloride solution are mixed.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 120 DEG C of dryings 4 hours, thus obtains according to iron content hydrated alumina forming matter of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Comparative example 5
At the temperature of 50 DEG C, with stirring, by 14.0g iron chloride (FeCl
36H
2o) be dissolved in 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 extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 120 DEG C of dryings 4 hours, thus obtains article shaped.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 7
The method identical with embodiment 6 is adopted to prepare iron content hydrated alumina forming matter, unlike, the content of hydroxypropyl methylcellulose is 6.8g, thus obtains according to iron content hydrated alumina forming matter of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 8
With stirring, by 10.0g ferric nitrate (Fe (NO
3)
39H
2o) be dissolved in 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 Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder and 90mL deionized water are mixed.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven 150 DEG C of dryings 12 hours, obtains dry bar.Above-mentioned dry bar dipping is placed in above-mentioned iron nitrate solution and floods 30min, wet bar is placed in baking oven 150 DEG C of dryings 12 hours, thus obtains according to iron content hydrated alumina forming matter of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 9
The method identical with embodiment 3 is adopted to prepare article shaped, unlike, the wet bar obtained is placed in baking oven, 120 DEG C of dryings 12 hours, thus obtain according to iron content hydrated alumina forming matter of the present invention, measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Embodiment 10
The method identical with embodiment 5 is adopted to prepare article shaped, unlike, the wet bar obtained is placed in baking oven, 300 DEG C of dryings 4 hours, thus obtain according to iron content hydrated alumina forming matter of the present invention, measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in Table 1.
Table 1
| Numbering | Crushing strength (N/mm) | Water absorption rate | δ value (%) |
| Embodiment 1 | 21.0 | 0.80 | 3.0 |
| Comparative example 1 | 19.0 | 0.84 | 64.9 |
| Comparative example 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 example 4 | 17.8 | 0.69 | 76.7 |
| Embodiment 5 | 20.6 | 0.72 | 3.0 |
| Embodiment 6 | 16.8 | 0.83 | 3.9 |
| Comparative example 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 display of table 1, iron content hydrated alumina forming matter according to the present invention has good strength retention, even if still have higher crushing strength after soaking in water.
Embodiment 11-20 is for illustration of iron content aluminium oxide article shaped of the present invention and preparation method thereof.
Embodiment 11
Carry out roasting under the condition listed at table 2 by the iron content hydrated alumina forming matter prepared according to the method identical with embodiment 1, thus obtain iron content aluminium oxide article shaped of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in table 2.
Embodiment 12
Carry out roasting under the condition listed at table 2 by the iron content hydrated alumina forming matter prepared according to the method identical with embodiment 3, thus obtain iron content aluminium oxide article shaped of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in table 2.
Embodiment 13
Carry out roasting under the condition listed at table 2 by the iron content hydrated alumina forming matter prepared according to the method identical with embodiment 8, thus obtain iron content aluminium oxide article shaped of the present invention.Measure the radial crushing strength of the article shaped obtained, water absorption rate and δ value, result is listed in table 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 radial crushing strength and radial crushing strength conservation rate.
Embodiment 14-23 is for illustration of the application of iron content hydrated alumina forming matter of the present invention as drier.
Embodiment 14-23
The iron content hydrated alumina forming matter prepared by embodiment 1-10 (is designated as N after weighing
1) be placed in atmospheric dryer respectively as drier, then in drier, place the beaker that fills 250mL water, close drier, and place 10 days in room temperature (25 DEG C).Then, taking-up article shaped is weighed and (is designated as N
2), by following formulae discovery hygroscopic capacity,
Test result is listed in table 3.
Embodiment 24-26 is for illustration of the application of iron content aluminium oxide article shaped of the present invention as drier.
Embodiment 24-26
The method identical with embodiment 14-23 is adopted to measure hygroscopic capacity, unlike, article shaped prepared by use embodiment 11-13 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 display of table 3, has 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 illustration of 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; The carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 69.3 % by weight) the solution impregnation 20.0g embodiment 1 obtained prepared, dip time is 4 hours.After filtration, by the solid product that obtains in 120 DEG C of dryings 4 hours, obtain catalyst B 1.Adopt XRF to analyze catalyst, result illustrates in table 4.
(2) with 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) as model compound, the hydrodesulfurization activity of evaluate catalysts B1 on high-pressure hydrogenation micro-reactor, actual conditions is as follows.
The n-decane solution of reaction raw materials: 4,6-DMDBT, wherein, concentration is 0.45 % by weight;
The conditions of vulcanization of catalyst: temperature is 360 DEG C, pressure is 4.2MPa, H
2flow velocity is 400mL/min, and sulfurized oil adopts CS
2mass fraction is the cyclohexane solution of 5 % by weight, and sulfurized oil feed rate is 0.4mL/min, and sulfuration carries out 3 hours altogether.
Hydrodesulfurization reaction condition: reaction temperature is 280 DEG C, pressure is 4.2MPa, H
2flow velocity is 400mL/min, and the feed rate of reaction raw materials is 0.2mL/min, stable reaction after 3 hours sampling gas-chromatography analyze.
According to following formulae discovery desulfurization degree, thus the hydrodesulfurization activity of evaluate catalysts, result is listed in table 5,
Conversion ratio × (the S of desulfurization degree (%)=4,6-DMDBT
dMBCH+ S
dMCHB+ S
dMBP) × 100%
Wherein, S
dMBCH, S
dMCHBand S
dMBPin the product that obtains of 4,6-DMDBT hydrodesulfurization respectively, dimethyl connection cyclohexane, Dimethylcyclohexyl benzene and dimethyl diphenyl selective.
