CN103480387B - There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and method for hydrotreating hydrocarbon oil - Google Patents
There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and method for hydrotreating hydrocarbon oil Download PDFInfo
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Abstract
The invention provides a kind of Catalysts and its preparation method and the application with hydrogenation catalyst effect, this catalyst contains carrier and load at least one group VIII metallic element on the carrier and at least one group vib metallic element, described group VIII metallic element and group vib metallic element are non-uniform Distribution along this catalyst radial section separately, wherein, along this catalyst radial section
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and the application with hydrogenation catalyst effect, the invention still further relates to a kind of method for hydrotreating hydrocarbon oil.
Background technology
Outside sulphur removal, nitrogen, also containing the metal impurities such as a large amount of Ni, V, Fe, Ca and asphalitine and colloid in heavy oil.In the hydroprocessing processes of this type of feedstock oil, these impurity can be adsorbed in catalyst surface covering activated centre or be deposited in catalyst duct and block duct, thus cause the inactivation of catalyst.Therefore, for the appearance metal ability of the catalyst of heavy-oil hydrogenation processing procedure and coking resistivity, the direct life cycle etc. to catalyst is had an impact.
US4760045 discloses a kind of heavy oil hydrogenating treatment catalyst, this catalyst contains the active metal component with hydrogenation catalyst effect that porous refractory oxides carrier and load at least one are on this carrier selected from VB race in the periodic table of elements, group vib and group VIII, wherein, along catalyst cross section, the distribution of the concentration of described metal component meets Cr
1<Cr
2and R
1>R
2, wherein, R
1and R
2represent the distance r from kernel of section to respective point respectively
1and r
2with the ratio of the distance from kernel of section to outer surface, Cr
1and Cr
2represent the concentration of the described metal component of described respective point respectively.
CN101376106B discloses a kind of heavy oil hydrogenating treatment catalyst, the at least one that this catalyst contains carrier and effective dose is selected from the metal component that group VIII and at least one are selected from group vib, wherein, the concentration of described group VIII metal component is non-uniform Distribution along catalyst radial section, wherein, the concentration of outer surface metal component is 0.1-0.85 with the ratio of the concentration of central metal component; The concentration of described group vib metal component is evenly distributed along catalyst radial section, and wherein, the concentration of outer surface metal component is 0.90-1.5 with the ratio of the concentration of central metal component.Carrier in this catalyst is aluminium oxide.
CN101462080A discloses a kind of preparation method of catalyst with non-uniform distribution of active metal component, comprise at least one adopting the method for dipping to introduce effective dose on carrier and be selected from the metal component that group VIII and at least one are selected from group vib, wherein, described dipping comprises the steps: that (1) order will be selected from nitric acid, phosphoric acid, oxalic acid, citric acid, tartaric acid, pimelic acid, one or more acid in adipic acid contain the compound of the metal component of group vib with being selected from least one, at least one is mixed into solution containing the compound of metal component of group VIII and water, wherein, the ratio of the compound molal quantity sum of the molal quantity of described acid and the metal component containing group vib and the metal component containing group VIII is 0.1-0.92, the consumption of described water makes the amount of final solution by volume be 0.85 η-1.1 η, η is the water absorption rate of carrier, (2) under room temperature with the mixed solution impregnated carrier that step (1) is prepared, dip time is 1-5 hour, (3) carrier after step (2) being flooded in being greater than 60 DEG C to 160 DEG C dry 2-10 hour, and at 400-600 DEG C of roasting 2-5 hour.
Practical application shows, above-mentioned heavy oil hydrogenating treatment catalyst has good stability in use in the hydroprocessing processes of heavy oil.
But heavily become bad along with oil property becomes, refinery has to process crude oil more inferior, therefore in the urgent need to having more high catalytic activity, better catalytic stability and the hydrogenation catalyst in longer service life.
Summary of the invention
The object of the present invention is to provide a kind of Catalysts and its preparation method with hydrogenation catalyst effect, catalyst according to the invention demonstrates higher catalytic activity, better catalytic stability and longer service life in the hydrotreatment of hydrocarbon ils (particularly heavy hydrocarbon oil).
The present inventor finds in research process, with by containing at least one hydrated alumina, at least one prepares formed body containing the compound of IVB race metallic element and the raw material of at least one cellulose ether, and the hydrated alumina forming matter described formed body being carried out drying and makes is as carrier, the compound of group VIII metallic element and on this carrier compound loaded containing group vib metallic element will be contained, and (namely group VIII metallic element and group vib metallic element are distributed in " yolk " type, the active metal concentrations at catalyst center place is higher than the active metal concentrations of catalyst external surface), the catalyst formed thus demonstrates higher catalytic activity in the hydrotreatment of hydrocarbon ils (particularly heavy hydrocarbon oil).This completes the present invention.
A first aspect of the present invention provides a kind of catalyst with catalytic hydrogenation, this catalyst contains carrier and load at least one group VIII metallic element on the carrier and at least one group vib metallic element, described group VIII metallic element and group vib metallic element are non-uniform Distribution along this catalyst radial section separately, wherein, along this catalyst radial section
for group VIII metallic element is in the mean concentration of the outer surface of described catalyst;
for group VIII metallic element is in the mean concentration of the center of described catalyst;
be the mean concentration of group vib metallic element at the outer surface of described catalyst;
be the mean concentration of group vib metallic element in the center of described catalyst;
Described carrier is hydrated alumina forming matter, makes containing the compound of IVB race metallic element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one.
A second aspect of the present invention provides a kind of method preparing the catalyst with hydrogenation catalyst effect, the method is included in supported on carriers at least one group VIII metallic element and at least one group vib metallic element, load is on the carrier substantially in a salt form for described group VIII metallic element and group vib metallic element, wherein, described carrier is hydrated alumina forming matter, by containing at least one hydrated alumina, at least one prepares formed body containing the compound of IVB race metallic element and the raw material of at least one cellulose ether, and described formed body is carried out drying at higher than 180 DEG C and not higher than the temperature of 300 DEG C and makes.
A third aspect of the present invention provides the catalyst prepared by method of the present invention.
A fourth aspect of the present invention provides the application of catalyst according to the invention in hydrocarbon oil hydrogenation process.
A fifth aspect of the present invention provides a kind of method for hydrotreating hydrocarbon oil, and the method comprises under hydroprocessing conditions, by hydrocarbon ils and catalyst exposure of the present invention.
Catalyst according to the invention demonstrates higher catalytic activity in the HDM reaction of hydrocarbon ils (particularly heavy hydrocarbon oil); Further, use in the hydroprocessing processes of catalyst of the present invention, metal trends towards the center being deposited on catalyst, and thus catalyst according to the invention has higher appearance metal ability, and then has higher stability and longer service life.
According to the preparation method with the catalyst of hydrogenation catalyst effect of the present invention, to prepare formed body by containing at least one hydrated alumina, at least one containing the compound of IVB race metallic element and the raw material of at least one cellulose ether, and described formed body is carried out drying at higher than 180 DEG C and not higher than the temperature of 300 DEG C and the article shaped made as carrier, adopt the conventional method of this area can prepare the catalyst of active component (that is, group VIII metallic element and group vib metallic element) distribution in " yolk " type.That is, method is simple according to of the present invention.
Detailed description of the invention
The invention provides a kind of catalyst with hydrogenation catalyst effect, this catalyst contains carrier and load at least one group VIII metallic element on the carrier and at least one group vib metallic element.Term " at least one " refers to one or more.
Catalyst according to the invention is using group VIII metallic element and group vib metallic element as the active component with catalytic hydrogenation.
Catalyst according to the invention, the content of described group VIII metallic element and group vib metallic element can carry out suitable selection according to the embody rule occasion of catalyst.Such as, when catalyst according to the invention is used for the hydrotreatment of hydrocarbon ils (particularly heavy hydrocarbon oil), with the total amount of described catalyst for benchmark, the content of described carrier can be 72-95 % by weight, is preferably 77.5-93 % by weight; With oxide basis, the content of described group VIII metallic element can be 1-8 % by weight, is preferably 1.5-4.5 % by weight; With oxide basis, the content of described group vib metallic element can be 3-20 % by weight, is preferably 5-18 % by weight.
