CN103480326A - Hydrated alumina molded matter and preparation method thereof, alumina molded matter and applications of hydrated alumina molded matter and alumina molded matter - Google Patents
Hydrated alumina molded matter and preparation method thereof, alumina molded matter and applications of hydrated alumina molded matter and alumina molded matter Download PDFInfo
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Abstract
The invention provides a hydrated alumina molded matter, and a preparation method and an application thereof. The hydrated alumina molded matter is prepared by molding raw materials comprising at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether. The water absorption rate of the hydrated alumina molded matter is 0.4-1.5, the delta value is 10% or less, and the Q1 is 12 N/mm or more. The invention also provides an alumina molded matter and an application thereof, wherein the alumina molded matter is prepared by calcination of the hydrated alumina molded matter. The molded matters provided by the invention have high strength and good strength retention rate. According to the method of the invention, a peptizing agent is not used during the molding process.
Description
Technical field
The present invention relates to a kind of hydrated alumina forming matter and its preparation method and application, the invention still further relates to a kind of aluminium oxide article shaped and application thereof.
Background technology
Aluminium oxide, particularly gama-alumina, because it has pore structure and heat-resistant stability preferably, and higher specific area, therefore the aluminium oxide article shaped is commonly used for the carrier of drier or loaded catalyst.Can carry out modulation to the character of aluminium oxide by introduce Y molecular sieve in the aluminium oxide article shaped, so that it meets the requirement of specific occasion.For example, adopt the aluminium oxide article shaped that contains Y molecular sieve as the carrier loaded active component with hydrogenation catalyst effect, the hydrogenation catalyst performance of the catalyst of preparation can be carried out modulation.
Can be by hydrated alumina and water, peptizing agent and optional extrusion aid are mixed containing the aluminium oxide article shaped of Y molecular sieve, and mixture is successively carried out to moulding, drying and high-temperature roasting and prepare.
Drying and without the article shaped of high-temperature roasting (, hydrated alumina forming matter) when the carrier as loaded catalyst has the active component of catalytic action or is used as drier by the method load of flooding, the phenomenon of be easy to dissolve, efflorescence and duct caving in, thereby make article shaped lose shape, therefore drying and can not be directly as drier or as the dipping carrier without the hydrated alumina forming matter of high-temperature roasting only, the process that must experience a high-temperature roasting could be as drier or as the dipping carrier.
And; usually use acid (for example: nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid) as peptizing agent; the existence of acid is easy to corrode former on the one hand; discharge on the other hand a large amount of sour gas in dry and roasting process; both unfavorable to operating personnel's health, also be unfavorable for environmental protection.
Summary of the invention
The object of the invention is to overcome prior art and must use peptizing agent when preparing the aluminium oxide article shaped, and the low technical problem of unfired hydrated alumina forming matter strength retention.The invention provides a kind of hydrated alumina forming matter and preparation method thereof, this hydrated alumina forming matter is not used peptizing agent in forming process, there is good strength retention, even carry out the long-time phenomenon that also can or substantially not there will be dissolving, efflorescence and duct to cave in of soaking in solution.The present invention also provides a kind of aluminium oxide article shaped of hydrated alumina forming matter of the present invention being carried out to roasting and obtaining, and this article shaped has good absorbent properties, high intensity and strength retention.
The present inventor finds in research process, hydrated alumina forming matter without high-temperature roasting is easy to occur dissolving in adsorption process and in dipping process, efflorescence and duct cave in, and then the reason of losing shape may be: the hydrated alumina forming matter without high-temperature roasting contains peptizing agent, the Main Function of described peptizing agent is to make as the various powder adhesion of raw material together, yet in absorption and dipping process, because peptizing agent dissolves, from article shaped, run off in a large number, and then make article shaped occur dissolving, efflorescence and the duct phenomenon of caving in, the final shape of losing.
The present inventor finds through further investigation: in the forming process of hydrated alumina, do not use peptizing agent, introduce cellulose ether simultaneously, even so the article shaped of preparation is not carried out high-temperature roasting, also there is good strength retention, carry out the phenomenon that long-time dipping can or not there will be dissolving, efflorescence and duct to cave in substantially yet in maceration extract, and this article shaped also have good absorbent properties.Completed thus the present invention.
A first aspect of the present invention provides a kind of hydrated alumina forming matter, this article shaped is made the material forming that contains at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, the water absorption rate of this article shaped is 0.4-1.5, and the δ value is below 10%, Q
1more than 12N/mm, wherein,
Q
1for the radially crushing strength of the article shaped without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radially crushing strength of the article shaped of 120 ℃ of dryings after 4 hours, in N/mm.
A second aspect of the present invention provides a kind of method for preparing hydrated alumina forming matter, and the method comprises the material forming that will contain at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, and the formed body obtained is carried out to drying.
A third aspect of the present invention provides a kind of hydrated alumina forming matter prepared by method of the present invention.
A fourth aspect of the present invention provides a kind of aluminium oxide article shaped, and this aluminium oxide article shaped is carried out hydrated alumina forming matter of the present invention roasting and makes.
A fifth aspect of the present invention provide a kind of according to hydrated alumina forming matter of the present invention or aluminium oxide article shaped as drier or as the application of the carrier of loaded catalyst.
