CN103480428B - Hydrated alumina forming matter and preparation method thereof and aluminium oxide article shaped and their application - Google Patents
Hydrated alumina forming matter and preparation method thereof and aluminium oxide article shaped and their application Download PDFInfo
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Abstract
The invention provides a kind of 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 compound and at least one cellulose ether containing group ivb metallic element, the water absorption rate of this article shaped is 0.4-1.5, δ-value is less than 10%, Q1For more than 12N/mm.Present invention also offers a kind of aluminium oxide article shaped and application thereof, this aluminium oxide article shaped is the hydrated alumina forming matter of the present invention to be carried out roasting and makes.The article shaped of the present invention has high intensity and good strength retention.The method according to the invention, does not use peptizer in forming process.
Description
Technical field
The present invention relates to a kind of hydrated alumina forming matter and its preparation method and application, the invention still further relates to a kind of aluminium oxide article shaped and application thereof.
Background technology
Aluminium oxide, particularly gama-alumina, because it has preferable pore structure and heat-resistant stability, and higher specific surface area, therefore aluminium oxide article shaped is commonly used for the carrier of desiccant or loaded catalyst.The character of aluminium oxide can be carried out modulation, so that it meets the requirement of specific occasion by introducing metallic element in aluminium oxide article shaped.Such as, the aluminium oxide article shaped containing group ivb metallic element is used can to carry out modulation as the carrier loaded active component with hydrogenation catalyst effect, the hydrogenation catalyst performance of the catalyst of preparation.
Aluminium oxide article shaped containing group ivb metallic element can be by mixing hydrated alumina with water, peptizer and optional extrusion aid, and mixture is successively shaped, is dried and high-temperature roasting obtains aluminium oxide article shaped, then with the compound dip forming thing containing group ivb metallic element and be then dried with roasting and prepare；By mix with water, peptizer and optional extrusion aid by hydrated alumina with containing the compound of group ivb metallic element, mixture priority can also be shaped, dry and high-temperature roasting and prepare.
Drying and without high-temperature roasting article shaped (i.e., hydrated alumina forming matter containing group ivb metallic element) when the carrier as loaded catalyst is had the active component of catalytic action by the method load of dipping or is used as desiccant, be prone to dissolve, phenomenon that efflorescence and duct cave in, so that article shaped loses shape, the most only drying and article shaped without high-temperature roasting can not be directly as desiccant or as dipping carrier, it is necessary to the process of one high-temperature roasting of experience just can be as desiccant or as dipping carrier.
And; generally use acid (such as: nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid) as peptizer; on the one hand the existence of acid is prone to corrode former; on the other hand it is being dried and roasting process is discharging a large amount of sour gas; both unfavorable to the health of operator, also it is unfavorable for environmental conservation.
Summary of the invention
It is an object of the invention to overcome prior art must use peptizer, and the unfired technical problem low containing the hydrated alumina forming matter strength retention of group ivb metallic element when preparation contains the aluminium oxide article shaped of group ivb metallic element.The invention provides a kind of hydrated alumina forming matter containing group ivb metallic element and preparation method thereof, this contains the hydrated alumina forming matter of group ivb metallic element and does not use peptizer in forming process, there is good strength retention, even if soaking the phenomenon also will not or caved in substantially without appearance dissolving, efflorescence and duct the most for a long time.The method according to the invention, does not use peptizer in forming process.
The present inventor finds in research process, in adsorption process and in dipping process, it is prone to that dissolving occurs without the hydrated alumina forming matter containing group ivb metallic element of high-temperature roasting, efflorescence and duct cave in, and then the reason losing shape is probably: contain peptizer without the hydrated alumina forming matter containing group ivb metallic element of high-temperature roasting, primarily serving the purpose of of described peptizer makes the various powder adhesion as raw material together, but in absorption and dipping process, owing to peptizer dissolves, run off in a large number from article shaped, and then make article shaped occur dissolving, efflorescence and duct cave in phenomenon, finally lose shape.
The present inventor finds through further investigation: in the forming process containing the hydrated alumina of group ivb metallic element, do not use peptizer, it is simultaneously introduced cellulose ether, even if thus prepared article shaped does not carry out high-temperature roasting, also there is good strength retention, in impregnation liquid, impregnate the phenomenon also will not or caved in substantially without appearance dissolving, efflorescence and duct for a long time, and this article shaped also has good absorbent properties.This completes the present invention.
A first aspect of the present invention provides a kind of hydrated alumina forming matter, this article shaped is made up of the raw material containing at least one hydrated alumina, at least one compound and at least one cellulose ether containing group ivb metallic element, the water absorption rate of this article shaped is 0.4-1.5, δ-value is less than 10%, Q1For more than 12N/mm,
Wherein,
Q1For the radial direction crushing strength of the article shaped without water soaking, in terms of N/mm,
Q2For through water soaking 30 minutes the radial direction crushing strength that is dried the article shaped after 4 hours at 120 DEG C, in terms of N/mm.
A second aspect of the present invention provides a kind of method preparing hydrated alumina forming matter, the method includes being prepared molded body by the raw material containing at least one hydrated alumina, at least one compound and at least one cellulose ether containing group ivb metallic element, and is dried by described molded body.
A third aspect of the present invention provides a kind of hydrated alumina forming matter prepared by the method for the present invention.
A fourth aspect of the present invention provides a kind of aluminium oxide article shaped, and this aluminium oxide article shaped is the hydrated alumina forming matter of the present invention to be carried out roasting and makes.
A fifth aspect of the present invention provides a kind of hydrated alumina forming matter according to the present invention or aluminium oxide article shaped as desiccant or the application of the carrier as loaded catalyst.
Hydrated alumina forming matter according to the present invention does not contains peptizer (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 impregnating the phenomenon also will not or caved in substantially without appearance dissolving, efflorescence and duct in impregnation liquid for a long time.Thus, i.e. can be used as desiccant or the carrier as loaded catalyst without high-temperature roasting according to the hydrated alumina forming matter of the present invention.Aluminium oxide article shaped according to the present invention is made by the hydrated alumina forming matter of the present invention is carried out roasting, has high intensity and strength retention, the most also has good absorbent properties.
Specifically, hydrated alumina forming matter and the radial direction crushing strength of aluminium oxide article shaped according to the present invention are able to reach more than 12N/mm, water absorption rate is able to reach 0.4-1.5, and δ-value (that is, the crushing strength loss rate after immersion) is able to be less than 10%.
The method according to the invention, does not use peptizer (that is, described raw material do not contain peptizer) in forming process, on the one hand decrease the corrosion to former, extend the service life of former, reduce production cost；On the other hand greatly reduce and be dried and the amount of the sour gas of release in roasting process, reduce the impact on operator's health, also help environmental conservation simultaneously.
Detailed description of the invention
A first aspect of the present invention provides a kind of hydrated alumina forming matter, and described article shaped is made up of the raw material containing at least one hydrated alumina, at least one compound and at least one cellulose ether containing group ivb metallic element.Term " at least one " refers to one or more.
Hydrated alumina forming matter according to the present invention, described raw material contains hydrated alumina, compound containing group ivb metallic element and cellulose ether, but not containing peptizer, the hydrated alumina forming matter made has good strength retention, the most also has good absorbent properties.