Catalyst according to the invention, the various elements with hydrogenation catalyst effect that described group VIII metallic element and described group vib metallic element can be commonly used for this area.Preferably, described group VIII metallic element is cobalt and/or nickel, and described group vib metallic element is molybdenum and/or tungsten.
Catalyst according to the invention, load is on the carrier in a salt form for described group VIII metallic element and described group vib metallic element basic (that is, mainly or in fact).That is, described group VIII metallic element preferably with the form load of the salt containing group VIII metallic element on the carrier, and described group vib metallic element preferably with the form load of the salt containing group vib metallic element on the carrier.Also namely, preferably basic (that is, mainly or in fact) with the form load of non-oxidized substance on the carrier for described group VIII metallic element and described group vib metallic element.
Catalyst according to the invention, described group VIII metallic element and group vib metallic element are non-uniform Distribution along the radial section of catalyst, wherein, along this catalyst radial section,
for group VIII metallic element is in the mean concentration of the outer surface of described catalyst;
for group VIII metallic element is in the mean concentration of the center of described catalyst;
be the mean concentration of group vib metallic element at the outer surface of described catalyst;
be the mean concentration of group vib metallic element in the center of described catalyst.
Preferably, along this catalyst radial section,
More preferably, along this catalyst radial section,
In the present invention, adopt SEM and energy disperse spectroscopy (that is, SEM-EDX) to measure the distribution of metallic element along catalyst radial section, calculate metallic element at the ratio of the mean concentration of catalyst granules outer surface with the mean concentration of center.Wherein, the mean concentration of outer surface is the mean value of outer surface 20 numerical point counting rates; Mean value (the note: the counting rate along the radial every bit of carrier in SEM-EDX characterization result is mutually corresponding with this tenor of 20 the numerical point counting rates in some place centered by the mean concentration of center, the size of counting rate reflects this tenor height, but does not represent the real content of this metal).
Catalyst according to the invention, described carrier is hydrated alumina forming matter, makes containing the compound of IVB race metallic element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one.
In the present invention, described raw material contains at least one hydrated alumina, at least one contains IVB race metallic element compound and at least one cellulose ether, but not containing peptizing agent (such as: Alumina gel, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid).
Catalyst according to the invention, the composition of described raw material can carry out suitable selection according to the application scenario of catalyst.Usually, with the total amount of described raw material for benchmark, the total content of described cellulose ether can be 0.5-10 % by weight, is preferably 1-8 % by weight, is more preferably 2-7 % by weight; Can be 0.5-55 % by weight with the total content of compound containing IVB race metallic element described in oxide basis, preferably 1-50 % by weight, be more preferably 1.5-45 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be 35-98 % by weight, is preferably 42-96 % by weight, is more preferably 48-95 % by weight.In the present invention, when calculating the total amount of described raw material, containing the compound of IVB race metallic element with oxide basis, hydrated alumina is with Al
2o
3meter, and described raw material does not comprise the water will introduced in described material forming process.
In the present invention, described cellulose ether refers to the ether system derivative formed after the hydrogen atom at least part of hydroxyl in cellulosic molecule is replaced by one or more alkyl, and wherein, multiple described alkyl can be identical, also can be different.Described alkyl is selected from the alkyl of replacement and unsubstituted alkyl.Described unsubstituted alkyl is preferably alkyl (such as: C
1-C
5alkyl).In the present invention, C
1-C
5the instantiation of alkyl comprise C
1-C
5straight chained alkyl and C
3-C
5branched alkyl, can for but be not limited to: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl and tertiary pentyl.The alkyl of described replacement can be such as by the alkyl of hydroxyl or carboxyl substituted (such as: C
1-C
5the alkyl be optionally substituted by a hydroxyl group, C
1-C
5by the alkyl of carboxyl substituted), its instantiation can include but not limited to: methylol, ethoxy, hydroxypropyl, hydroxyl butyl, carboxymethyl, carboxyethyl and carboxylic propyl group.
The present invention is not particularly limited for the substituent quantity of the hydrogen atom in the kind of described cellulose ether and the hydroxyl in substituted cellulose molecule, can be common various cellulose ethers.Particularly, described cellulose ether can be selected from but be not limited to: methylcellulose, ethyl cellulose, hydroxyethylcellulose, HEMC, hydroxypropyl cellulose, hydroxypropyl methylcellulose, carboxymethyl cellulose, carboxyethyl cellulose and carboxymethyl hydroxyethyl cellulose.Preferably, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
According to the present invention, the various IVB races metallic element that described IVB race metallic element can be commonly used for this area, such as, can be selected from titanium, zirconium and hafnium, be preferably selected from titanium and zirconium, be more preferably titanium.
According to the present invention, the compound containing IVB race metallic element in the various molecular structures that the described compound containing IVB race metallic element can be commonly used for this area.Such as, when described IVB race metallic element is selected from titanium and zirconium, the described compound containing IVB race metallic element can be selected from basic zirconium chloride (as ZrOCl
28H
2o), zirconium acetate, zirconium sulfate, zirconium nitrate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium are (as (NH
4)
2zrO (CO
3)
2nH
2o), zirconium dioxide, metatitanic acid, metatitanic acid (H
2tiO
3), titanium dioxide, the compound shown in titanium sulfate and formula I,
TiX
n(OR)
4-n（I），
In formula I, X is halogen (such as: can be chlorine, bromine and iodine, be preferably chlorine), and R is C
1-C
5alkyl, n is the integer (can be such as 0,1,2,3 or 4, be preferably 0 or 4) of 0-4.
Preferably, the described compound containing IVB race metallic element is selected from zirconium acetate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium, zirconium dioxide, metatitanic acid, metatitanic acid, titanium dioxide, titanium sulfate, titanium tetrachloride, tetra-n-butyl titanate, tetrabutyl titanate and tetraisopropyl titanate.More preferably, the described compound containing IVB race metallic element is selected from metatitanic acid and titanium dioxide.
In the present invention, the kind of described hydrated alumina is not particularly limited, and can be that the routine of this area is selected.Preferably, described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.More preferably, described hydrated alumina is boehmite.
According to the present invention, described raw material can also contain at least one extrusion aid.The content of described extrusion aid can be the routine selection of this area.Usually, with the total amount of described raw material for benchmark, the total content of described extrusion aid can be 0.1-8 % by weight, is preferably 0.5-5 % by weight.The present invention is not particularly limited for the kind of described extrusion aid, can be that the routine of this area is selected.Preferably, described extrusion aid is starch (that is, described raw material is also containing starch).As the starch in the various sources that the starch of extrusion aid can be commonly used for this area, such as: by vegetable seeds through pulverizing the powder obtained, as sesbania powder.
Catalyst according to the invention, described carrier can be prepared formed body containing the compound of IVB race metallic element and the raw material of at least one cellulose ether, and described formed body carried out drying and obtains by containing at least one hydrated alumina, at least one.The various methods that this area can be adopted conventional, to prepare described formed body, are not particularly limited.Such as: directly by least one hydrated alumina, at least one cellulose ether and at least one compound mixed-forming containing IVB race metallic element, thus described formed body can be obtained; Also can first by least one hydrated alumina and at least one cellulose ether mixed-forming, obtained preform, then on this preform, load at least one contains the compound of IVB race metallic element, thus obtains described formed body.
One of the present invention preferred embodiment in, the method being prepared described formed body by described raw material comprises: at least one hydrated alumina, at least one are mixed with water containing the compound of IVB race metallic element and at least one cellulose ether, obtain the first mixture, and by shaping for described first mixture.
In another preferred embodiment of the present invention, the method being prepared described formed body by described raw material comprises: at least one hydrated alumina and at least one cellulose ether are mixed with water, obtain the second mixture, and described second mixture is successively carried out shaping and dehydration, obtain preform, on described preform, load at least one is containing the compound of IVB race metallic element.