Do not contain peptizing agent (for example: aluminium colloidal sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid) according to hydrated alumina forming matter of the present invention, there is good strength retention, even carry out the phenomenon that long-time dipping can or not there will be dissolving, efflorescence and duct to cave in substantially yet in maceration extract.Thereby, can be as drier or as the carrier of loaded catalyst according to hydrated alumina forming matter of the present invention.Aluminium oxide article shaped according to the present invention is made by hydrated alumina forming matter of the present invention is carried out to roasting, has good intensity and strength retention, also has good absorbent properties simultaneously.
Particularly, more than can reaching 12N/mm respectively according to the radially crushing strength of hydrated alumina forming matter of the present invention and aluminium oxide article shaped, water absorption rate can reach 0.4-1.5 respectively, and δ value (that is, the crushing strength loss late after immersion) respectively can be for below 10%.
The method according to this invention, do not used peptizing agent (that is, described raw material does not contain peptizing agent) in forming process, reduced the corrosion to former on the one hand, extended the service life of former, reduced production cost; Greatly reduce on the other hand the amount of the sour gas discharged in dry and roasting process, reduced the impact on operator ' s health, also helped environmental protection simultaneously.
The specific embodiment
A first aspect of the present invention provides a kind of hydrated alumina forming matter, and this article shaped is made the material forming that contains at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether.Term " at least one " refers to one or more.
According to hydrated alumina forming matter of the present invention, described raw material contains hydrated alumina, Y molecular sieve and cellulose ether, but does not contain peptizing agent, and the hydrated alumina forming matter of making has good strength retention, also has good absorbent properties simultaneously.
According to hydrated alumina forming matter of the present invention, the composition that is used to form the raw material of described article shaped can carry out suitable selection according to the concrete application scenario of the article shaped of expecting.Usually, the total amount of described raw material of take is benchmark, and the total content of described cellulose ether can be the 0.5-8 % by weight, is preferably the 1-6 % by weight, more preferably the 2-5 % by weight; The total content of described Y molecular sieve can be the 0.5-55 % by weight, is preferably the 1-50 % by weight, more preferably the 2-45 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be the 37-98 % by weight, is preferably the 44-97 % by weight; 50-95 % by weight more preferably.In the present invention, while calculating the total amount of described raw material, hydrated alumina is with Al
2o
3meter, and described raw material does not comprise the water of introducing in described material forming process.
According to the present invention, described cellulose ether refers to after the hydrogen atom at least part of hydroxyl in cellulosic molecule is replaced by one or more alkyl that the ether formed is derivative, and wherein, a plurality of described alkyl can, for identical, can be also difference.Described alkyl is selected from alkyl and the unsubstituted alkyl of replacement.Described unsubstituted alkyl (for example: C is preferably alkyl
1-C
5alkyl).In the present invention, C
1-C
5alkyl comprise C
1-C
5straight chained alkyl and C
3-C
5branched alkyl, its instantiation can include but not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl and tertiary pentyl.The alkyl of described replacement for example can for the alkyl by hydroxyl or carboxyl substituted (for example: C
1-C
5the alkyl replaced by hydroxyl, C
1-C
5by the alkyl of carboxyl substituted), its instantiation can include but not limited to: methylol, ethoxy, hydroxypropyl, hydroxyl butyl, carboxymethyl, carboxyethyl and carboxylic propyl group.
The present invention is not particularly limited for the kind of described cellulose ether and for the substituent amount of the hydrogen atom on the hydroxyl of substituted cellulose molecule, can be common various cellulose ethers.Particularly, described cellulose ether can be selected from but be not limited to: methylcellulose, ethyl cellulose, hydroxyethylcellulose, HEMC, hydroxypropyl cellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose, carboxyethyl cellulose and carboxymethyl hydroxyethyl cellulose.Preferably, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
In the present invention, described Y molecular sieve can be this area various Y molecular sieves commonly used.When article shaped according to the present invention is used as the carrier of the catalyst with hydrogenation catalyst effect, described Y molecular sieve can be selected from NaY molecular sieve, CaY molecular sieve, NH
4y molecular sieve, HY molecular sieve, REY molecular sieve and ultra-steady Y molecular sieve.Preferably, described Y molecular sieve is selected from NH
4y molecular sieve, HY molecular sieve, REY molecular sieve and ultra-steady Y molecular sieve.
The present invention is not particularly limited for the kind of described hydrated alumina, can select for the routine of this area.Preferably, described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.More preferably, described hydrated alumina is boehmite.
According to hydrated alumina forming matter of the present invention, described article shaped is made the material forming that contains at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether.
Can adopt this area the whole bag of tricks commonly used by described material forming, be not particularly limited.In one embodiment of the invention, described article shaped is that at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether are mixed with water, by the mixture moulding obtained, and the formed body obtained is carried out to drying and make.According to the present invention, for the preparation of the consumption of the water of described mixture, be not particularly limited, as long as the consumption of water can be guaranteed various components are mixed.
According to hydrated alumina forming matter of the present invention, the mode of described moulding is not particularly limited, and can adopt this area various molding modes commonly used, for example: extrusion, spraying, round as a ball, compressing tablet or their combination.Of the present invention a kind of preferred embodiment in, carry out moulding by the mode of extrusion.
According to hydrated alumina forming matter of the present invention, described formed body is carried out to dry temperature and can select for the routine of this area.Usually, the temperature of described drying can, for more than 60 ℃ and lower than 350 ℃, be preferably 80-300 ℃, more preferably 120-250 ℃.The time of described drying can be carried out suitable selection according to dry temperature, can make in the article shaped finally obtained volatile matter content meet instructions for use, is as the criterion.Usually, the time of described drying can be 1-48 hour, is preferably 2-24 hour, more preferably 2-12 hour.