According to the hydrated alumina forming matter of the present invention, the composition of the raw material for forming described article shaped can carry out suitable selection according to the concrete application scenario of intended article shaped.Usually, on the basis of the total amount of described raw material, the total content of described cellulose ether can be 0.5-10 weight %, preferably 1-8 weight %, more preferably 2-7 weight %；Can be 0.5-55 weight % with the total content of compound containing group ivb metallic element described in oxide is counted, preferably 1-50 weight %, more preferably 1.5-45 weight %；With Al2O3The total content of the described hydrated alumina of meter can be 35-98 weight %, preferably 42-96 weight %, more preferably 48-95 weight %.In the present invention, when calculating the total amount of described raw material, the described compound containing group ivb metallic element is in terms of oxide, and described hydrated alumina is with Al2O3Meter, described raw material does not include the water that will introduce during described raw material molding.
According to the present invention, described cellulose ether refers to the ether system derivant that the hydrogen atom at least part of hydroxyl in cellulosic molecule is formed after being replaced by one or more alkyl, and wherein, multiple described alkyl can be identical, it is also possible to for difference.Described alkyl is selected from substituted alkyl and unsubstituted alkyl.Described unsubstituted alkyl is preferably alkyl (such as: C1-C5Alkyl).In the present invention, C1-C5Alkyl include C1-C5Straight chained alkyl and C3-C5Branched 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.Described substituted alkyl can be such as by the alkyl of hydroxyl or carboxyl replacement (such as: C1-C5The alkyl being optionally substituted by a hydroxyl group, C1-C5The alkyl replaced by carboxyl), 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 amount of the substituent group of the hydrogen atom in the kind of described cellulose ether and the hydroxyl in substituted cellulose molecule, can be common various cellulose ethers.Specifically, described cellulose ether can be selected from, but not limited to: methylcellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxyethylmethyl-cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose and carboxymethyl hydroxyethyl cellulose.Preferably, described cellulose ether is selected from methylcellulose, hydroxyethylmethyl-cellulose and hydroxypropyl methyl cellulose.
According to the present invention, described group ivb metallic element can be various group ivb metallic elements commonly used in the art, such as, can be selected from titanium, zirconium and hafnium, be preferably selected from titanium and zirconium, more preferably titanium.
According to the present invention, the described compound containing group ivb metallic element can be the compound in various molecular structures commonly used in the art containing group ivb metallic element.Such as, when described group ivb metallic element is selected from titanium and zirconium, the described compound containing group ivb metallic element can be selected from basic zirconium chloride (such as ZrOCl2·8H2O), zirconium acetate, Disulfatozirconic acid., zirconium nitrate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium are (such as (NH4)2ZrO(CO3)2·nH2O), zirconium dioxide, metatitanic acid, metatitanic acid (H2TiO3), titanium dioxide, titanium sulfate and the compound shown in Formulas I,
TiXn(OR)4-n(I),
In Formulas I, X is halogen (such as: can be chlorine, bromine and iodine, preferably chlorine), and R is C1-C5Alkyl, n is the integer (can be such as 0,1,2,3 or 4, preferably 0 or 4) of 0-4.
Preferably, the described compound containing group ivb metallic element is selected from zirconium acetate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium, zirconium dioxide, metatitanic acid, metatitanic acid, titanium dioxide, titanium sulfate, titanium tetrachloride, tetra-n-butyl titanate, tetrabutyl titanate and tetraisopropyl titanate.It is highly preferred that the described compound containing group ivb metallic element is selected from metatitanic acid and titanium dioxide.
The present invention is not particularly limited for the kind of described hydrated alumina, can be the conventional selection of this area.Preferably, described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.It is highly preferred that described hydrated alumina is boehmite.
Hydrated alumina forming matter according to the present invention, described article shaped is to be prepared molded body by containing at least one hydrated alumina, at least one raw material containing the compound of group ivb metallic element and at least one cellulose ether, and is dried by described molded body and prepares.
Various methods commonly used in the art can be used to prepare described molded body, be not particularly limited.Such as: directly by hydrated alumina, cellulose ether and the compound mixed-forming containing group ivb metallic element, thus described molded body can be obtained；Preform, the then load compound containing group ivb metallic element on this preform can also be prepared first by hydrated alumina and cellulose ether mixed-forming, thus obtain described molded body.
The present invention one preferred embodiment in, described molded body is at least one hydrated alumina, at least one compound containing group ivb metallic element and at least one cellulose ether to be mixed with water, obtain the first mixture, and described first mixture forming is made.
In another preferred embodiment of the present invention, described molded body is at least one hydrated alumina and at least one cellulose ether to be mixed with water, obtain the second mixture, and described second mixture is successively shaped and is dehydrated, obtain preform, described preform loads at least one compound containing group ivb metallic element and makes.
In this embodiment, the mode loading at least one compound containing group ivb metallic element on described preform can be the conventional selection of this area, such as: can be by described preform is contacted with containing at least one solution of compound containing group ivb metallic element, thus by described compound loaded on described preform containing group ivb metallic element.Can be the conventional selection of this area by the mode that described preform contacts with the solution containing at least one compound containing group ivb metallic element, such as: by dipping or spray, described preform can be contacted with the solution of compound containing group ivb metallic element containing at least one, thus by described compound loaded on described preform containing group ivb metallic element.Use the mode of dipping by described containing group ivb metallic element compound loaded on described preform time, described dipping can be saturated dipping, it is also possible to for supersaturation dipping.The solvent of the described solution containing at least one compound containing group ivb metallic element can be the conventional selection of this area, preferably water.The concentration of solution and the number of times of described contact of the described compound containing group ivb metallic element containing at least one are not particularly limited, so that the amount containing the compound of group ivb metallic element being supported on described preform disclosure satisfy that requirement (the most previously described content) is as the criterion.
In this embodiment, the condition of described dehydration is not particularly limited, and can be the conventional selection of this area, is as the criterion can remove water.Usually, described dehydration can be carried out at a temperature of 350 DEG C at 60 DEG C, preferably carries out at a temperature of 80-300 DEG C, more preferably carries out at a 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, preferably 2-24 hour, more preferably 2-12 hour.
According to the hydrated alumina forming matter of the present invention, the consumption of the water for preparing described first mixture or described second mixture is not particularly limited, as long as the consumption of water is able to ensure that various component mix homogeneously.
According to the hydrated alumina forming matter of the present invention, the mode of described molding is not particularly limited, and can use various molding modes commonly used in the art, such as: extrusion, spraying, round as a ball, tabletting or combinations thereof.The present invention one preferred embodiment in, by the way of extrusion, carry out molding.
According to the hydrated alumina forming matter of the present invention, described article shaped can have variously-shaped according to specifically used requirement, such as: spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.
According to the hydrated alumina forming matter of the present invention, the temperature being dried by described molded body can be the conventional selection of this area.Usually, described dry temperature can be 60 DEG C less than 350 DEG C, preferably 80-300 DEG C, more preferably 120-250 DEG C.The described dry time can carry out suitable selection according to dry temperature, and to enable to, volatile matter content in the article shaped finally given is satisfied uses requirement to be as the criterion.Usually, the described dry time can be 1-48 hour, preferably 2-24 hour, more preferably 2-12 hour.