In this embodiment, on described preform, load at least one contains the routine selection that the mode of the compound of IVB race metallic element can be this area, such as: by being contacted with containing the solution of at least one containing the compound of IVB race metallic element by described preform, thus the compound loaded on described preform of IVB race metallic element can be contained by described.The mode contacted with described solution by described preform can be selected for the routine of this area, such as: by flooding or spraying, described preform can be contacted with containing the solution of at least one containing the compound of IVB race metallic element, thus contain the compound loaded on described preform of IVB race metallic element by described.Adopt the mode of dipping by described contain IVB race metallic element compound loaded on described preform time, described dipping can be saturated dipping, also can flood for supersaturation.The described solvent containing the solution of the compound of IVB race metallic element containing at least one can be that the routine of this area is selected, and is preferably water.Describedly to be not particularly limited containing the concentration of solution of at least one containing the compound of IVB race metallic element, with enable the amount of the compound containing IVB race metallic element of load on described preform meet the demands (such as previously described content) be as the criterion.
In this embodiment, the condition of described dehydration is not particularly limited, and can be that the routine of this area is selected, be as the criterion can remove water.Usually, described dehydration can be carried out lower than at the temperature of 350 DEG C more than 60 DEG C, preferably carries out at higher than 180 DEG C and not higher than the temperature of 300 DEG C (as 190-300 DEG C), more preferably carries out at the temperature of 200-260 DEG C.The time of described dehydration can carry out suitable selection according to the temperature of dehydration, is not particularly limited.Usually, the time of described dehydration can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
Catalyst according to the invention, the consumption for the preparation of the water of described first mixture or described second mixture is not particularly limited, as long as the consumption of water can guarantee various component to mix.
Catalyst according to the invention, described shaping mode is not particularly limited, and can adopt the various molding modes that this area is conventional, such as: extrusion, spraying, round as a ball, compressing tablet or their combination.One of the present invention preferred embodiment in, come shaping by the mode of extrusion.
Catalyst according to the invention, described carrier can have various shape according to concrete instructions for use, such as: spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.
Catalyst according to the invention, carries out dry condition and is not particularly limited by described formed body, can be that the routine of this area is selected, be as the criterion with the volatile component that can remove on described formed body.Such as: the temperature of described drying can be more than 60 DEG C and lower than 350 DEG C.Preferably, the temperature of described drying is higher than 180 DEG C and not higher than 300 DEG C (as 190-300 DEG C).More preferably, the temperature of described drying is 200-260 DEG C.According to the present invention, the time of described drying can carry out suitable selection according to the temperature of drying, meets instructions for use be as the criterion can make volatile matter content in the article shaped that finally obtains.Usually, the time of described drying can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
Catalyst according to the invention, described carrier has good intensity and absorbent properties.
Particularly, the δ value of described carrier is less than 10%, can be even less than 5%; Without radial crushing strength (that is, the Q of the carrier of water soaking
1) can be more than 12N/mm, being even more than 15N/mm, such as, can be 15-30N/mm.
In the present invention, δ value is used for the strength retention of evaluation carrier, is defined by following formula:
Wherein, Q
1for the radial crushing strength of the carrier without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radial crushing strength of the carrier of 120 DEG C of dryings after 4 hours, in N/mm.
In the present invention, described radial crushing strength according to " Petrochemical Engineering Analysis method " (Science Press, nineteen ninety the first edition, the volumes such as Yang Cuiding) in the RIPP25-90 that records the method that specifies measure.
According to the present invention, the water absorption rate of described carrier is 0.4-1.5, is generally 0.6-1.In the present invention, described water absorption rate refers to that the dry excessive deionized water of carrier soaks the ratio of the weight of the weight change value of 30 minutes front and back and the carrier of described drying.Concrete method of testing is: by carrier to be measured 120 DEG C of dryings 4 hours, then sieves with 40 object standard screens, takes 20g oversize and (be designated as w as testing sample
1), testing sample 50g deionized water is soaked 30 minutes, after filtration, solid phase is drained 5 minutes, the weight then weighing the solid phase drained (is designated as w
2), with following formulae discovery water absorption rate:
Catalyst according to the invention, described catalyst can also can improve the component of the catalytic performance of catalyst containing at least one, such as: P elements.The present invention is not particularly limited for the described content that can improve the component of the catalytic performance of catalyst, can be that the routine of this area is selected.Usually, with the total amount of catalyst for benchmark, with oxide basis, the described content that can improve the component of the catalytic performance of catalyst can be 0.1-10 % by weight, is preferably 0.5-5 % by weight.
Catalyst according to the invention can adopt this area to be usually used in preparing the method preparation of active component distribution in " yolk " type.The present inventor finds in research process: with by containing at least one hydrated alumina, at least one prepares formed body containing the compound of IVB race metallic element and the raw material of at least one cellulose ether, and when the compound of the supported on carriers described formed body being carried out drying and makes containing group vib metallic element and the compound containing group VIII metallic element, if the temperature of drying is higher than 180 DEG C and not higher than 300 DEG C, adopt conventional method (such as: dipping) the load above-claimed cpd on the carrier of this area, in obtained catalyst, group vib metallic element and group VIII metallic element can present the distribution of " yolk " type.
Thus, a second aspect of the present invention provides a kind of method preparing described catalyst, the method is included in supported on carriers at least one group VIII metallic element and at least one group vib metallic element, wherein, described carrier is hydrated alumina forming matter, prepare formed body by containing at least one hydrated alumina, at least one containing the compound of IVB race metallic element and the raw material of at least one cellulose ether, and described formed body is carried out drying at higher than 180 DEG C and not higher than the temperature of 300 DEG C and makes.
According to method of the present invention, described group VIII metallic element and group vib metallic element load capacity on the carrier, to make in the catalyst of final preparation, the content of group VIII metallic element and group vib metallic element can meet concrete instructions for use and be as the criterion.Such as, when catalyst according to the invention is used for carrying out hydrotreatment to hydrocarbon ils (particularly heavy hydrocarbon oil), described group vib metallic element and group VIII metallic element load capacity on the carrier make, with the total amount of the catalyst finally prepared for benchmark, the content of described carrier can be 72-95 % by weight, is preferably 77.5-93 % by weight; With oxide basis, the content of described group VIII metallic element can be 1-8 % by weight, is preferably 1.5-4.5 % by weight; With oxide basis, the content of described group vib metallic element can be 3-20 % by weight, is preferably 5-18 % by weight.
According to method of the present invention, described group VIII metallic element is preferably cobalt and/or nickel, and described group vib metallic element is preferably molybdenum and/or tungsten.
According to method of the present invention, load is on the carrier in a salt form for described group VIII metallic element and described group vib metallic element basic (that is, mainly or in fact).Also namely, described group VIII metallic element and described group vib metallic element basic (that is, mainly or in fact) are with the form load of non-oxidized substance on the carrier.
The various modes that this area can be adopted conventional by described group VIII metallic element and described group vib metallic element substantially with the form load of salt (that is, substantially with non-oxidized substance) on the carrier, such as: dipping.Described dipping can be saturated dipping, also can be excessive dipping.According to method of the present invention, can on the carrier by group VIII metallic element and the load of group vib metallic element simultaneously, also can gradation by described group VIII metallic element and the load of described group vib metallic element on the carrier.Such as: can with containing at least one containing the solution of the component of group VIII metallic element and containing at least one containing the solution gradation of the component of group vib metallic element or simultaneously impregnated carrier, thus by the described component containing group VIII metallic element and the component load containing group vib metallic element on the carrier.
In one embodiment of the invention, described group VIII metallic element and described group vib metallic element load mode are on the carrier comprised: with containing at least one containing the salt of group VIII metallic element and at least one containing the compound of group vib metallic element aqueous impregnation described in carrier, and carry out drying by flooding the carrier obtained.