According to hydrated alumina forming matter of the present invention, can there are various shapes according to concrete instructions for use, for example: spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.
According to hydrated alumina forming matter of the present invention, described raw material can also contain at least one extrusion aid.The consumption of described extrusion aid and kind can be selected for the routine of this area.Usually, the total amount of described raw material of take is benchmark, and the content of described extrusion aid can be the 0.1-8 % by weight, is preferably the 0.5-5 % by weight.According to hydrated alumina forming matter of the present invention, described extrusion aid is preferably starch (that is, described raw material also contains starch).Starch as extrusion aid can be the starch in various sources commonly used, this area, for example: the powder obtained through pulverizing by vegetable seeds, as the sesbania powder.
According to hydrated alumina forming matter of the present invention, the radially crushing strength loss late (that is, δ value) of described article shaped after immersion is below 10%, is generally (as below 4%) below 5%; Radially crushing strength (that is, Q without the article shaped of water soaking
1) can, for more than 12N/mm, be even more than 15N/mm.Particularly, according to the Q of article shaped of the present invention
1can be for 15-30N/mm(as 15-25N/mm).The water absorption rate of described article shaped is 0.4-1.5, is generally 0.6-1.
In the present invention, the δ value, for estimating the strength retention of article shaped, is defined by following formula:
Wherein, Q
1for the radially crushing strength of the article shaped without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radially crushing strength of the article shaped of 120 ℃ of dryings after 4 hours, in N/mm.
In the present invention, described radially crushing strength according to " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety front page, the volumes such as Yang Cuiding) in the RIPP 25-90 of record the method stipulated measure.
In the present invention, described water absorption rate refers to that dry article shaped soaks the ratio of weight of the article shaped of weight change value before and after 30 minutes and described drying by excessive deionized water.Concrete method of testing is: article shaped to be measured, 120 ℃ of dryings 4 hours, is then sieved with 40 purpose standard screens, take the 20g oversize and (be designated as w as testing sample
1), testing sample is soaked 30 minutes by the 50g deionized water, after filtration, solid phase is drained to 5 minutes, the weight of the solid phase that then weighing drains (is designated as w
2), calculate water absorption rate with following formula:
Not only there are good absorbent properties according to hydrated alumina forming matter of the present invention, and there is excellent strength retention, even long-time immersion still has higher intensity in water.Therefore, hydrated alumina forming matter according to the present invention is suitable for the carrier as drier or loaded catalyst.
A second aspect of the present invention provides a kind of method for preparing hydrated alumina forming matter, and the method comprises the material forming that will contain at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, and the formed body obtained is carried out to drying.
The method according to this invention, the raw material that contains at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether by use, do not use peptizing agent, also can prepare article shaped, and the article shaped of preparation not only has good absorbent properties, and has high strength retention.
The method according to this invention, the composition of described raw material can carry out suitable selection according to the concrete application scenario of the article shaped of final preparation.Usually, the total amount of described raw material of take is benchmark, and the total content of described cellulose ether can be the 0.5-8 % by weight, is preferably the 1-6 % by weight, more preferably the 2-5 % by weight; The total content of described Y molecular sieve can be the 0.5-55 % by weight, is preferably the 1-50 % by weight, more preferably the 2-45 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be the 37-98 % by weight, is preferably the 44-97 % by weight; 50-95 % by weight more preferably.
The method according to this invention, the kind of described cellulose ether, Y molecular sieve and hydrated alumina, with described identical above, does not repeat them here.
The method according to this invention, can adopt this area the whole bag of tricks commonly used by described material forming, thereby obtain described formed body.For example: at least one hydrated alumina, at least one cellulose ether and at least one Y molecular sieve can be mixed with water, and the mixture obtained is carried out to moulding, thereby obtain described formed body.According to the present invention, for the preparation of the consumption of the water of described mixture, be not particularly limited, as long as the consumption of water can be guaranteed various components are mixed.
The method according to this invention, the mode of described moulding is not particularly limited, and can adopt this area various molding modes commonly used, for example: extrusion, spraying, round as a ball, compressing tablet or their combination.Of the present invention a kind of preferred embodiment in, carry out moulding by the mode of extrusion.
The method according to this invention, described article shaped (that is, formed body) can have various shapes according to concrete instructions for use, for example: spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.
The method according to this invention, carry out dry temperature by described formed body and can select for the routine of this area.Usually, the temperature of described drying can, for more than 60 ℃ and lower than 350 ℃, be preferably 80-300 ℃, more preferably 120-250 ℃.The time of described drying can be carried out suitable selection according to dry temperature, meets instructions for use with volatile matter content in the article shaped that can make finally to obtain and is as the criterion.Usually, the time of described drying can be 1-48 hour, is preferably 2-24 hour, more preferably 2-12 hour.
The method according to this invention, described raw material can also contain at least one extrusion aid.The consumption of described extrusion aid and kind can be selected for the routine of this area.Usually, the total amount of described raw material of take is benchmark, and the content of described extrusion aid can be the 0.1-8 % by weight, is preferably the 0.5-5 % by weight.Described extrusion aid is preferably starch (that is, described raw material also contains starch).Starch as extrusion aid can be the starch in various sources commonly used, this area, for example: the powder obtained through pulverizing by vegetable seeds, as the sesbania powder.