According to the 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 the conventional selection of this area.Usually, on the basis of the total amount of described raw material, the content of described extrusion aid can be 0.1-8 weight %, preferably 0.5-5 weight %.According to the hydrated alumina forming matter of the present invention, described extrusion aid is preferably starch (that is, described raw material possibly together with starch).Can be the starch in various sources commonly used in the art as the starch of extrusion aid, such as: the powder body being grinding to obtain by plant seed, such as sesbania powder.Described extrusion aid can use various methods commonly used in the art 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 the hydrated alumina forming matter of the present invention, described article shaped radial direction crushing strength loss rate (that is, δ-value) after steeping is less than 10%, generally less than 5%；Radial direction crushing strength (that is, Q without the article shaped of water soaking1) can be more than 12N/mm, even more than 15N/mm.Specifically, according to the Q of the article shaped of the present invention1Can be 15-30N/mm.The water absorption rate of described article shaped is 0.4-1.5, generally 0.6-1.
In the present invention, δ-value, for evaluating the strength retention of article shaped, is defined by below equation:
Wherein, Q1For the radial direction crushing strength of the article shaped without water soaking, in terms of N/mm,
Q2For through water soaking 30 minutes the radial direction crushing strength that is dried the article shaped after 4 hours at 120 DEG C, in terms of N/mm.
In the present invention, described radial direction crushing strength measures according to the method for regulation in the RIPP25-90 described in " Petrochemical Engineering Analysis method " (Yang Cui surely waits and compiles for Science Press, the nineteen ninety first edition).
In the present invention, the article shaped excess deionized water that described water absorption rate refers to be dried soak 30 minutes before and after the ratio of weight changing value and the weight of described dry article shaped.Concrete method of testing is: article shaped to be measured is dried 4 hours at 120 DEG C, then sieves with the standard screen of 40 mesh, weigh 20g oversize and (be designated as w as testing sample1), testing sample 50g deionized water to be soaked 30 minutes, after filtration, solid phase is drained 5 minutes, the weight then weighing the solid phase drained (is designated as w2), calculate water absorption rate by below equation:
Hydrated alumina forming matter according to the present invention not only has good absorbent properties, and has the strength retention of excellence, even if long-time immersion still has higher intensity in water.Therefore, the carrier of desiccant or loaded catalyst it is adapted as according to the hydrated alumina forming matter of the present invention.
A second aspect of the present invention provides a kind of method preparing hydrated alumina forming matter, the method includes being prepared molded body by the raw material containing at least one hydrated alumina, at least one compound and at least one cellulose ether containing group ivb metallic element, and is dried by described molded body.
The method according to the invention, by using containing at least one hydrated alumina, at least one compound containing group ivb metallic element and raw material of at least one cellulose ether, do not use peptizer, article shaped can also be prepared, and the article shaped of preparation not only has good absorbent properties, and there is high strength retention.
The method according to the invention, the composition of described raw material can carry out suitable selection according to the concrete application scenario of the article shaped of final preparation.Usually, on the basis of the total amount of described raw material, the total content of described cellulose ether can be 0.5-10 weight %, preferably 1-8 weight %, more preferably 2-7 weight %；Can be 0.5-55 weight % with the total content of compound containing group ivb metallic element described in oxide is counted, preferably 1-50 weight %, more preferably 1.5-45 weight %；With Al2O3The total content of the described hydrated alumina of meter can be 35-98 weight %, preferably 42-96 weight %, more preferably 48-95 weight %.
The method according to the invention, described cellulose ether, identical with described previously containing the compound of group ivb metallic element and the kind of hydrated alumina, do not repeat them here.
Method according to the invention it is possible to use various methods commonly used in the art to prepare described molded body, it is not particularly limited.Such as: directly by hydrated alumina, cellulose ether and the compound mixing aftershaping containing group ivb metallic element, thus described molded body can be obtained；First hydrated alumina and cellulose ether can also be mixed and molding, prepare preform, the then load compound containing group ivb metallic element on this preform, thus obtain described molded body.
The present invention one preferred embodiment in, the method being prepared described molded body by described raw material includes: at least one hydrated alumina, at least one compound containing group ivb metallic element and at least one cellulose ether are mixed with water, obtain the first mixture, and by described first mixture forming.
In another preferred embodiment of the present invention, the method being prepared described molded body by described raw material includes: 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 shaped and is dehydrated, obtain preform, described preform loads at least one compound containing group ivb metallic element.
In this embodiment, the mode loading at least one compound containing group ivb metallic element on described preform can be the conventional selection of this area, such as: can be by described preform is contacted with containing at least one solution of compound containing group ivb metallic element, thus by described compound loaded on described preform containing group ivb metallic element.Can be the conventional selection of this area by the mode that described preform contacts with the solution containing at least one compound containing group ivb metallic element, such as: by dipping or spray, described preform can be contacted with the solution of compound containing group ivb metallic element containing at least one, thus by described compound loaded on described preform containing group ivb metallic element.Use the mode of dipping by described containing group ivb metallic element compound loaded on described preform time, described dipping can be saturated dipping, it is also possible to for supersaturation dipping.The solvent of the described solution containing at least one compound containing group ivb metallic element can be the conventional selection of this area, preferably water.The concentration of solution and the number of times of described contact of the described compound containing group ivb metallic element containing at least one are not particularly limited, so that the amount containing the compound of group ivb metallic element being supported on described preform disclosure satisfy that requirement (the most previously described content) is as the criterion.
The method according to the invention, the consumption of the water for preparing described first mixture or described second mixture is not particularly limited, as long as the consumption of water is able to ensure that various component mix homogeneously.
The method according to the invention, the mode of described molding is not particularly limited, and can use various molding modes commonly used in the art, such as: extrusion, spraying, round as a ball, tabletting or combinations thereof.The present invention one preferred embodiment in, by the way of extrusion, carry out molding.
The method according to the invention, described article shaped can have variously-shaped according to specifically used requirement, such as: spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.
The method according to the invention, described dry temperature can be the conventional selection of this area.Usually, described dry temperature can be 60 DEG C less than 350 DEG C, preferably 80-300 DEG C, more preferably 120-250 DEG C.The described dry time can carry out suitable selection according to dry temperature, and to enable to, volatile matter content in the article shaped finally given is satisfied uses requirement to be as the criterion.Usually, the described dry time can be 1-48 hour, preferably 2-24 hour, more preferably 2-12 hour.
The method according to the invention, described raw material can also contain at least one extrusion aid.The consumption of described extrusion aid and kind can be the conventional selection of this area.Usually, on the basis of the total amount of described raw material, the content of described extrusion aid can be 0.1-8 weight %, preferably 0.5-5 weight %.The method according to the invention, described extrusion aid is preferably starch (that is, described raw material possibly together with starch).Can be the starch in various sources commonly used in the art as the starch of extrusion aid, such as: the powder body being grinding to obtain by plant seed, such as sesbania powder.Described extrusion aid can use various methods commonly used in the art to add in raw material, such as: can be added in above-mentioned first mixture and the second mixture by described extrusion aid respectively.