In another embodiment of the invention, described group VIII metallic element and described group vib metallic element load mode are on the carrier comprised: with containing at least one containing group VIII metallic element salt aqueous impregnation described in carrier, and carry out drying by flooding the carrier obtained, there is the carrier of the described salt containing group VIII metallic element with the aqueous impregnation load of the compound containing group vib metallic element containing at least one, and carry out drying by flooding the carrier obtained.
In another embodiment of the present invention, described group VIII metallic element and described group vib metallic element load mode are on the carrier comprised: with containing at least one containing group vib metallic element compound aqueous impregnation described in carrier, and carry out drying by flooding the carrier obtained, there is the carrier of the described compound containing group vib metallic element with the aqueous impregnation load of the salt containing group VIII metallic element containing at least one, and carry out drying by flooding the carrier obtained.
According to the present invention, the various water soluble salts containing group VIII metallic element that the described salt containing group VIII metallic element can be commonly used for this area, such as: the described salt containing group VIII metallic element can be selected from the water-soluble group VIII slaine of inorganic acid, the water-soluble group VIII slaine of organic acid and the water-insoluble compound containing group VIII metallic element and contact with sour (as phosphoric acid) and/or alkali (as ammoniacal liquor) water soluble salt formed in water.
Particularly, the described salt containing group VIII metallic element can be selected from but be not limited to: the water soluble salt that cobalt nitrate, cobalt acetate, basic cobaltous carbonate contact with acid (as phosphoric acid) and/or alkali (as ammoniacal liquor) and formed in water, cobalt chloride, aqueous cobalt complex compound, nickel nitrate, nickel acetate, basic nickel carbonate contact with acid (as phosphoric acid) and/or alkali (as ammoniacal liquor) water soluble salt, nickel chloride and the water-soluble nickel complex that are formed in water.Described aqueous cobalt complex compound can be such as Cobalt Edetate; Described water-soluble nickel complex can be such as citric acid nickel.Preferably, the described salt containing group VIII metallic element is selected from cobalt nitrate, basic cobaltous carbonate and in water, contact the water soluble salt, the basic nickel carbonate that are formed with acid (as phosphoric acid) and/or alkali (as ammoniacal liquor) contact with sour (as phosphoric acid) and/or alkali (as ammoniacal liquor) water soluble salt and nickel nitrate that are formed in water.
According to the present invention, the described kind containing the compound of group vib metallic element is not particularly limited, can be the conventional various water soluble compounds containing group vib metallic element of this area, such as can be selected from the water-soluble group vib slaine of inorganic acid, the water-soluble group vib slaine of organic acid, containing group vib metallic element heteropoly acid, in water, contact with acid (as phosphoric acid) or alkali the water soluble compound formed containing the heteropolyacid salt of group vib metallic element and the oxide of group vib metal.
Particularly, the described compound containing group vib metallic element can be selected from the water soluble salt of molybdic acid, the water soluble salt of para-molybdic acid, ammonium tungstate, ammonium metatungstate, ammonium paratungstate, ethyl ammonium metatungstate, phosphotungstic acid, phosphomolybdic acid, phosphotungstic acid nickel, phosphotungstic acid cobalt, silico-tungstic acid nickel, silico-tungstic acid cobalt, phosphomolybdic acid nickel, phosphomolybdic acid cobalt, P-Mo-Wo acid nickel, P-Mo-Wo acid cobalt, silicomolybdic acid nickel, silicomolybdic acid cobalt, silicon molybdenum nickel tungstate, silicon molybdenum cobaltous tungstate and molybdenum oxide in water, contact the water soluble compound formed with phosphoric acid.In the present invention, the water soluble salt of described molybdic acid comprises water-soluble metal salt and the ammonium molybdate of molybdic acid; The water soluble compound of described para-molybdic acid comprises water-soluble metal salt and the ammonium paramolybdate of para-molybdic acid.Preferably, the described salt containing group vib metallic element is selected from ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, ammonium tungstate and molybdenum oxide in water, contacts the water soluble compound formed with phosphoric acid.
According to method of the present invention, the present invention is also not particularly limited for the concentration of the described aqueous solution, as long as can make in the catalyst of final preparation, the content of group VIII metallic element and group vib metallic element meets instructions for use (such as previously described requirement).
According to method of the present invention, under the condition can commonly used in this area, carry out drying by flooding the carrier obtained.Particularly, the condition of described drying comprises: temperature can be 100-200 DEG C, is preferably 120-150 DEG C; Time can be 1-15 hour, is preferably 3-10 hour.
According to method of the present invention, described carrier prepares formed body by containing at least one hydrated alumina, at least one containing the compound of IVB race metallic element and the raw material of at least one cellulose ether, and described formed body is carried out drying at higher than 180 DEG C and not higher than the temperature of 300 DEG C and makes.Preferably, the temperature of described drying is 200-260 DEG C.
According to method of the present invention, the time of described drying can carry out suitable selection according to the temperature of drying, is as the criterion with the volatile ingredient that can remove on carrier.Such as, the time of described drying can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
According to method of the present invention, described raw material contains at least one hydrated alumina, at least one contains IVB race metallic element compound and at least one cellulose ether, but not containing peptizing agent (such as: Alumina gel, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid).
According to method of the present invention, the composition of described raw material can carry out suitable selection according to the application scenario of catalyst.Usually, with the total amount of described raw material for benchmark, the total content of described cellulose ether can be 0.5-10 % by weight, is preferably 1-8 % by weight, is more preferably 2-7 % by weight; Can be 0.5-55 % by weight with the total content of compound containing IVB race metallic element described in oxide basis, preferably 1-50 % by weight, be more preferably 1.5-45 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be 35-98 % by weight, is preferably 42-96 % by weight, is more preferably 48-95 % by weight.
According to method of the present invention, the kind of described cellulose ether, the described compound and described hydrated alumina that contain IVB race metallic element has been described in detail above, does not repeat them here.
According to method of the present invention, described raw material can also contain at least one extrusion aid.The content of described extrusion aid can be the routine selection of this area.Usually, with the total amount of described raw material for benchmark, the total content of described extrusion aid can be 0.1-8 % by weight, is preferably 0.5-5 % by weight.The kind of described extrusion aid, with described identical above, does not repeat them here.
Method according to the present invention is by preparing formed body by by containing at least one hydrated alumina, at least one containing the compound of IVB race metallic element and the raw material of at least one cellulose ether, and the article shaped of described formed body being carried out drying and preparing carrys out Kaolinite Preparation of Catalyst as carrier.The various methods that this area can be adopted conventional, to prepare described formed body, are not particularly limited.Such as: directly by least one hydrated alumina, at least one cellulose ether and at least one compound mixed-forming containing IVB race metallic element, thus described formed body can be obtained; Also can first by least one hydrated alumina and at least one cellulose ether mixed-forming, obtained preform, then on this preform, load at least one contains the compound of IVB race metallic element, thus obtains described formed body.
One of the present invention preferred embodiment in, the method being prepared described formed body by described raw material comprises: at least one hydrated alumina, at least one are mixed with water containing the compound of IVB race metallic element and at least one cellulose ether, obtain the first mixture, and by shaping for described first mixture.
In another preferred embodiment of the present invention, the method being prepared described formed body by described raw material comprises: at least one hydrated alumina and at least one cellulose ether are mixed with water, obtain the second mixture, and described second mixture is successively carried out shaping and dehydration, obtain preform, on described preform, load at least one is containing the compound of IVB race metallic element.