Prepared according to the methods of the invention hydrated alumina forming matter (that is, only drying and unfired article shaped) has good strength retention and absorbent properties.Usually, for the hydrated alumina forming matter prepared by method of the present invention, radially crushing strength can be even more than 15N/mm for more than 12N/mm, for example can be for 15-30N/mm(as 15-25N/mm); The δ value can, for below 10%, be generally (as below 4%) below 5%; Water absorption rate can be 0.4-1.5, can be for example 0.6-1.Therefore, the method according to this invention in forming process without using peptizing agent, and the hydrated alumina forming matter of preparation has good strength retention and absorbent properties, be suitable for coming load to there is the active component of catalytic action as drier or as the carrier of loaded catalyst.
Thus, a third aspect of the present invention provides a kind of hydrated alumina forming matter prepared by method of the present invention.
A fourth aspect of the present invention provides a kind of aluminium oxide article shaped, and this aluminium oxide article shaped is carried out hydrated alumina forming matter of the present invention roasting and makes.
The present invention is not particularly limited for the condition of roasting, can select for the routine of this area.Particularly, the temperature of described roasting can be 450-950 ℃, is preferably 500-900 ℃; The time of described roasting can be 2-8 hour, is preferably 3-6 hour.
Aluminium oxide article shaped according to the present invention has high intensity and strength retention and good absorbent properties.Usually, the radially crushing strength of described aluminium oxide article shaped can be even more than 15N/mm for more than 12N/mm, generally can be for 15-30N/mm(as 20-25N/mm); The δ value is below 10%, is generally (as below 4%) below 5%; Water absorption rate is 0.4-1.5, can be for example 0.6-1.
A fifth aspect of the present invention provides according to hydrated alumina forming matter of the present invention or aluminium oxide article shaped as drier or as the application of the carrier of loaded catalyst.
In the present invention, described loaded catalyst can be usingd hydrated alumina or the aluminium oxide article shaped catalyst as carrier for commonly used various in this area.Preferably, described catalyst is the catalyst with hydrogenation catalyst effect.That is, according to hydrated alumina forming matter of the present invention and aluminium oxide article shaped, be particularly suitable for as the carrier with catalyst of hydrogenation catalyst effect.
In hydrated alumina forming matter according to the present invention or aluminium oxide article shaped during as the carrier of the catalyst with hydrogenation catalyst effect, can adopt this area the whole bag of tricks commonly used (for example: dipping) will there is the active constituent loading of hydrogenation catalyst effect on hydrated alumina forming matter according to the present invention or aluminium oxide article shaped, for example: the aqueous solution that can contain described active component by use floods article shaped of the present invention, then load there is is the article shaped of described active component to carry out drying and optional roasting, thereby obtain having the catalyst of hydrogenation catalyst effect.
Describe the present invention in detail below in conjunction with embodiment and Comparative Examples.
In following examples and Comparative Examples, adopt the method for stipulating in RIPP 25-90 to measure the radially crushing strength of the article shaped of preparation.
In following examples and Comparative Examples, adopt following methods to measure the δ value of the article shaped of preparation: the radially crushing strength that the method for stipulating in employing RIPP 25-90 is measured without the article shaped of water soaking (is designated as Q
1); The article shaped of preparation is placed in to the 50g deionized water, soaks 30 minutes, then filter, by the solid that obtains, 120 ℃ of dryings 4 hours, the radially crushing strength of measuring dry solid according to the method for stipulating in RIPP 25-90 (was designated as Q
2), adopt following formula to calculate the δ value,
In following examples and Comparative Examples, adopt following methods to measure the water absorption rate of the article shaped of preparation: article shaped to be measured, 120 ℃ of dryings 4 hours, then to be sieved with 40 purpose standard screens, take the 20g oversize and (be designated as w as testing sample
1), testing sample is soaked 30 minutes by the 50g deionized water, after filtration, solid phase is drained to 5 minutes, the weight of the solid phase that then weighing drains (is designated as w
2), calculate water absorption rate with following formula:
In following examples and Comparative Examples, contents on dry basis was measured testing sample 600 ℃ of roastings 4 hours.
In following examples and Comparative Examples, by the x ray fluorescence spectrometry, (that is, XRF) measure the composition of catalyst.
Embodiment 1-9 is for illustrating hydrated alumina forming matter of the present invention and its preparation method and application.
Embodiment 1
(1) by 100.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 4.0g methylcellulose (purchased from Shen, Zhejiang sea chemical industry Co., Ltd), 3.0g sesbania powder, (purchased from Sinopec catalyst Chang Ling branch company, lattice constant is the 20.0g ultra-steady Y molecular sieve
contents on dry basis is 95 % by weight, Na
2the content of O is 0.05 % by weight) and the 85g deionized water mix.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar of extruding is placed in to baking oven, 150 ℃ of dryings 12 hours, thereby obtains hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
(2) 4.71 gram basic nickel carbonates (NiO content is 51 % by weight), 12.0 gram molybdenum oxides and 2.24 gram phosphoric acid are dissolved in the water, are mixed with 60mL solution; Article shaped prepared by the solution impregnation 20.3g step (1) obtained (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.5 % by weight), dip time is 4 hours.After filtration, the solid product that obtains, in 150 ℃ of dryings 2 hours, is obtained to catalyst B 1.The composition of catalyst is listed in table 2.
(3) with 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) as model compound, the catalytic activity of catalyst prepared by evaluation procedure on the high-pressure hydrogenation micro-reactor (2), actual conditions is as follows.