Prepared according to the methods of the invention hydrated alumina forming matter (i.e., only drying and unfired article shaped) has good strength retention and absorbent properties.Typically, for the hydrated alumina forming matter prepared by the method for the present invention, radially crushing strength can be more than 12N/mm, even more than 15N/mm, such as, can be 15-30N/mm；δ-value can be less than 10%, generally less than 5%；Water absorption rate can be 0.4-1.5, such as, can be 0.6-1.Therefore, the method according to the invention in forming process without using peptizer, and the hydrated alumina forming matter of preparation has good strength retention and absorbent properties, it is adapted as desiccant or the carrier as loaded catalyst loads the active component with catalytic action.
Thus, a third aspect of the present invention provides a kind of hydrated alumina forming matter prepared by the method for the present invention.
A fourth aspect of the present invention provides a kind of aluminium oxide article shaped, and this aluminium oxide article shaped is the hydrated alumina forming matter of the present invention to be carried out roasting and makes.
The present invention is not particularly limited for the condition of roasting, can be the conventional selection of this area.Specifically, the temperature of described roasting can be 450-950 DEG C, preferably 500-900 DEG C；The time of described roasting can be 2-8 hour, preferably 3-6 hour.
Aluminium oxide article shaped according to the present invention has high intensity and strength retention and good absorbent properties.Usually, the radial direction crushing strength of described aluminium oxide article shaped can be more than 12N/mm, even more than 15N/mm, such as, can be 15-30N/mm；δ-value is less than 10%, generally less than 5%；Water absorption rate is 0.4-1.5, such as, can be 0.6-1.
A fifth aspect of the present invention provides the hydrated alumina forming matter according to the present invention or aluminium oxide article shaped as desiccant or the application of the carrier as loaded catalyst.
In the present invention, described loaded catalyst can be commonly used in the art various can be using hydrated alumina or aluminium oxide article shaped as the catalyst of carrier.Preferably, described catalyst is the catalyst with hydrogenation catalyst effect, is i.e. particularly suitable as the carrier with the catalyst of hydrogenation catalyst effect according to the hydrated alumina forming matter of the present invention and aluminium oxide article shaped.
When the carrier of the catalyst that the hydrated alumina forming matter according to the present invention or aluminium oxide article shaped are used as to have hydrogenation catalyst effect, various methods (such as: dipping) commonly used in the art can be used the active component with hydrogenation catalyst effect to be supported in the hydrated alumina forming matter according to the present invention or aluminium oxide article shaped, such as: can pass through by the article shaped of the aqueous impregnation present invention containing described active component, then the article shaped being loaded with described active component is dried 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 example and comparative example, the method for regulation in RIPP25-90 is used to measure the radial direction crushing strength of the article shaped of preparation.
In following example and comparative example, following methods is used to measure the δ-value of the article shaped prepared: to use the method for regulation in RIPP25-90 to measure and (be designated as Q without the radial direction crushing strength of the article shaped of water soaking1)；The article shaped of preparation being placed in 50g deionized water, soak 30 minutes, then filter, be dried 4 hours at 120 DEG C by the solid obtained, the radial direction crushing strength measuring the solid being dried according to the method for regulation in RIPP25-90 (is designated as Q2), use below equation to calculate δ-value,
In following example and comparative example, following methods is used to measure the water absorption rate of the article shaped prepared: article shaped to be measured to be dried 4 hours at 120 DEG C, then sieve with the standard screen of 40 mesh, weigh 20g oversize and (be designated as w as testing sample1), testing sample 50g deionized water to be soaked 30 minutes, after filtration, solid phase is drained 5 minutes, the weight then weighing the solid phase drained (is designated as w2), calculate water absorption rate by below equation:
In following example and comparative example, testing sample was measured by contents on dry basis 600 DEG C of roastings 4 hours.
Embodiment 1-16 for explanation according to hydrated alumina forming matter of the present invention and preparation method thereof.
Embodiment 1
By 100.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 weight %), 4.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder, 20.2g metatitanic acid serosity (with TiO2Meter, Ti content is 40 weight %) and 80g deionized water mix homogeneously.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar of extrusion and be dried 12 hours at 150 DEG C, thus obtain the hydrated alumina forming matter according to the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Comparative example 1
Using method same as in Example 1 to prepare hydrated alumina forming matter, except for the difference that, do not use methylcellulose, but use 2.5mL concentrated nitric acid, thus obtain hydrated alumina forming matter, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Comparative example 2
Using the method identical with comparative example 1 to prepare article shaped, except for the difference that, by dried for the wet bar of extrusion then 600 DEG C of roastings 4 hours, thus obtain article shaped, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Comparative example 3
Using method same as in Example 1 to prepare article shaped, except for the difference that, do not use methylcellulose, result cannot prepare article shaped.
Embodiment 2
(1) in the retort of a 2L, the 2000mL concentration aluminum sulfate solution as 48g/L and sodium aluminate solution (Al are added with also stream mode2O3Content is 200g/L, and causticity coefficient is 1.58) carry out precipitation, reaction temperature is 50 DEG C, and pH value is 6.0, and reaction time is 15 minutes；The serosity vacuum filter obtained is filtered, to be filtered complete after, filter cake supplements and adds 20L deionized water (temperature is 40 ± 5 DEG C) and rinse filter cake about 60 minutes.Filter cake after washing is joined in 1.5L deionized water and stirs into serosity, serosity is dried with being pumped into 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, Al2O3Content is 63 weight %, is defined as amorphous state through XRD analysis.