In this embodiment, the various methods that this area can be adopted to commonly use contain the compound loaded on described preform of IVB race metallic element by described, such as: described preform can be contacted with containing the solution of at least one containing the compound of IVB race metallic element, thus contain the on the carrier compound loaded of IVB race metallic element by described.The mode that described preform contacts with the solution of the compound containing IVB race metallic element containing at least one can be selected for the routine of this area, such as: by flooding or spraying, described preform can be contacted with containing the solution of at least one containing the compound of IVB race metallic element, thus contain the compound loaded on described preform of IVB race metallic element by described.Adopt the mode of dipping by described contain IVB race metallic element compound loaded on described preform time, described dipping can be saturated dipping, also can flood for supersaturation.The described solvent containing the solution of the compound of IVB race metallic element containing at least one can be that the routine of this area is selected, and is preferably water.Describedly to be not particularly limited containing the concentration of solution of at least one containing the compound of IVB race metallic element, with enable the amount of the compound containing IVB race metallic element of load on described preform meet the demands (such as previously described content) be as the criterion.
In this embodiment, the condition of described dehydration is not particularly limited, and can be that the routine of this area is selected, be as the criterion can remove water.Usually, described dehydration can be carried out at higher than 180 DEG C and not higher than the temperature of 300 DEG C (as 190-300 DEG C), preferably carries out at the temperature of 200-260 DEG C.The time of described dehydration can carry out suitable selection according to the temperature of dehydration, is not particularly limited.Usually, the time of described dehydration can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
According to the present invention, the consumption for the preparation of the water of described first mixture or described second mixture is not particularly limited, as long as the consumption of water can guarantee various component to mix.
According to method of the present invention, described shaping mode is not particularly limited, and can adopt the various molding modes that this area is conventional, such as: extrusion, spraying, round as a ball, compressing tablet or their combination.One of the present invention preferred embodiment in, come shaping by the mode of extrusion.
According to method of the present invention, described carrier can have various shape according to concrete instructions for use, such as: spherical, bar shaped, annular, cloverleaf pattern, honeycombed or butterfly.
According to method of the present invention, described carrier has good absorbent properties, high intensity and strength retention.Usually, the δ value of described carrier is less than 10%, can be even less than 5%; Without radial crushing strength (that is, the Q of the carrier of water soaking
1) can be more than 12N/mm, being even more than 15N/mm, such as, can be 15-30N/mm; The water absorption rate of described carrier is 0.4-1.5, is generally 0.6-1.
According to method of the present invention, can also comprise and introduce the component that at least one can improve the catalytic performance of the catalyst of final preparation on described carrier, such as: P elements.By before group VIII metallic element described in load and group vib metallic element, described component can be introduced on described carrier; Also can while group VIII metallic element described in load and group vib metallic element, by described component load on the carrier.The described introduction volume can improving the component of the performance of catalyst can be selected for the routine of this area.Usually, the described introduction volume can improving the component of the performance of catalyst makes in the catalyst of final preparation, and with oxide basis, the described content that can improve the component of the performance of catalyst can be 0.1-10 % by weight, is preferably 0.5-5 % by weight.
In prepared according to the methods of the invention catalyst, group vib metallic element and the group VIII metallic element with hydrogenation catalyst effect present the distribution of " yolk " type, in the hydrotreatment of hydrocarbon ils (particularly heavy hydrocarbon oil), show higher activity.
Thus, a third aspect of the present invention provides a kind of catalyst prepared by method of the present invention.
According to catalyst of the present invention, described group VIII metallic element and group vib metallic element are non-uniform Distribution along the radial section of catalyst, wherein, along this catalyst radial section,
for group VIII metallic element is in the mean concentration of the outer surface of described catalyst;
for group VIII metallic element is in the mean concentration of the center of described catalyst;
be the mean concentration of group vib metallic element at the outer surface of described catalyst;
be the mean concentration of group vib metallic element in the center of described catalyst.
Preferably, along this catalyst radial section,
More preferably, along this catalyst radial section,
Catalyst according to the invention demonstrates higher catalytic activity, better stability and longer service life in the hydrotreatment of hydrocarbon ils (particularly heavy hydrocarbon oil).
Thus, a fourth aspect of the present invention additionally provides the application of a kind of catalyst according to the invention in hydrocarbon oil hydrogenation process.
A fifth aspect of the present invention additionally provides a kind of method for hydrotreating hydrocarbon oil, and the method comprises under hydroprocessing conditions, by hydrocarbon ils and catalyst exposure of the present invention.
In the present invention, described hydrocarbon ils can for the various hydrocarbon raw material carrying out hydrotreatment that needs, and being preferably variously needs the heavier hydrocarbon feeds of carrying out HDM process.Particularly, described hydrocarbon ils can be crude oil, reduced crude and decompression residuum.
Method for hydrotreating hydrocarbon oil according to the present invention is by by hydrocarbon ils and catalyst exposure provided by the invention, and with higher efficiency, hydrotreatment is carried out to hydrocarbon ils, all the other conditions for hydrotreatment are not particularly limited, can according to pending hydrocarbon oil properties, the Conventional wisdom according to this area carries out suitable selection.Such as, when described hydrocarbon ils is heavy hydrocarbon oil, described hydroprocessing condition can comprise: temperature can be 300-450 DEG C, is preferably 330-400 DEG C; Hydrogen dividing potential drop can be 5-20MPa, is preferably 6-18MPa; The volume space velocity of hydrocarbon ils can be 0.1-3 hour
-1, be preferably 0.15-2 hour
-1; Hydrogen to oil volume ratio can be 200-2500, is preferably 300-2000.
According to method for hydrotreating hydrocarbon oil of the present invention, described catalyst before the use, can carry out presulfurization under the normal condition of this area.The condition of presulfurization can be such as in presence of hydrogen, at the temperature of 140-370 DEG C, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, and described presulfurization can be carried out outside reactor also can be In-situ sulphiding in reactor.
The present invention is described in detail below in conjunction with embodiment and comparative example.
In following examples and comparative example, the method specified in RIPP25-90 is adopted to measure the radial crushing strength of carrier.
In following examples and comparative example, following methods is adopted to measure the δ value of carrier: to adopt the method mensuration that specifies in RIPP25-90 (to be designated as Q without the radial crushing strength of the carrier of water soaking
1); Carrier is placed in 50g deionized water, soaks 30 minutes, then filter, by the solid that obtains 120 DEG C of dryings 4 hours, the radial crushing strength measuring dry solid according to the method specified in RIPP25-90 (is designated as Q
2), adopt following formulae discovery δ value,
In following examples and comparative example, following methods is adopted to measure the water absorption rate of carrier: by carrier to be measured 120 DEG C of dryings 4 hours, then to sieve with 40 object standard screens, take 20g oversize and (be designated as w as testing sample
1), testing sample 50g deionized water is soaked 30 minutes, after filtration, solid phase is drained 5 minutes, the weight then weighing the solid phase drained (is designated as w
2), with following formulae discovery water absorption rate:
In following examples and comparative example, testing sample measures 600 DEG C of roastings 4 hours by contents on dry basis.In following examples and comparative example, measure forming of catalyst by x-ray fluorescent spectrometry (that is, XRF).
In following examples and comparative example, adopt SEM-EDX to measure the distribution of metallic element along catalyst radial section, calculate metallic element at the ratio of the mean concentration of catalyst granules outer surface with the mean concentration of center.Wherein, the mean concentration of outer surface is the mean value of outer surface 20 numerical point counting rates; Mean value (the note: the counting rate along the radial every bit of carrier in SEM-EDX characterization result is mutually corresponding with this tenor of 20 the numerical point counting rates in some place centered by the mean concentration of center, the size of counting rate reflects this tenor height, but does not represent the real content of this metal).
Embodiment 1-11 is for illustration of Catalysts and its preparation method of the present invention.
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 Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder, 20.2g metatitanic acid slurries (with TiO
2meter, Ti content is 40 % by weight) and 80.0g deionized water mix.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven, 190 DEG C of dryings 12 hours, obtains the carrier in catalyst of the present invention.
(2) 0.47g basic nickel carbonate (NiO content is 51 % by weight), 1.2g molybdenum oxide and 0.23g phosphoric acid are dissolved in the water, are mixed with 60mL solution; The carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 73.5 % by weight) the solution impregnation 20.1g step (1) obtained prepared, dip time is 4 hours.After filtration, by the solid product that obtains in 120 DEG C of dryings 4 hours, obtain catalyst according to the invention B1.