The n-decane solution of reaction raw materials: 4,6-DMDBT, wherein, concentration is 0.45 % by weight;
The conditions of vulcanization of catalyst: the useful load of catalyst is 0.15g, and temperature is 360 ℃, and pressure is 4.2MPa, H
2flow velocity is 400mL/min, and sulfurized oil adopts CS
2the cyclohexane solution that mass fraction is 5 % by weight, the sulfurized oil feed rate is 0.4mL/min, sulfuration is carried out 3 hours altogether.
The hydrodesulfurization reaction condition: reaction temperature is 280 ℃, and pressure is 4.2MPa, H
2flow velocity is 400mL/min, and the reaction oil feed rate is 0.2mL/min, and stable reaction sampled and analyzed by gas-chromatography after 3 hours.
Calculate desulfurization degree according to following formula, result is listed in table 3.
Desulfurization degree (%)=4, the conversion ratio of 6-DMDBT * (S
dMBCH+ S
dMCHB+ S
dMBP) * 100%
Wherein, S
dMBCH, S
dMCHBand S
dMBPrespectively in the product that obtains of 4,6-DMDBT hydrodesulfurization, dimethyl connection cyclohexane, Dimethylcyclohexyl benzene and dimethyl diphenyl selective.
Comparative Examples 1
(1) adopt the method identical with embodiment 1 to prepare article shaped, different, do not use methylcellulose, but use the 2.5mL red fuming nitric acid (RFNA), and the wet bar obtained after 12 hours, then 600 ℃ of roastings 4 hours, thereby is obtained to article shaped 150 ℃ of dryings.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
(2) 2.03 gram basic nickel carbonates (NiO content is 51 % by weight), 5.18 gram molybdenum oxides and 1.32 gram phosphoric acid are dissolved in the water, are mixed with 12.3mL solution.Article shaped prepared by the solution impregnation 14.3g step (1) obtained (diameter is 1.1mm, and particle length is 2-5mm), dip time is 1 hour.The solid product that obtains, in 120 ℃ of dryings 4 hours, then, at 400 ℃ of roasting 3h, is obtained to catalyst A 1.The composition of catalyst is listed in table 2.
(3) catalytic activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 3.
Comparative Examples 2
(1) adopt the method identical with Comparative Examples 1 to prepare carrier, different, at 600 ℃, do not carry out roasting, thereby obtain article shaped.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
(2) adopt the method Kaolinite Preparation of Catalyst identical with Comparative Examples 1, different, carrier is article shaped prepared by Comparative Examples 2 steps (1), and in dipping process, the phenomenon of dissolving and structure is caved in appears in carrier, and result can't obtain the catalyst of moulding.
Comparative Examples 3
Adopt the method identical with embodiment 1 to prepare article shaped, different, do not use methylcellulose, result can't make article shaped.
Comparative Examples 4
Adopt the method identical with Comparative Examples 1 to prepare article shaped and catalyst, different, in step (2), at 400 ℃, do not carry out roasting, thereby obtain catalyst A 2, the composition of catalyst is listed in table 2.The catalytic activity of the catalyst that adopts the method evaluation identical with embodiment 1 step (3) to prepare, result is listed in table 3.
Embodiment 2
(1) in the retort of a 2L, take and the stream mode add aluminum sulfate solution and the sodium aluminate solution (Al that 2000mL concentration is 48g/L
2o
3content is 200g/L, and the causticity coefficient is 1.58) carry out precipitation reaction, reaction temperature is 50 ℃, and the pH value is 6.0, and reaction time is 15 minutes; The slurries that obtain are filtered with vacuum filter, after to be filtered completing, on filter cake, supplement and add 20L deionized water (temperature is 40 ± 5 ℃) flush cake approximately 60 minutes.Filter cake after washing is joined to the 1.5L deionized water for stirring and become slurries, slurries are carried out to drying with being pumped into spray dryer, control the outlet temperature of spray dryer within the scope of 100-110 ℃, the dry materials time is 2 minutes, obtain hydrated alumina, wherein, Al
2o
3content is 63 % by weight, through XRD analysis, is defined as amorphous state.
(2) by 50.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company; contents on dry basis is 69.5 % by weight), the amorphous hydrated aluminium oxide for preparing of 50.0g step (1), 2.0g methylcellulose (purchased from sea, Zhejiang Shen chemical industry Co., Ltd), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), (purchased from Sinopec Shandong catalyst branch company, lattice constant is 5.0g REY molecular sieve
contents on dry basis is 94 % by weight, Na
2o content is 0.31 % by weight, and in oxide, ree content is 23.5 % by weight) and the 92g deionized water mix.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 220 ℃ of dryings 6 hours, thereby obtains according to hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
(3) 3.43 gram basic cobaltous carbonates (CoO content is 70 % by weight), 12.00 gram molybdenum oxides and 2.24 gram phosphoric acid are dissolved in the water, are mixed with 60mL solution.To obtain article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 69.8 % by weight) prepared by solution impregnation 20.5g step (2), dip time is 4 hours.After filtration, the solid that obtains, in 140 ℃ of dryings 3 hours, is obtained to catalyst B 2.The composition of catalyst is listed in table 2.
(3) catalytic activity of the catalyst that adopts the method evaluation step (3) identical with embodiment 1 step (3) to prepare, result is listed in table 3.