(2) the amorphous hydrated aluminium oxide 50.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 weight %), 50.0g step (1) prepared, 2.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g hydroxyethylmethyl-cellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 5.0g metatitanic acid serosity are (with TiO2Meter, Ti content is 40 weight %) and 90g deionized water mix homogeneously.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar obtained, be dried 6 hours at 220 DEG C, thus obtain the hydrated alumina forming matter according to the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 3
By 60.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 weight %), 40.0g gibbsite (purchased from Pingguo Aluminium Industry Co., Guangxi, contents on dry basis is 64.5 weight %), 1.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 2.0g hydroxypropyl methyl cellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder, 30.0g titanium dioxide and 120g deionized water stir.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar obtained, be dried 12 hours at 80 DEG C, thus obtain the hydrated alumina forming matter according to the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 4
100.0g boehmite SB powder (purchased from Sasol company, contents on dry basis is 75.0 weight %), 3.0g hydroxyethylmethyl-cellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 75.0g titanium dioxide and 150g deionized water are stirred.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar obtained, be dried 12 hours at 150 DEG C, thus obtain the hydrated alumina forming matter according to the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Comparative example 4
Use method the same as in Example 4 to prepare hydrated alumina forming matter, except for the difference that, do not use hydroxyethylmethyl-cellulose, but use 20mL Alumina gel (purchased from this promise of Dalian New Chemical Material science and technology company limited, Al2O3Content is 10 weight %), thus obtain hydrated alumina forming matter, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 5
100.0g boehmite SB powder (purchased from Sasol company, contents on dry basis is 75.0 weight %), 3.0g hydroxyethylmethyl-cellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 2.0g hydroxypropyl methyl cellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 20.0g titanium dioxide are mixed homogeneously with 115g deionized water.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar obtained, be dried 4 hours at 250 DEG C, thus obtain the hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 6
By 100.0g boehmite (purchased from Yantai, Shandong Heng Hui Chemical Co., Ltd., contents on dry basis is 71.0 weight %), 5.0g hydroxypropyl methyl cellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder, 70.0g metatitanic acid serosity (with TiO2Meter, the content of titanium is 40 weight %) mix homogeneously with 55g deionized water.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar obtained, be dried 4 hours at 180 DEG C, obtain the hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Comparative example 5
Using method same as in Example 6 to prepare hydrated alumina forming matter, except for the difference that, do not use hydroxypropyl methyl cellulose, but use 5.0mL acetic acid, thus obtain hydrated alumina forming matter, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 7
Method same as in Example 2 is used to prepare hydrated alumina forming matter, except for the difference that, the content of methylcellulose is 2.0g, the content of hydroxyethylmethyl-cellulose is 5.0g, thus obtaining the hydrated alumina forming matter according to the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 8
By 100.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 weight %), 4.0g methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd) and 3.0g sesbania powder mix homogeneously.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar of extrusion is placed in baking oven, is dried 12 hours at 150 DEG C.Weigh 50g shaping and drying bar, put into and be dissolved in deionized water in the 100mL solution of preparation by 12.0g tetra-n-butyl titanate, filter after impregnating 4 hours, be dried 6 hours at 120 DEG C, thus obtaining the hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 9
Using method same as in Example 3 to prepare article shaped, except for the difference that, be placed in baking oven by the wet bar obtained, be dried 12 hours at 120 DEG C, thus obtain the hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 10
Using method same as in Example 5 to prepare article shaped, except for the difference that, be placed in baking oven by the wet bar obtained, be dried 4 hours at 300 DEG C, thus obtain the hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 11
By 100.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 weight %), 4.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder, 25.0g zirconium hydroxide (with ZrO2Meter, zirconium content is 35 weight %) and 85g deionized water mix homogeneously.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar of extrusion, be dried 12 hours at 150 DEG C, thus obtain the hydrated alumina forming matter according to the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Comparative example 6
Use the method identical with embodiment 11 to prepare hydrated alumina forming matter, except for the difference that, do not use methylcellulose, but use 2.5mL concentrated nitric acid, thus obtain hydrated alumina forming matter.The radial direction crushing strength, water absorption rate and the δ-value that measure the article shaped obtained are listed in Table 1.
Comparative example 7
Using the method identical with comparative example 6 to prepare article shaped, except for the difference that, by dried for the wet bar of extrusion then 600 DEG C of roastings 4 hours, thus obtain article shaped, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Comparative example 8
Using the method identical with embodiment 11 to prepare article shaped, except for the difference that, do not use methylcellulose, result cannot prepare article shaped.
Embodiment 12
(1) method same as in Example 2 is used to prepare amorphous hydrated aluminium oxide.
(2) the amorphous hydrated aluminium oxide 50.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, butt is 69.5 weight %), 50.0g step (1) prepared, 2.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g hydroxyethylmethyl-cellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 5.0g zirconium hydroxide are (with ZrO2Meter, zirconium content is 35 weight %) and 90g deionized water mix homogeneously.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar obtained, be dried 6 hours at 220 DEG C, obtain the hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 13
By 60.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 weight %), 40.0g gibbsite (purchased from Pingguo Aluminium Industry Co., Guangxi, contents on dry basis is 64.5 weight %), 1.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 2.0g hydroxypropyl methyl cellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder, 32.0g zirconium dioxide and 122g deionized water stir.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar obtained, be dried 12 hours at 80 DEG C, thus obtain the hydrated alumina forming matter according to the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 14
100.0g boehmite SB powder (purchased from Sasol company, contents on dry basis is 75.0 weight %), 3.0g hydroxyethylmethyl-cellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 67.0g zirconium dioxide and 150g deionized water are stirred.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar obtained, be dried 12 hours at 150 DEG C, obtain the hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 15
100.0g boehmite SB powder (purchased from Sasol company, contents on dry basis is 75.0 weight %), 3.0g hydroxyethylmethyl-cellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 2.0g hydroxypropyl methyl cellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder, 18.0g zirconium dioxide are mixed homogeneously with 115g deionized water.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar obtained, be dried 4 hours at 250 DEG C, obtain the hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Comparative example 9
Use the method identical with embodiment 15 to prepare hydrated alumina forming matter, except for the difference that, do not use hydroxyethylmethyl-cellulose and hydroxypropyl methyl cellulose, but use 20mL Alumina gel (purchased from this promise of Dalian New Chemical Material science and technology company limited, Al2O3Content is 10 weight %), thus obtain hydrated alumina forming matter, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Embodiment 16
By 100.0g boehmite (purchased from Yantai, Shandong Heng Hui Chemical Co., Ltd., contents on dry basis is 71.0 weight %), 5.0g hydroxypropyl methyl cellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder, 70.0g zirconium hydroxide (with ZrO2Meter, the content of zirconium is 35 weight %) mix homogeneously with 55g deionized water.The mixture obtained is sent in extruder and extrudes, obtain wet bar.Being placed in baking oven by the wet bar obtained, be dried 4 hours at 180 DEG C, obtain the hydrated alumina forming matter of the present invention, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Comparative example 10
Using the method identical with embodiment 16 to prepare hydrated alumina forming matter, except for the difference that, do not use hydroxypropyl methyl fiber, but use 5.0mL acetic acid, thus obtain hydrated alumina forming matter, radially crushing strength, water absorption rate and δ-value are listed in Table 1 for they.
Table 1
| Numbering | Crushing strength (N/mm) | Water absorption rate | δ-value (%) |
| Embodiment 1 | 22.2 | 0.85 | 3.4 |
| Comparative example 1 | 16.5 | 0.64 | 64.2 |
| Comparative example 2 | 25.8 | 0.85 | 3.1 |
| Embodiment 2 | 19.8 | 0.71 | 2.8 |
| Embodiment 3 | 15.1 | 0.68 | 3.9 |
| Embodiment 4 | 19.7 | 0.70 | 3.1 |
| Comparative example 4 | 19.1 | 0.68 | 76.1 |
| Embodiment 5 | 22.8 | 0.67 | 2.5 |
| Embodiment 6 | 19.7 | 0.78 | 2.8 |
| Comparative example 5 | 15.2 | 0.78 | 59.4 |
| Embodiment 7 | 19.9 | 0.70 | 2.9 |
| Embodiment 8 | 20.5 | 0.73 | 3.1 |
| Embodiment 9 | 16.8 | 0.88 | 3.0 |
| Embodiment 10 | 20.6 | 0.73 | 2.8 |
| Embodiment 11 | 23.1 | 0.83 | 3.3 |
| Comparative example 6 | 17.1 | 0.63 | 63.6 |
| Comparative example 7 | 24.3 | 0.83 | 4.2 |
| Embodiment 12 | 18.9 | 0.71 | 2.7 |
| Embodiment 13 | 16.2 | 0.84 | 3.7 |
| Embodiment 14 | 19.4 | 0.71 | 3.2 |
| Embodiment 15 | 19.5 | 0.68 | 2.7 |
| Comparative example 9 | 18.2 | 0.65 | 75.4 |
| Embodiment 16 | 18.6 | 0.76 | 2.6 |
| Comparative example 10 | 16.1 | 0.77 | 60.3 |
Embodiment 17-27 is for illustrating the aluminium oxide article shaped according to the present invention.