Comparative example 6
2.03g 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.The carrier (diameter is 1.1mm, and particle length is 2-5mm) the solution impregnation 15.0g comparative example 2 obtained prepared, dip time is 1 hour.After filtration, by the solid product that obtains in 120 DEG C of dryings 4 hours, then at 600 DEG C of roasting 3h, obtain catalyst A 1.Adopt XRF to analyze 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 example 7
Adopt the method Kaolinite Preparation of Catalyst identical with comparative example 6, unlike, do not carry out roasting at 600 DEG C, thus 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.By the article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.4 % by weight) obtaining solution impregnation 20.0g embodiment 2 and prepare, dip time is 4 hours.After filtration, by the solid that obtains in 140 DEG C of dryings 4 hours, obtain catalyst B 2.Adopt XRF to analyze 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.The article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 68.8 % by weight) the solution impregnation 20.0g embodiment 3 obtained prepared, dip time is 1 hour.By the carrier that obtains in 120 DEG C of dryings 4 hours, thus obtain catalyst B 3.Adopt XRF to analyze 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.The article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 67.6 % by weight) the solution impregnation 20.0g embodiment 4 obtained prepared, dip time is 4 hours.After filtration, by the solid product that obtains in 120 DEG C of dryings 4 hours, thus obtain catalyst B 4.Adopt XRF to analyze 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.The article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 76.4 % by weight) the solution impregnation 20.0g embodiment 5 obtained prepared, dip time is 4 hours.After filtration, by the solid that obtains in 150 DEG C of dryings 3 hours, thus obtain catalyst B 5.Adopt XRF to analyze 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.The article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 67.7 % by weight) the solution impregnation 20.0g embodiment 6 obtained prepared, dip time is 4 hours, and temperature is 60 DEG C.After filtration, by the solid product that obtains in 120 DEG C of dryings 4 hours, thus obtain catalyst B 6.Adopt XRF to analyze 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, unlike, carrier is article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 67.0 % by weight) prepared by embodiment 7, obtains catalyst B 7.Adopt XRF to analyze 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, unlike, carrier is article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 69.2 % by weight) prepared by embodiment 8, obtains catalyst B 8.Adopt XRF to analyze 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, unlike, carrier is article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 68.5 % by weight) prepared by embodiment 9, obtains catalyst B 9.Adopt XRF to analyze 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, unlike, 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 step (1), thus obtains catalyst B 10.Adopt XRF to analyze 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 | Catalyst is numbered | Desulfurization degree (%) |
| Embodiment 27 | B1 | 77.1 |
| Comparative example 6 | A1 | 50.2 |
| Comparative example 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 illustration of 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 evaluated, unlike, carrier is iron content aluminium oxide article shaped prepared by embodiment 11, thus obtains 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 evaluated, unlike, carrier is iron content aluminium oxide article shaped prepared by embodiment 12, thus obtains 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 evaluated, unlike, carrier is iron content aluminium oxide article shaped prepared by embodiment 13, thus obtains 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 | Catalyst is numbered | 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 using article shaped according to the present invention as carrier demonstrates higher catalytic activity in the hydrotreatment of hydrocarbon ils.
Claims (15)
1. an iron content hydrated alumina forming matter, this article shaped is made up of a kind of raw material, described raw material by least one hydrated alumina, at least one iron containing compounds, at least one cellulose ether and containing or at least one extrusion aid that do not contain form, the water absorption rate of this article shaped is 0.4-1.5, δ value is less than 10%, Q
1for more than 12N/mm,
Wherein,
Q
1for the radial crushing strength of the article shaped without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radial crushing strength of the article shaped of 120 DEG C of dryings after 4 hours, in N/mm.
2. article shaped according to claim 1, wherein, described article shaped prepares formed body by described raw material, and described formed body is carried out drying make.
3. article shaped according to claim 2, wherein, described formed body is mixed with water by described raw material, obtains the first mixture, and make shaping for described first mixture; Or
Described formed body is mixed with water at least one hydrated alumina and at least one cellulose ether, obtain the second mixture, and described second mixture is successively carried out shaping and dehydration, obtain preform, and load at least one iron containing compounds is made on described preform.
4., according to the article shaped in claim 1-3 described in any one, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-10 % by weight, with Fe
2o
3the total content of the described iron containing compounds of meter is 0.5-8 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 82-98 % by weight.
5. article shaped according to claim 4, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 3-8 % by weight, with Fe
2o
3the total content of the described iron containing compounds of meter is 1.5-6 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 86-95 % by weight.
6. according to the article shaped in claim 1-3 described in any one, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
7. according to the article shaped in claim 1-3 described in any one, wherein, described 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, δ value is less than 5%, Q
1for 15-30N/mm.
9. article shaped according to claim 1, wherein, with the total amount of described raw material for benchmark, the content of described extrusion aid is 0.1-8 % by weight.
10. article shaped according to claim 9, wherein, with the total amount of described raw material for benchmark, the content of described extrusion aid is 0.5-5 % by weight.
11. according to the article shaped in claim 1,9 and 10 described in any one, and wherein, described extrusion aid is starch.
12. according to the article shaped in claim 1,9 and 10 described in any one, and wherein, described extrusion aid is sesbania powder.
13. 1 kinds of iron content aluminium oxide article shaped, the iron content hydrated alumina forming matter in claim 1-12 described in any one is carried out roasting and makes by this article shaped.
Iron content hydrated alumina forming matter in 14. claim 1-12 described in any one or iron content aluminium oxide article shaped according to claim 13 are as the application of drier or the carrier as loaded catalyst.
15. application according to claim 14, wherein, described catalyst is the catalyst with hydrogenation catalyst effect.
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|---|---|---|---|---|
| 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 |
-
2012
- 2012-06-12 CN CN201210193937.6A patent/CN103480327B/en active Active
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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