Embodiment 3
(1) by the 60.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), the 40.0g gibbsite is (purchased from Pingguo Aluminium Industry Co., Guangxi, contents on dry basis is 64.5 % by weight), 1.0g methylcellulose (purchased from Shen, Zhejiang sea chemical industry Co., Ltd), 2.0g hydroxypropyl methylcellulose (purchased from sea, Zhejiang Shen chemical industry Co., Ltd), 3.0g sesbania powder, (purchased from Sinopec Shandong catalyst branch company, lattice constant is 30.0g NaY molecular sieve
contents on dry basis is 96 % by weight) and the 120g deionized water and stirring even.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 80 ℃ of dryings 12 hours, obtains hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
(2) by 3.85 gram nickel nitrate (Ni (NO
3)
26H
2o), 5.65 gram ammonium metatungstate ((NH
4)
6w
7o
244H
2o) be dissolved in the water, be mixed with 14.4mL solution.Article shaped prepared by the solution impregnation 19.4g step (1) obtained (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 67.3 % by weight), dip time is 1 hour.The solid that obtains, in 120 ℃ of dryings 4 hours, is obtained to catalyst B 3.The composition of catalyst is listed in table 2.
(3) catalytic activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 3.
Embodiment 4
(1) 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), (purchased from Sinopec Shandong catalyst branch company, lattice constant is the 67.0gHY molecular sieve
contents on dry basis is 92 % by weight) and the 150g deionized water and stirring even.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 150 ℃ of dryings 12 hours, thereby obtains according to hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
(2) 1.18 gram basic nickel carbonates (NiO content is 51 % by weight), 3.00 gram molybdenum oxides and 0.68 gram phosphoric acid are dissolved in the water, are mixed with 60mL solution.Article shaped prepared by the solution impregnation 19.2g step (1) obtained (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 74.6 % by weight), dip time is 4 hours.After filtration, the solid product that obtains, in 120 ℃ of dryings 4 hours, is obtained to catalyst B 4.The composition of catalyst is listed in table 2.
(3) catalytic activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 3.
Comparative Examples 5
Adopt the method identical with embodiment 4 to prepare hydrated alumina forming matter, no, do not use HEMC, but use 20mL aluminium colloidal sol (purchased from this promise New Chemical Material science and technology Co., Ltd of Dalian, Al
2o
3content is 10 % by weight), the radially crushing strength of the article shaped obtained, water absorption rate and δ value are listed in table 1.
Embodiment 5
(1) by 100.0g boehmite SB powder (purchased from Sasol company; contents on dry basis is 75.0 % by weight), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 2.0g hydroxypropyl methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder, (purchased from Sinopec Shandong catalyst branch company, lattice constant is the 20.0gNaY molecular sieve
contents on dry basis is 96 % by weight) with the 115g deionized water, mix.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 250 ℃ of dryings 4 hours, thereby obtains according to hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
(2) 3.53 gram basic nickel carbonates (NiO content is 51 % by weight), 9.00 gram molybdenum oxides and 1.38 gram phosphoric acid are dissolved in the water, are mixed with 60mL solution.Article shaped prepared by the solution impregnation 19.7g step (1) obtained (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 72.5 % by weight), dip time is 4 hours.After filtration, the solid that obtains, in 120 ℃ of dryings 4 hours, is obtained to catalyst B 5.The composition of catalyst is listed in table 2.
(3) catalytic activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 3.
Embodiment 6
(1) by 100.0g boehmite (purchased from Yantai, Shandong permanent brightness chemical industry Co., Ltd, contents on dry basis is 71.0 % by weight), 5.0g hydroxypropyl methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder, 35.0g NH
4(purchased from Sinopec Shandong catalyst branch company, lattice constant is Y molecular sieve
contents on dry basis is 91 % by weight) with the 110g deionized water, mix.The mixture obtained is sent in extruder and extruded, obtain wet bar.The wet bar obtained is placed in to baking oven, 180 ℃ of dryings 4 hours, thereby obtains according to hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
(2) 14.12 gram basic nickel carbonates (NiO content is 51 % by weight), 36.00 gram molybdenum oxides and 6.7 gram phosphoric acid are dissolved in the water, are mixed with 60mL solution.The article shaped that the solution impregnation 19.5g step (1) obtained is obtained (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 73.3 % by weight), dip time is 4 hours.After filtration, the solid product that obtains, in 120 ℃ of dryings 4 hours, is obtained to catalyst B 6.The composition of catalyst is listed in table 2.
(3) catalytic activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 3.
Comparative Examples 6
Adopt the method identical with embodiment 6 to prepare hydrated alumina forming matter, different, do not use hydroxypropyl methylcellulose, but use 5.0mL acetic acid, the radially crushing strength of the hydrated alumina forming matter obtained, water absorption rate and δ value, result is listed in table 1.
Embodiment 7
(1) adopt the method identical with embodiment 2 to prepare hydrated alumina forming matter, different, the content of methylcellulose is 4.0g, and the content of HEMC is 5.0g, obtains hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
(2) adopt the method Kaolinite Preparation of Catalyst identical with embodiment 2, different, carrier is article shaped (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.4 % by weight) prepared by embodiment 7 steps (1), obtains catalyst B 7.The composition of catalyst is listed in table 2.
(3) catalytic activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 3.
Embodiment 8
(1) adopt the method identical with embodiment 3 to prepare article shaped, different, the wet bar obtained is placed in to baking oven, 120 ℃ of dryings 12 hours, obtain hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
(2) adopt the method Kaolinite Preparation of Catalyst B8 identical with embodiment 3, different, carrier is article shaped prepared by embodiment 8 steps (1), and the composition of catalyst is listed in table 2.
(3) catalytic activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 3.