Embodiment 17-27
Hydrated alumina forming matter embodiment 1-11 prepared carries out roasting respectively under conditions of table 2 is listed, thus obtains the aluminium oxide article shaped according to the present invention, and radially crushing strength, water absorption rate and δ-value are listed in table 2 for they.
Table 2
The result of Tables 1 and 2 shows, has good radial direction crushing strength and radial direction crushing strength conservation rate according to article shaped of the present invention, the most also has good absorbent properties.
Embodiment 28-59 is for illustrating the article shaped application as desiccant of the present invention.
Embodiment 28-43
Hydrated alumina forming matter embodiment 1-16 prepared (is designated as N after weighing1) be respectively placed in atmospheric dryer as desiccant, in exsiccator, then place a beaker filling 250mL water, close exsiccator, and place 10 days in room temperature (25 DEG C).Then, taking-up article shaped is weighed and (is designated as N2), calculating hygroscopic capacity by below equation, result is listed in table 3,
Embodiment 44-54
Use the method identical with embodiment 28-43 to measure hygroscopic capacity, except for the difference that, use article shaped prepared by embodiment 17-27 as desiccant.Test result is listed in table 3.
Embodiment 55-59
The method identical with embodiment 28-43 is used to measure hygroscopic capacity, except for the difference that, hydrated alumina forming matter embodiment 12-16 prepared was 600 DEG C of roastings 4 hours, thus obtained the aluminium oxide article shaped of the present invention, and the aluminium oxide article shaped effect desiccant that will obtain.Test result illustrates in table 3.
Table 3
| Numbering | Article shaped | N1(g) | Contents on dry basis (weight %) | Hygroscopic capacity (%) |
| Embodiment 28 | Embodiment 1 | 20.0 | 71.3 | 68.2 |
| Embodiment 29 | Embodiment 2 | 20.0 | 70.5 | 62.5 |
| Embodiment 30 | Embodiment 3 | 20.0 | 70.2 | 77.3 |
| Embodiment 31 | Embodiment 4 | 20.0 | 78.2 | 60.3 |
| Embodiment 32 | Embodiment 5 | 20.0 | 73.4 | 56.6 |
| Embodiment 33 | Embodiment 6 | 20.0 | 74.1 | 69.2 |
| Embodiment 34 | Embodiment 7 | 20.0 | 70.9 | 68.5 |
| Embodiment 35 | Embodiment 8 | 20.0 | 67.3 | 66.8 |
| Embodiment 36 | Embodiment 9 | 20.0 | 74.8 | 78.6 |
| Embodiment 37 | Embodiment 10 | 20.0 | 78.6 | 63.6 |
| Embodiment 38 | Embodiment 11 | 20.0 | 70.6 | 67.3 |
| Embodiment 39 | Embodiment 12 | 20.0 | 71.2 | 61.6 |
| Embodiment 40 | Embodiment 13 | 20.0 | 73.7 | 78.2 |
| Embodiment 41 | Embodiment 14 | 20.0 | 77.6 | 61.2 |
| Embodiment 42 | Embodiment 15 | 20.0 | 72.8 | 57.8 |
| Embodiment 43 | Embodiment 16 | 20.0 | 73.4 | 68.6 |
| Embodiment 44 | Embodiment 17 | 20.0 | 100.0 | 67.3 |
| Embodiment 45 | Embodiment 18 | 20.0 | 100.0 | 60.6 |
| Embodiment 46 | Embodiment 19 | 20.0 | 100.0 | 75.8 |
| Embodiment 47 | Embodiment 20 | 20.0 | 100.0 | 58.3 |
| Embodiment 48 | Embodiment 21 | 20.0 | 100.0 | 55.1 |
| Embodiment 49 | Embodiment 22 | 20.0 | 100.0 | 66.4 |
| Embodiment 50 | Embodiment 23 | 20.0 | 100.0 | 67.4 |
| Embodiment 51 | Embodiment 24 | 20.0 | 100.0 | 68.5 |
| Embodiment 52 | Embodiment 25 | 20.0 | 100.0 | 79.8 |
| Embodiment 53 | Embodiment 26 | 20.0 | 100.0 | 65.9 |
| Embodiment 54 | Embodiment 27 | 20.0 | 100.0 | 66.9 |
| Embodiment 55 | Embodiment 12* | 20.0 | 100.0 | 61.2 |
| Embodiment 56 | Embodiment 13* | 20.0 | 100.0 | 76.3 |
| Embodiment 57 | Embodiment 14* | 20.0 | 100.0 | 59.3 |
| Embodiment 58 | Embodiment 15* | 20.0 | 100.0 | 56.9 |
| Embodiment 59 | Embodiment 16* | 20.0 | 100.0 | 67.5 |
*: the aluminium oxide article shaped that hydrated alumina forming matter embodiment 12-16 prepared obtains 600 DEG C of roastings for 4 hours.
The result of table 3 shows, has good absorbent properties according to the article shaped of the present invention, is adapted as desiccant.
Embodiment 60-77 is for illustrating the article shaped application as the carrier of loaded catalyst of the present invention.
Embodiment 60
(1) 4.71g basic nickel carbonate (NiO content is 51 weight %), 12.0g molybdenum oxide and 2.24g phosphoric acid are dissolved in the water, are configured to 60mL solution；The article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 71.3 weight %) the solution impregnation 20.1g embodiment 1 obtained prepared, dip time is 4 hours.After filtration, the solid product obtained is dried 3 hours in 150 DEG C, obtains catalyst B1.Using XRF to be analyzed catalyst, result illustrates in table 4.
(2) with 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) is as model compound, and the activity of catalyst prepared by evaluation procedure (1) on high-pressure hydrogenation micro-reactor, actual conditions is as follows.
Reaction raw materials: the n-decane solution of 4,6-DMDBT, wherein, concentration is 0.45 weight %.
The conditions of vulcanization of catalyst: the useful load of catalyst is 0.15g, temperature is 360 DEG C, and pressure is 4.2MPa, H2Flow velocity is 400mL/min, and sulfurized oil uses CS2Mass fraction is the cyclohexane solution of 5 weight %, and sulfurized oil feed rate is 0.4mL/min, and sulfuration is carried out 3 hours altogether.
Hydrodesulfurization reaction condition: reaction temperature is 280 DEG C, pressure is 4.2MPa, H2Flow velocity is 400mL/min, and the feed rate of reaction raw materials is 0.2mL/min, stable reaction after 3 hours sampling gas chromatogram be analyzed.