Comparative example 1
(1) method identical with embodiment 1 is adopted to prepare article shaped, unlike, do not use methylcellulose, but use 2.5mL red fuming nitric acid (RFNA), and the wet bar extruded is placed in baking oven 190 DEG C of dryings and, after 12 hours, then 600 DEG C of roastings 4 hours, thus obtains carrier.
(2) 4.71g basic nickel carbonate (NiO content is 51 % by weight), 12.0g molybdenum oxide and 2.24g phosphoric acid are dissolved in the water, are mixed with 60mL solution.The carrier (diameter is 1.1mm, and particle length is 2-5mm) the solution impregnation 14.3g step (1) obtained prepared, dip time is 1 hour.After filtration, by the solid product that obtains in 120 DEG C of dryings 4 hours, obtain catalyst A 1.
Comparative example 2
(1) method identical with comparative example 1 is adopted to prepare carrier, unlike, do not carry out roasting at 600 DEG C, thus obtain carrier.
(2) the method Kaolinite Preparation of Catalyst identical with comparative example 1 is adopted, unlike, carrier is carrier prepared by comparative example 2 step (1), and in dipping process, the phenomenon of dissolving and structural breakdown appears in carrier, and the catalyst A 2 obtained cannot use as preformed catalyst.
Comparative example 3
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, unlike, in step (1), the wet bar extruded is placed in baking oven, drying 12 hours at the temperature of 175 DEG C, thus obtains carrier, the catalyst obtained is designated as A3.
Comparative example 4
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, unlike, in step (1), by the wet bar extruded 190 DEG C of dryings after 12 hours, then 500 DEG C of roastings 3 hours, thus obtain carrier, the catalyst obtained is designated as A4.
Comparative example 5
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, unlike, in step (2), the solid product obtained after 4 hours, then 500 DEG C of roastings 3 hours, thus is obtained catalyst A 5 in 120 DEG C of dryings.
Embodiment 2
(1) in the retort of a 2L with and the mode of flowing adds the aluminum sulfate solution and sodium aluminate solution (Al that 2000mL concentration is 48g/L
2o
3content is 200g/L, and causticity coefficient is 1.58) carry out precipitation reaction, reaction temperature is 50 DEG C, and pH value is 6.0, and reaction time is 15 minutes; The slurries vacuum filter obtained is filtered, to be filtered complete after, on filter cake supplement add 20L deionized water (temperature is 40 ± 5 DEG C) flush cake about 60 minutes.Filter cake after washing is joined 1.5L deionized water for stirring and becomes slurries, slurries are carried out drying with being pumped 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, Al
2o
3content is 63 % by weight, is defined as amorphous state through XRD analysis.
(2) amorphous hydrated aluminium oxide 50.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 50.0g step (1) prepared, 2.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 5.0g metatitanic acid slurries are (with TiO
2meter, Ti content is 40 % by weight) and 90g deionized water mix.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 220 DEG C of dryings 6 hours, obtains the carrier in catalyst of the present invention.
(3) 1.18g basic nickel carbonate (NiO content is 51 % by weight), 3.00g molybdenum oxide and 0.65g phosphoric acid are dissolved in the water, are mixed with 60mL solution.By the carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.5 % by weight) obtaining solution impregnation 20.3g step (2) and prepare, dip time is 4 hours.After filtration, by the solid that obtains in 120 DEG C of dryings 4 hours, obtain catalyst B 2 of the present invention.
Embodiment 3
(1) by 60.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 40.0g gibbsite (purchased from Pingguo Aluminium Industry Co., Guangxi, contents on dry basis is 64.5 % by weight), 1.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 2.0g hydroxypropyl methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder, 30.0g titanium dioxide and 120g deionized water and stirring be even.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 200 DEG C of dryings 8 hours, obtains the carrier in catalyst of the present invention.
(2) 0.34g basic cobaltous carbonate (CoO content is 70 % by weight), 1.2g molybdenum oxide and 0.23g phosphoric acid are dissolved in the water, are mixed with 60mL solution.The carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 74.8 % by weight) the solution impregnation 19.1g step (1) obtained prepared, dip time is 1 hour.After filtration, by the carrier that obtains in 120 DEG C of dryings 4 hours, thus obtain catalyst according to the invention B3.
Embodiment 4
(1) by even to 100.0g boehmite SB powder (purchased from Sasol company, contents on dry basis is 75.0 % by weight), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 75.0g titanium dioxide and 150g deionized water and stirring.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 260 DEG C of dryings 4 hours, obtains the carrier in catalyst of the present invention.
(2) by 2.71g nickel nitrate (Ni (NO
3)
26H2O) with 4.11g ammonium metatungstate ((NH
4)
6w
7o
244H
2o) be dissolved in the water, be mixed with 12.8mL solution.The carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 79.1 % by weight) the solution impregnation 17.6g step (1) obtained prepared, dip time is 1 hour.By the solid product that obtains in 160 DEG C of dryings 2 hours, thus obtain catalyst according to the invention B4.
Comparative example 6
The method identical with embodiment 4 is adopted to prepare carrier, unlike, in step (1), the wet bar obtained is placed in baking oven, drying 2 hours at the temperature of 330 DEG C, thus obtains carrier, and then obtain catalyst A 6.
Embodiment 5
(1) 100.0g boehmite SB powder (purchased from Sasol company, contents on dry basis is 75.0 % by weight), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 2.0g hydroxypropyl methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 20.0g titanium dioxide are mixed with 115g deionized water.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 290 DEG C of dryings 4 hours, obtains the carrier in catalyst according to the invention.
(2) 0.78g basic nickel carbonate (NiO content is 51 % by weight), 2.0g molybdenum oxide and 0.38g phosphoric acid are dissolved in the water, are mixed with 60mL solution.The carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 74.5 % by weight) the solution impregnation 19.5g step (1) obtained prepared, dip time is 4 hours.After filtration, by the solid that obtains in 120 DEG C of dryings 4 hours, obtain catalyst B 5 of the present invention.
Embodiment 6
(1) by 100.0g boehmite (purchased from Yantai, Shandong Heng Hui Chemical Co., Ltd., contents on dry basis is 71.0 % by weight), 5.0g hydroxypropyl methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder, 70.0g metatitanic acid slurries (with TiO
2meter, Ti content is 40 % by weight) mix with 55g deionized water.The mixture obtained is sent in extruder and extrudes, obtain wet bar.By the wet bar that obtains in baking oven, 210 DEG C of dryings 4 hours, obtain the carrier in catalyst of the present invention.
(2) 1.76g basic nickel carbonate (NiO content is 51 % by weight), 4.50g molybdenum oxide and 0.84g phosphoric acid are dissolved in the water, are mixed with 60mL solution.The carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 76.2 % by weight) the solution impregnation 18.8g step (1) obtained obtained, dip time is 4 hours.After filtration, by the solid product that obtains in 150 DEG C of dryings 3 hours, thus obtain catalyst according to the invention B6.
Embodiment 7
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 2, unlike, in step (1), the content of methylcellulose is 2.0g, the content of HEMC is 5.0g, thus the carrier obtaining in catalyst according to the invention (diameter is 1.1mm, and particle length is 2-5mm, contents on dry basis is 73.3 % by weight), and then obtain catalyst according to the invention B7.
Embodiment 8
(1) 100.0g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 4.0g methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd) and 3.0g sesbania powder are mixed.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven at the temperature of 185 DEG C dry 12 hours.Take the shaping and drying bar of 50g, put into and be dissolved in by 12.0g tetra-n-butyl titanate the 100mL solution that deionized water prepares, soak after 4 hours and filter, 220 DEG C of dryings 6 hours, obtain the carrier in catalyst according to the invention.
(2) the method Kaolinite Preparation of Catalyst identical with embodiment 1 is adopted, be that (diameter is 1.1mm to the carrier prepared of 18.9g embodiment 8 step (1), and particle length is 2-5mm unlike, carrier, contents on dry basis is 75.5 % by weight), thus obtain catalyst according to the invention B8.