Embodiment 9
(1) adopt the method identical with embodiment 5 to prepare article shaped, different, the wet bar obtained is placed in to baking oven, 300 ℃ of dryings 4 hours, obtain hydrated alumina forming matter of the present invention.The radially crushing strength of the article shaped that mensuration obtains, water absorption rate and δ value, result is listed in table 1.
(2) adopt the method Kaolinite Preparation of Catalyst B9 identical with embodiment 5, different, the article shaped that adopts embodiment 9 steps (1) to prepare.The composition of catalyst is listed in table 2.
(3) catalytic activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 3.
Table 1
| Numbering | Crushing strength (N/mm) | Water absorption rate (%) | δ value (%) |
| Embodiment 1 | 22.2 | 0.84 | 3.6 |
| Comparative Examples 1 | 25.8 | 0.83 | 2.8 |
| Comparative Examples 2 | 16.5 | 0.63 | 63.3 |
| Comparative Examples 4 | 25.8 | 0.83 | 2.8 |
| Embodiment 2 | 19.8 | 0.70 | 2.5 |
| Embodiment 3 | 15.1 | 0.83 | 3.7 |
| Embodiment 4 | 19.7 | 0.68 | 3.0 |
| Comparative Examples 5 | 19.1 | 0.61 | 74.1 |
| Embodiment 5 | 20.6 | 0.62 | 2.6 |
| Embodiment 6 | 19.7 | 0.76 | 2.9 |
| Comparative Examples 6 | 15.2 | 0.75 | 60.4 |
| Embodiment 7 | 20.2 | 0.69 | 2.4 |
| Embodiment 8 | 20.5 | 0.84 | 3.1 |
| Embodiment 9 | 22.1 | 0.65 | 2.9 |
As can be seen from Table 1, hydrated alumina forming matter according to the present invention has good strength retention, even higher crushing strength still after soaking in water.
Table 2
Table 3
| Numbering | The catalyst numbering | Desulfurization degree (%) |
| Embodiment 1 | B1 | 95 |
| Comparative Examples 1 | A1 | 76 |
| Comparative Examples 4 | A2 | 78 |
| Embodiment 2 | B2 | 96 |
| Embodiment 3 | B3 | 86 |
| Embodiment 4 | B4 | 83 |
| Embodiment 5 | B5 | 94 |
| Embodiment 6 | B6 | 98 |
| Embodiment 7 | B7 | 93 |
| Embodiment 8 | B8 | 88 |
| Embodiment 9 | B9 | 93 |
Embodiment 10-13 is for illustrating aluminium oxide article shaped of the present invention and application thereof.
Embodiment 10
(1) adopt the method identical with embodiment 1 step (1) to prepare hydrated alumina forming matter, and carry out roasting under the condition that the hydrated alumina forming matter of preparation is listed at table 4, to obtain according to aluminium oxide article shaped of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 4 for they.
(2) article shaped (diameter is 1.1mm, and particle length is 2-5mm) that adopts step (1) to prepare is as carrier, according to the method Kaolinite Preparation of Catalyst B10 identical with embodiment 1.The composition of catalyst is listed in table 2.
(3) activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 6.
Embodiment 11
(1) adopt the method identical with embodiment 2 steps (1) to prepare hydrated alumina forming matter, and carry out roasting under the condition that the hydrated alumina forming matter of preparation is listed at table 4, to obtain according to aluminium oxide article shaped of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 4 for they.
(2) article shaped (diameter is 1.1mm, and particle length is 2-5mm) that adopts step (1) to prepare is as carrier, according to the method Kaolinite Preparation of Catalyst B11 identical with embodiment 2.The composition of catalyst is listed in table 2.
(3) activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 6.
Embodiment 12
(1) adopt the method identical with embodiment 3 steps (1) to prepare hydrated alumina forming matter, and carry out roasting under the condition that the hydrated alumina forming matter of preparation is listed at table 4, to obtain according to aluminium oxide article shaped of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 4 for they.
(2) article shaped (diameter is 1.1mm, and particle length is 2-5mm) that adopts step (1) to prepare is as carrier, according to the method Kaolinite Preparation of Catalyst B12 identical with embodiment 3.The composition of catalyst is listed in table 2.
(3) activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 6.
Embodiment 13
(1) adopt the method identical with embodiment 6 steps (1) to prepare hydrated alumina forming matter, and carry out roasting under the condition that the hydrated alumina forming matter of preparation is listed at table 4, to obtain according to aluminium oxide article shaped of the present invention, radially crushing strength, water absorption rate and δ value are listed in table 4 for they.
(2) article shaped (diameter is 1.1mm, and particle length is 2-5mm) that adopts step (1) to prepare is as carrier, according to the method Kaolinite Preparation of Catalyst B13 identical with embodiment 6.The composition of catalyst is listed in table 2.
(3) activity of the catalyst that adopts the method evaluation step (2) identical with embodiment 1 step (3) to prepare, result is listed in table 6.
Table 4
Table 5
Table 6
| Numbering | The catalyst numbering | Desulfurization degree (%) |
| Embodiment 19 | B10 | 90 |
| Embodiment 20 | B11 | 93 |
| Embodiment 21 | B12 | 82 |
| Embodiment 22 | B13 | 92 |
From table 3 and table 6, can find out, the catalyst with hydrogenation catalyst effect prepared as carrier by the article shaped according to the present invention of usining shows and lists higher catalytic activity in the hydrotreatment of hydrocarbon ils.
Embodiment 23-34 is the application as drier for explanation article shaped according to the present invention.