Calculating desulfurization degree according to below equation, result is listed in table 4.
Conversion ratio × (the S of desulfurization degree (%)=4,6-DMDBTDMBCH+SDMCHB+SDMBP) × 100%
Wherein, SDMBCH、SDMCHBAnd SDMBPIt is 4 respectively, in the product that 6-DMDBT hydrodesulfurization obtains, dimethyl connection hexamethylene, Dimethylcyclohexyl benzene and the selectivity of dimethyl diphenyl.
Comparative example 11
2.03g basic nickel carbonate (NiO content is 51 weight %), 5.18g molybdenum oxide and 1.32g phosphoric acid are dissolved in the water, are configured to 12.0mL solution.The article shaped (a diameter of 1.1mm, particle length is 2-5mm) the solution impregnation 14.3g comparative example 2 obtained prepared, dip time is 1 hour.The solid product obtained is dried 3 hours in 150 DEG C, then at 400 DEG C of roasting 3h, obtains catalyst A1.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Comparative example 12
Use the method identical with comparative example 11 to prepare catalyst, except for the difference that, in step (2), do not carry out roasting at 400 DEG C, thus obtain catalyst A2.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 61
3.43g basic cobaltous carbonate (CoO content is 70 weight %), 12.00g molybdenum oxide and 2.24g phosphoric acid are dissolved in the water, are configured to 60mL solution.To obtain article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 70.5 weight %) prepared by solution impregnation 20.3g embodiment 2, dip time is 4 hours.After filtration, the solid obtained is dried 4 hours in 160 DEG C, obtains catalyst B2.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 62
By 3.85g nickel nitrate (Ni (NO3)2·6H2O), 5.65g ammonium metatungstate ((NH4)6W7O24·4H2O) it is dissolved in the water, is configured to 17.9mL solution.The article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 70.2 weight %) the solution impregnation 19.1g embodiment 3 obtained prepared, dip time is 1 hour.The solid product obtained is dried 4 hours in 120 DEG C, obtains catalyst B3.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 63
1.18g basic nickel carbonate (NiO content is 51 weight %), 3.00g molybdenum oxide and 0.68g phosphoric acid are dissolved in the water, are configured to 60mL solution.The article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 78.2 weight %) the solution impregnation 18.3g embodiment 4 obtained prepared, dip time is 4 hours.After filtration, the solid product obtained is dried 4 hours in 120 DEG C, obtains catalyst B4.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 64
3.53g basic nickel carbonate (NiO content is 51 weight %), 9.00g molybdenum oxide and 1.38g phosphoric acid are dissolved in the water, are configured to 60mL solution.The article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 73.4 weight %) the solution impregnation 19.5g embodiment 5 obtained prepared, dip time is 4 hours.After filtration, the solid obtained is dried 4 hours in 120 DEG C, obtains catalyst B5.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 65
14.12g basic nickel carbonate (NiO content is 51 weight %), 36.00g molybdenum oxide and 6.70g phosphoric acid are dissolved in the water, are configured to 60mL solution.The article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 74.1 weight %) the solution impregnation 19.3g embodiment 6 obtained obtained, dip time is 4 hours.After filtration, the solid product obtained is dried 4 hours in 120 DEG C, obtains catalyst B6.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 66
Use the method identical with embodiment 61 to prepare catalyst, except for the difference that, use the article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 70.4 weight %) of embodiment 7 preparation, thus obtain catalyst B7.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 67
Use the method identical with embodiment 60 to prepare catalyst, except for the difference that, use the article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 67.3 weight %) of embodiment 8 preparation, thus obtain catalyst B8.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 68
Use the method identical with embodiment 62 to prepare catalyst, except for the difference that, use the article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 74.8 weight %) of embodiment 9 preparation, thus obtain catalyst B9.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 69
Use the method identical with embodiment 64 to prepare catalyst, except for the difference that, use the article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 78.6 weight %) of embodiment 10 preparation, thus obtain catalyst B10.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 70
4.71g basic nickel carbonate (NiO content is 51 weight %), 12.0g molybdenum oxide and 2.24g phosphoric acid are dissolved in the water, are configured to 60mL solution；The article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 70.6 weight %) the solution impregnation 20.1g embodiment 11 obtained prepared, dip time is 4 hours.After filtration, the solid product obtained is dried 4 hours in 120 DEG C, obtains catalyst B11.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Comparative example 13
2.03g basic nickel carbonate (NiO content is 51 weight %), 5.18g molybdenum oxide and 1.32g phosphoric acid are dissolved in the water, are configured to 11.9mL solution.The article shaped (a diameter of 1.1mm, particle length is 2-5mm) the solution impregnation 14.3g comparative example 7 obtained prepared, dip time is 1 hour.The solid product obtained is dried 4 hours in 120 DEG C, then at 400 DEG C of roasting 3h, obtains catalyst A3.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Comparative example 14
Use the method identical with comparative example 13 to prepare catalyst, except for the difference that, do not carry out roasting at 400 DEG C, obtain catalyst A4.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 71
3.43g basic cobaltous carbonate (CoO content is 70 weight %), 12.00g molybdenum oxide and 2.24g phosphoric acid are dissolved in the water, are configured to 60mL solution.To obtain article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 71.2 weight %) prepared by solution impregnation 20.1g embodiment 12, dip time is 4 hours.After filtration, the solid obtained is dried 4 hours in 120 DEG C, obtains catalyst B12.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 72
By 3.85g nickel nitrate (Ni (NO3)2·6H2O), 5.65g ammonium metatungstate ((NH4)6W7O24·4H2O) it is dissolved in the water, is configured to 16.1mL solution.The article shaped (a diameter of 1.1mm, particle length is 2-5mm, and contents on dry basis is 73.7 weight %) the solution impregnation 19.4g embodiment 13 obtained prepared, dip time is 1 hour.The carrier obtained is dried 4 hours in 120 DEG C, obtains catalyst B13.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 73
Use the method identical with embodiment 60 to prepare catalyst, except for the difference that, use the article shaped (a diameter of 1.1mm, particle length is 2-5mm) of embodiment 17 preparation, obtain catalyst B14.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 74
Use the method identical with embodiment 66 to prepare catalyst, except for the difference that, use the article shaped (a diameter of 1.1mm, particle length is 2-5mm) of embodiment 23 preparation, obtain catalyst B15.Using XRF to be analyzed catalyst, use the method identical with embodiment 60 to evaluate the performance of catalyst, result is listed in table 4.
Embodiment 75
Using the method identical with embodiment 67 prepare catalyst and evaluate the performance of catalyst, except for the difference that, use the article shaped (a diameter of 1.1mm, particle length is 2-5mm) of embodiment 24 preparation, obtain catalyst B16, its composition and desulfurization degree are listed in table 4.
Embodiment 76
Using the method identical with embodiment 70 prepare catalyst and evaluate the performance of catalyst, except for the difference that, use the article shaped (a diameter of 1.1mm, particle length is 2-5mm) of embodiment 27 preparation, obtain catalyst B17, its composition and desulfurization degree are listed in table 4.