Embodiment 9
(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 Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder, 25.0g zirconium hydroxide (with ZrO
2meter, zirconium content is 35 % by weight) and 85g deionized water mix.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven, 200 DEG C of dryings 6 hours, obtains the carrier in catalyst according to the invention.
(2) 0.47g basic nickel carbonate (NiO content is 51 % by weight), 1.20g molybdenum oxide and 0.23g phosphoric acid are dissolved in the water, are mixed with 60mL solution; The carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 74.3 % by weight) the solution impregnation 19.2g step (1) obtained prepared, dip time is 4 hours.After filtration, by the solid product that obtains in 150 DEG C of dryings 3 hours, obtain catalyst according to the invention B9.
Comparative example 7
(1) method identical with embodiment 9 is adopted to prepare carrier, unlike, do not use methylcellulose, but use 2.5mL red fuming nitric acid (RFNA), and the wet bar extruded is placed in baking oven, 200 DEG C of dryings 6 hours, then 600 DEG C of roastings 4 hours, thus carrier is obtained.
(2) 4.71g basic nickel carbonate (NiO content is 51 % by weight), 12.00g molybdenum oxide and 2.24g phosphoric acid are dissolved in the water, are mixed with 60mL solution.The carrier (diameter is 1.1mm, and particle length is 2-5mm) the solution impregnation 14.3g step (1) obtained prepared, dip time is 1 hour.After filtration, by the solid product that obtains in 150 DEG C of dryings 3 hours, obtain catalyst A 7.
Embodiment 10
(1) method identical with embodiment 2 is adopted to prepare amorphous hydrated aluminium oxide.
(2) amorphous hydrated aluminium oxide 50.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 50.0g step (1) prepared, 2.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 5.0g zirconium hydroxide are (with ZrO
2meter, zirconium content is 35 % by weight) and 90g deionized water mix.The mixture obtained is sent in extruder and extrudes, obtain wet bar.By the wet bar that obtains in baking oven, 220 DEG C of dryings 6 hours, obtain the carrier in catalyst of the present invention.
(3) 1.18g basic nickel carbonate (NiO content is 51 % by weight), 3.00g molybdenum oxide and 0.65g phosphoric acid are dissolved in the water, are mixed with 60mL solution.By the carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.5 % by weight) obtaining solution impregnation 20.3g step (2) and prepare, dip time is 4 hours.After filtration, by the solid that obtains in 140 DEG C of dryings 2 hours, obtain catalyst B 10.
Embodiment 11
(1) 100.0g boehmite SB powder (purchased from Sasol company, contents on dry basis is 75.0 % by weight), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 2.0g hydroxypropyl methylcellulose (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd), 3.0g sesbania powder, 18.0g zirconium dioxide are mixed with 115g deionized water.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 250 DEG C of dryings 4 hours, obtains the carrier in catalyst according to the invention.
(2) 0.78g basic nickel carbonate (NiO content is 51 % by weight), 2.00g molybdenum oxide and 0.38g phosphoric acid are dissolved in the water, are mixed with 60mL solution.The carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 73.4 % by weight) the solution impregnation 19.5g step (1) obtained prepared, dip time is 4 hours.After filtration, by the solid that obtains in 120 DEG C of dryings 4 hours, thus obtain catalyst according to the invention B11.
Table 1 lists the radial crushing strength of carrier prepared by embodiment 1-11 and comparative example 1-7, water absorption rate and δ value.
Table 1
| Numbering | Crushing strength (N/mm) | Water absorption rate | δ value (%) |
| Embodiment 1 | 23.3 | 0.87 | 2.9 |
| Comparative example 1 | 25.8 | 0.85 | 3.1 |
| Comparative example 2 | 16.9 | 0.67 | 62.4 |
| Comparative example 3 | 22.8 | 0.86 | 3.1 |
| Comparative example 4 | 25.3 | 0.85 | 3.2 |
| Comparative example 5 | 23.3 | 0.87 | 2.9 |
| Embodiment 2 | 19.8 | 0.71 | 2.8 |
| Embodiment 3 | 16.2 | 0.63 | 3.6 |
| Embodiment 4 | 21.6 | 0.73 | 2.8 |
| Comparative example 6 | 23.8 | 0.75 | 3.4 |
| Embodiment 5 | 23.8 | 0.68 | 2.6 |
| Embodiment 6 | 21.6 | 0.79 | 2.7 |
| Embodiment 7 | 24.1 | 0.83 | 3.3 |
| Embodiment 8 | 22.7 | 0.75 | 2.8 |
| Embodiment 9 | 24.2 | 0.84 | 3.0 |
| Comparative example 7 | 24.3 | 0.83 | 4.2 |
| Embodiment 10 | 18.9 | 0.71 | 2.7 |
| Embodiment 11 | 19.5 | 0.68 | 2.7 |
The result display of table 1, the carrier in catalyst according to the invention has good strength retention, even if crushing strength still higher after soaking in water.
Embodiment 12-22 is for illustration of catalyst of the present invention and application thereof and method for hydrotreating hydrocarbon oil.
Embodiment 12-22
Be that raw material is evaluated catalyst prepared by embodiment 1-11 respectively with decompression residuum, the feedstock oil character of decompression residuum is listed in table 2.Evaluate and carry out in magnetic agitation autoclave device.
Table 2
| Feedstock oil | Slag is subtracted in sand |
| Density (20 DEG C)/gcm -3 | 1.04 |
| Carbon residue/wt% | 25.68 |
| Sulfur content/wt% | 7.23 |
| Nickel content/wppm | 73.9 |
| Content of vanadium/wppm | 183.4 |
Reaction condition comprises: agent oil quality ratio is 0.05, and reaction temperature is 400 DEG C, and the reaction initial pressure of hydrogen is 8MPa, reacts sample analysis after 6 hours.Nickel in the oil adopting plasma emission spectrum (AES/ICP) method assaying reaction to generate, the content of vanadium.By following formulae discovery demetallization per, result is listed in table 3:
Adopt SEM-EDX to characterize the distribution of vanadium on catalyst radial section that reacted catalyst deposits, and calculate the ratio (V of the mean concentration of the center of the mean concentration of vanadium on the outer surface of catalyst and catalyst
outer surface/ V
center), result is listed in table 3.
Comparative example 8-13
Adopt the performance of the catalyst prepared in the method evaluation comparative example 1 identical with embodiment 12-22 and 3-7, result is listed in table 3.
Table 3 lists the composition of the catalyst prepared in embodiment 1-11 and comparative example 1 and 3-7, metal component along the distributed data of catalyst radial section and demetallization per.
From the results shown in Table 3, catalyst according to the invention has higher HDM activity.And, when catalyst according to the invention is used for the HDM reaction of heavy hydrocarbon oil, the metal removed trends towards depositing in the center of catalyst, make catalyst according to the invention have higher appearance metal ability, thus catalyst according to the invention has better stability and longer service life.
Table 3
Claims (32)
1. one kind has the catalyst of hydrogenation catalyst effect, this catalyst contains carrier and load at least one group VIII metallic element on the carrier and at least one group vib metallic element, described group VIII metallic element and group vib metallic element are non-uniform Distribution along this catalyst radial section separately, wherein, along this catalyst radial section
for group VIII metallic element is in the mean concentration of the outer surface of described catalyst;
for group VIII metallic element is in the mean concentration of the center of described catalyst;
be the mean concentration of group vib metallic element at the outer surface of described catalyst;
be the mean concentration of group vib metallic element in the center of described catalyst;
Described carrier is hydrated alumina forming matter, prepares formed body by a kind of raw material, and described formed body is carried out drying and makes, and the temperature of described drying is higher than 180 DEG C and not higher than 300 DEG C,
Described raw material is made up of containing the compound of IVB race metallic element and at least one cellulose ether at least one hydrated alumina, at least one, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-10 % by weight, to contain the total content of the compound of IVB race metallic element described in oxide basis for 0.5-55 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 35-98 % by weight; Or
Described raw material is made up of containing the compound of IVB race metallic element, at least one cellulose ether and at least one extrusion aid at least one hydrated alumina, at least one, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-10 % by weight, to contain the total content of the compound of IVB race metallic element described in oxide basis for 0.5-55 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 35-98 % by weight, and the content of described extrusion aid is 0.1-8 % by weight.