Embodiment 23-28
Hydrated alumina forming matter prepared by embodiment 1-6 (is designated as N after weighing
1) be placed in respectively atmospheric dryer as drier, then in drier, place a beaker that fills 250mL water, close drier, and place 10 days in room temperature (25 ℃).Then, the taking-up article shaped is weighed and (is designated as N
2), calculate hygroscopic capacity with following formula,
Test result is listed in table 7.
Embodiment 29-34 is the application as drier for explanation aluminium oxide article shaped according to the present invention.
Embodiment 29-34
Aluminium oxide article shaped prepared by embodiment 1-6 is respectively 600 ℃ of roastings 4 hours, to obtain according to aluminium oxide article shaped of the present invention, adopt the method identical with embodiment 23-28 to measure the hygroscopic capacity of the aluminium oxide article shaped of preparation, test result is listed in table 7.
Table 7
| Numbering | N 1（g） | Contents on dry basis (% by weight) | Hygroscopic capacity (%) |
| Embodiment 23 | 20.0 | 70.5 | 68.2 |
| Embodiment 24 | 20.0 | 69.8 | 62.5 |
| Embodiment 25 | 20.0 | 73.7 | 77.3 |
| Embodiment 26 | 20.0 | 74.6 | 60.3 |
| Embodiment 27 | 20.0 | 72.5 | 56.6 |
| Embodiment 28 | 20.0 | 73.3 | 69.2 |
| Embodiment 29 | 20.0 | 100.0 | 67.3 |
| Embodiment 30 | 20.0 | 100.0 | 60.6 |
| Embodiment 31 | 20.0 | 100.0 | 75.8 |
| Embodiment 32 | 20.0 | 100.0 | 58.3 |
| Embodiment 33 | 20.0 | 100.0 | 55.1 |
| Embodiment 34 | 20.0 | 100.0 | 66.4 |
As can be seen from Table 7, article shaped according to the present invention has good absorbent properties, is suitable for as drier.
Claims (17)
1. a hydrated alumina forming matter, this article shaped is made the material forming that contains at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, and the water absorption rate of this article shaped is 0.4-1.5, and the δ value is below 10%, Q
1more than 12N/mm,
Wherein,
Q
1for the radially crushing strength of the article shaped without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radially crushing strength of the article shaped of 120 ℃ of dryings after 4 hours, in N/mm.
2. article shaped according to claim 1, wherein, the total amount of described raw material of take is benchmark, and the total content of described cellulose ether is the 0.5-8 % by weight, and the total content of described Y molecular sieve is the 0.5-55 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 37-98 % by weight.
3. catalyst according to claim 2, wherein, the total amount of described raw material of take is benchmark, and the total content of described cellulose ether is the 2-5 % by weight, and the total content of described Y molecular sieve is the 2-45 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 50-95 % by weight.
4. according to the described article shaped of any one in claim 1-3, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
5. according to the described article shaped of any one in claim 1-3, wherein, described Y molecular sieve is selected from NaY molecular sieve, CaY molecular sieve, NH
4y molecular sieve, HY molecular sieve, REY molecular sieve and ultra-steady Y molecular sieve;
Described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
6. article shaped according to claim 1, wherein, the water absorption rate of described article shaped is 0.6-1, the δ value is below 5%, Q
1for 15-30N/mm.
7. a method for preparing hydrated alumina forming matter, the method comprises the material forming that will contain at least one hydrated alumina, at least one Y molecular sieve and at least one cellulose ether, and the formed body obtained is carried out to drying.
8. method according to claim 7, wherein, the total amount of described raw material of take is benchmark, and the total content of described cellulose ether is the 0.5-8 % by weight, and the total content of described Y molecular sieve is the 0.5-55 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 37-98 % by weight.
9. method according to claim 8, wherein, the total amount of described raw material of take is benchmark, and the total content of described cellulose ether is the 2-5 % by weight, and the total content of described Y molecular sieve is the 2-45 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is the 50-95 % by weight.
10. according to the described method of any one in claim 7-9, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
11., according to the described method of any one in claim 7-9, wherein, described Y molecular sieve is selected from NaY molecular sieve, CaY molecular sieve, NH
4y molecular sieve, HY molecular sieve, REY molecular sieve and ultra-steady Y molecular sieve;
Described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
12. method according to claim 7, wherein, the temperature of described drying is more than 60 ℃ and lower than 350 ℃.
13. method according to claim 12, wherein, the temperature of described drying is 80-300 ℃.
14. the hydrated alumina forming matter that in claim 7-13 prepared by the described method of any one.
15. an aluminium oxide article shaped, this aluminium oxide article shaped is carried out the described hydrated alumina forming matter of any one in claim 1-6 and 14 roasting and makes.
16. in claim 1-6 and 14, the described aluminium oxide article shaped of the described hydrated alumina forming matter of any one or claim 15 is as drier or as the application of the carrier of loaded catalyst.
17. application according to claim 16, wherein, described catalyst is the catalyst with hydrogenation catalyst effect.
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| CN106914279A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Alumina support and preparation method thereof |
| CN106914249A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Residuum hydrogenating and metal-eliminating catalyst and preparation method thereof |
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| 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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| CN106914279A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Alumina support and preparation method thereof |
| CN106914249A (en) * | 2015-12-24 | 2017-07-04 | 中国石油天然气股份有限公司 | Residuum hydrogenating and metal-eliminating catalyst and preparation method thereof |
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| CN106914249B (en) * | 2015-12-24 | 2019-11-08 | 中国石油天然气股份有限公司 | Residuum hydrogenating and metal-eliminating catalyst and preparation method thereof |
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