Table 4
As can be seen from Table 4, in the hydrotreating of hydrocarbon ils, higher catalysis activity is showed using the article shaped of the present invention as the catalyst with hydrogenation catalyst effect prepared by carrier.
Claims (28)
1. a hydrated alumina forming matter, this article shaped is prepared molded body by a kind of raw material, and described molded body is dried and makes, described raw material by least one hydrated alumina, at least one containing the compound of group ivb metallic element, at least one cellulose ether and with or without at least one extrusion aid form, on the basis of the total amount of described raw material, the total content of described cellulose ether is 0.5-10 weight %, with the total content of compound containing group ivb metallic element described in oxide is counted for 0.5-55 weight %, with Al2O3The total content of the described hydrated alumina of meter is 35-98 weight %, and the water absorption rate of this article shaped is 0.4-1.5, and δ-value is less than 10%, Q1For more than 12N/mm,
Wherein,
Q1For the radial direction crushing strength of the article shaped without water soaking, in terms of N/mm,
Q2For through water soaking 30 minutes the radial direction crushing strength that is dried the article shaped after 4 hours at 120 DEG C, in terms of N/mm.
Article shaped the most according to claim 1, wherein, described molded body is at least one hydrated alumina, at least one compound containing group ivb metallic element and at least one cellulose ether to be mixed with water, obtains the first mixture, and is made by described first mixture forming；Or
Described molded body is at least one hydrated alumina and at least one cellulose ether to be mixed with water, obtain the second mixture, and described second mixture is successively shaped and is dehydrated, obtain preform, and on described preform, load at least one compound containing group ivb metallic element and make.
Article shaped the most according to claim 1 and 2, wherein, on the basis of the total amount of described raw material, the total content of described cellulose ether is 1-8 weight %, with the total content of compound containing group ivb metallic element described in oxide is counted for 1-50 weight %, with Al2O3The total content of the described hydrated alumina of meter is 42-96 weight %.
Article shaped the most according to claim 1 and 2, wherein, described cellulose ether is selected from methylcellulose, hydroxyethylmethyl-cellulose and hydroxypropyl methyl cellulose.
Article shaped the most according to claim 1 and 2, wherein, described group ivb metallic element is selected from titanium and zirconium.
Article shaped the most according to claim 1 and 2, wherein, the described compound containing group ivb metallic element is selected from basic zirconium chloride, zirconium acetate, Disulfatozirconic acid., zirconium nitrate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium, zirconium dioxide, metatitanic acid, metatitanic acid, titanium dioxide, titanium sulfate and the compound shown in Formulas I
TiXn(OR)4-n(I),
In Formulas I, X is halogen, and R is C1-C5Alkyl, n is the integer of 0-4.
Article shaped the most according to claim 1 and 2, wherein, described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
Article shaped the most according to claim 1 and 2, wherein, the water absorption rate of described article shaped is 0.6-1, and δ-value is less than 5%, Q1For 15-30N/mm.
Article shaped the most according to claim 1, wherein, on the basis of the total amount of described raw material, the content of described extrusion aid is 0.1-8 weight %.
Article shaped the most according to claim 9, wherein, on the basis of the total amount of described raw material, the content of described extrusion aid is 0.5-5 weight %.
11. according to the article shaped described in any one in claim 1,9 and 10, and wherein, described extrusion aid is starch.
12. according to the article shaped described in any one in claim 1,9 and 10, and wherein, described extrusion aid is sesbania powder.
13. 1 kinds of methods preparing hydrated alumina forming matter, the method includes being prepared molded body by a kind of raw material, and described molded body is dried, thus obtain described hydrated alumina forming matter, described raw material is by least one hydrated alumina, at least one compound containing group ivb metallic element, at least one cellulose ether and with or without at least one extrusion aid composition, on the basis of the total amount of described raw material, the total content of described cellulose ether is 0.5-10 weight %, with the total content of compound containing group ivb metallic element described in oxide is counted for 0.5-55 weight %, with Al2O3The total content of the described hydrated alumina of meter is 35-98 weight %.
14. methods according to claim 13, wherein, described raw material the mode preparing described molded body includes:
At least one hydrated alumina, at least one compound containing group ivb metallic element and at least one cellulose ether are mixed with water, obtains the first mixture, and by described first mixture forming；Or
At least one hydrated alumina and at least one cellulose ether are mixed with water, obtain the second mixture, and described second mixture is successively shaped and is dehydrated, obtain preform, described preform loads at least one compound containing group ivb metallic element.
15. according to the method described in claim 13 or 14, and wherein, on the basis of the total amount of described raw material, the total content of described cellulose ether is 1-8 weight %, with the total content of compound containing group ivb metallic element described in oxide is counted for 1-50 weight %, with Al2O3The total content of the described hydrated alumina of meter is 42-96 weight %.
16. according to the method described in claim 13 or 14, and wherein, described cellulose ether is selected from methylcellulose, hydroxyethylmethyl-cellulose and hydroxypropyl methyl cellulose.
17. according to the method described in claim 13 or 14, and wherein, described group ivb metallic element is selected from titanium and zirconium.
18. according to the method described in claim 13 or 14, wherein, the described compound containing group ivb metallic element is selected from basic zirconium chloride, zirconium acetate, Disulfatozirconic acid., zirconium nitrate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium, zirconium dioxide, metatitanic acid, metatitanic acid, titanium dioxide, titanium sulfate and the compound shown in Formulas I
TiXn(OR)4-n(I),
In Formulas I, X is halogen, and R is C1-C5Alkyl, n is the integer of 0-4.
19. according to the method described in claim 13 or 14, and wherein, described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
20. methods according to claim 13, wherein, described dry temperature be 60 DEG C less than 350 DEG C.
21. methods according to claim 20, wherein, described dry temperature is 80-300 DEG C.
22. methods according to claim 13, wherein, on the basis of the total amount of described raw material, the content of described extrusion aid is 0.1-8 weight %.
23. methods according to claim 22, wherein, on the basis of the total amount of described raw material, the content of described extrusion aid is 0.5-5 weight %.
24. according to the method described in any one in claim 13,22 and 23, and wherein, described extrusion aid is starch.
25. according to the method described in any one in claim 13,22 and 23, and wherein, described extrusion aid is sesbania powder.
The hydrated alumina forming matter that in 26. claim 13-25 prepared by method described in any one.
In 27. claim 1-12 and 26, the hydrated alumina forming matter described in any one is as desiccant or the application of the carrier as loaded catalyst.
28. application according to claim 27, wherein, described catalyst is the catalyst with hydrogenation catalyst effect.
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| US6593270B1 (en) * | 1997-11-13 | 2003-07-15 | Degussa Ag | Moldings based on pyrogenic silicon dioxide |
| CN101722006A (en) * | 2009-11-24 | 2010-06-09 | 山东齐鲁科力化工研究院有限公司 | Dual-functional hydrogenation catalyst |
| CN102240555A (en) * | 2010-05-13 | 2011-11-16 | 中国石油化工股份有限公司 | Residual oil hydrogenation catalyst and use thereof |
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| US6593270B1 (en) * | 1997-11-13 | 2003-07-15 | Degussa Ag | Moldings based on pyrogenic silicon dioxide |
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