2. catalyst according to claim 1, wherein, along this catalyst radial section,
3. catalyst according to claim 1, wherein, with the total amount of catalyst for benchmark, the content of described carrier is 72-95 % by weight, with oxide basis, the content of described group VIII metallic element is 1-8 % by weight, and the content of described group vib metallic element is 3-20 % by weight.
4. catalyst according to claim 1, wherein, the temperature of described drying is 200-260 DEG C.
5. catalyst according to claim 1, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 1-8 % by weight, to contain the total content of the compound of IVB race metallic element described in oxide basis for 1-50 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 42-96 % by weight.
6. catalyst according to claim 1 or 5, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
7. catalyst according to claim 1 or 5, wherein, described IVB race metallic element is selected from titanium and zirconium.
8. catalyst according to claim 1 or 5, wherein, the described compound containing IVB race metallic element is selected from basic zirconium chloride, zirconium acetate, zirconium sulfate, zirconium nitrate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium, zirconium dioxide, metatitanic acid, metatitanic acid, titanium dioxide, the compound shown in titanium sulfate and formula I
TiX
n(OR)
4-n(I)，
In formula I, X is halogen, and R is C
1-C
5alkyl, n is the integer of 0-4;
Described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
9. the catalyst according to claim 1 or 3, wherein, the water absorption rate of described carrier is 0.4-1.5, δ value is less than 10%, Q
1for more than 12N/mm,
Wherein,
Q
1for the radial crushing strength of the carrier without water soaking, in N/mm,
Q
2for through water soaking 30 minutes and in the radial crushing strength of the carrier of 120 DEG C of dryings after 4 hours, in N/mm.
10. catalyst according to claim 9, wherein, the water absorption rate of described carrier is 0.6-1, δ value is less than 5%, Q
1for 15-30N/mm.
11. according to the catalyst in claim 1-3 described in any one, and wherein, described group VIII metallic element is cobalt and/or nickel, and described group vib metal is molybdenum and/or tungsten.
12. catalyst according to claim 1, wherein, with the total amount of described raw material for benchmark, the content of described extrusion aid is 0.5-5 % by weight.
13. catalyst according to claim 1 or 12, wherein, described extrusion aid is starch.
14. catalyst according to claim 1 or 12, wherein, described extrusion aid is sesbania powder.
15. 1 kinds of methods preparing the catalyst with hydrogenation catalyst effect, the method is included in supported on carriers at least one group VIII metallic element and at least one group vib metallic element, load is on the carrier substantially in a salt form for described group VIII metallic element and group vib metallic element, it is characterized in that, described carrier is hydrated alumina forming matter, formed body is prepared by a kind of raw material, and described formed body is carried out drying at higher than 180 DEG C and not higher than the temperature of 300 DEG C and makes
Described raw material is made up of containing the compound of IVB race metallic element and at least one cellulose ether at least one hydrated alumina, at least one, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-10 % by weight, to contain the total content of the compound of IVB race metallic element described in oxide basis for 0.5-55 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 35-98 % by weight; Or
Described raw material is made up of containing the compound of IVB race metallic element, at least one cellulose ether and at least one extrusion aid at least one hydrated alumina, at least one, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-10 % by weight, to contain the total content of the compound of IVB race metallic element described in oxide basis for 0.5-55 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 35-98 % by weight, and the content of described extrusion aid is 0.1-8 % by weight.
16. methods according to claim 15, wherein, the temperature of described drying is 200-260 DEG C.
17. methods according to claim 15, wherein, the mode being prepared formed body by described raw material comprises:
At least one hydrated alumina, at least one are mixed with water containing the compound of IVB race metallic element and at least one cellulose ether, obtains the first mixture, and by shaping for described first mixture; 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 carried out shaping and dehydration, obtain preform, on described preform, load at least one is containing the compound of IVB race metallic element.
18. methods according to claim 15 or 17, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 1-8 % by weight, with described in oxide basis containing the total content of the compound of IVB race metallic element for 1-50 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 42-96 % by weight.
19. methods according to claim 15 or 17, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
20. methods according to claim 15 or 17, wherein, described IVB race metallic element is for being selected from titanium and zirconium.
21. methods according to claim 15 or 17, wherein, the described compound containing IVB race metallic element is selected from basic zirconium chloride, zirconium acetate, zirconium sulfate, zirconium nitrate, zirconium carbonate, zirconium hydroxide, alkali formula zirconium ammonium, zirconium dioxide, metatitanic acid, metatitanic acid, titanium dioxide, the compound shown in titanium sulfate and formula I
TiX
n(OR)
4-n(I)，
In formula I, X is halogen, and R is C
1-C
5alkyl, n is the integer of 0-4;
Described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
22. methods according to claim 15, wherein, described group vib metallic element and group VIII metallic element load capacity on the carrier make, with the total amount of the catalyst finally prepared for benchmark, the content of described carrier is 72-95 % by weight, with oxide basis, the content of described group VIII metallic element is 1-8 % by weight, and the content of described group vib metallic element is 3-20 % by weight.
23. methods according to claim 15 or 22, wherein, by being immersed in supported on carriers at least one containing the component of group VIII metallic element and at least one component containing group vib metallic element.
24. methods according to claim 23, wherein, the method also comprises carries out drying by flooding the carrier obtained, and the condition of described drying comprises: temperature is 100-200 DEG C, and the time is 1-15 hour.
25. methods according to claim 15 or 22, wherein, described group VIII metallic element is cobalt and/or nickel, and described group vib metal is molybdenum and/or tungsten.
26. methods according to claim 15, wherein, with the total amount of described raw material for benchmark, the content of described extrusion aid is 0.5-5 % by weight.
27. methods according to claim 15 or 26, wherein, described extrusion aid is starch.
28. methods according to claim 15 or 26, wherein, described extrusion aid is sesbania powder.
Catalyst prepared by the method in 29. claim 15-28 described in any one.
The application of catalyst in hydrocarbon oil hydrogenation process in 30. claim 1-14 and claim 29 described in any one.
31. 1 kinds of method for hydrotreating hydrocarbon oil, the method comprises under hydroprocessing conditions, by the catalyst exposure in hydrocarbon ils and claim 1-14 and claim 29 described in any one.
32. methods according to claim 31, wherein, described hydrocarbon ils is one or more in crude oil, reduced crude and decompression residuum.
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Citations (5)
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|---|---|---|---|---|
| US5266188A (en) * | 1991-04-22 | 1993-11-30 | Amoco Corporation | Selective hydrotreating |
| US5358633A (en) * | 1993-05-28 | 1994-10-25 | Texaco Inc. | Hydrodesulfurization of cracked naphtha with low levels of olefin saturation |
| US5525211A (en) * | 1994-10-06 | 1996-06-11 | Texaco Inc. | Selective hydrodesulfurization of naphtha using selectively poisoned hydroprocessing catalyst |
| CN1289647A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing catalyst with non-uniform distribution of active metals |
| 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 |
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2012
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5266188A (en) * | 1991-04-22 | 1993-11-30 | Amoco Corporation | Selective hydrotreating |
| US5358633A (en) * | 1993-05-28 | 1994-10-25 | Texaco Inc. | Hydrodesulfurization of cracked naphtha with low levels of olefin saturation |
| US5525211A (en) * | 1994-10-06 | 1996-06-11 | Texaco Inc. | Selective hydrodesulfurization of naphtha using selectively poisoned hydroprocessing catalyst |
| CN1289647A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing catalyst with non-uniform distribution of active metals |
| 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 |
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