CN103480423B - There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and hydrotreating method - Google Patents
There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and hydrotreating method 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, wherein, described carrier is hydrated alumina forming matter or aluminium oxide article shaped, makes containing rare earth element by containing at least one hydrated alumina, at least one with the raw material of at least one cellulose ether.Present invention also offers a kind of method for hydrotreating hydrocarbon oil, the method comprises under hydroprocessing conditions, by hydrocarbon ils and catalyst exposure of the present invention.Catalyst of the present invention demonstrates higher catalytic activity in the hydrotreatment of hydrocarbon ils.
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 hydrotreating method.
Background technology
Hydrogen addition technology reduces one of impurity content, the major technique improving oil quality in oil product, and its core is hydrogenation catalyst.Conventional hydrogenation catalyst can by preparing the active component load with hydrogenation catalyst effect on porous support, and wherein, the most frequently used porous carrier is aluminium oxide article shaped.
The heavy-oil hydrogenation catalyst that Richard A.Kemp reports adds in boehmite gel by the solution containing active metal component, then carry out extrusion molding, drying and roasting and prepare (RichardA.Kemp, Charles T.Adam, Applied Catalysis A:General, 134 (1996): 299-317).
The Hydrobon catalyst of D.Minoux report is by nickel nitrate and ammonium molybdate being mixed with boehmite, then carry out shaping, dry and roasting and prepare (D.Minoux, F.Diehl, P.Euzen, Jean-Pierre Jolivetb, Edmond Payen, Studies in Surface Science and Catalysis, 143 (2002): 767-775).
But along with environmental requirement increasingly stringent in world wide, various countries are day by day harsh to the quality requirement of vehicle fuel; And because petroleum resources reduce, oil property becomes and heavily becomes bad, and refinery has to process crude oil more inferior, therefore in the urgent need to having the hydrogenation catalyst of more high catalytic activity.
Summary of the invention
The object of the present invention is to provide a kind of there is hydrogenation catalyst effect Catalysts and its preparation method and application and hydrotreating method, catalyst according to the invention has the catalytic activity of raising.
A first aspect of the present 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, wherein, described carrier is hydrated alumina forming matter or aluminium oxide article shaped, makes containing the compound of rare earth 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, wherein, described carrier is hydrated alumina forming matter or aluminium oxide article shaped, makes containing the compound of rare earth element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one; 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.
A third aspect of the present invention provides a kind of catalyst with hydrogenation catalyst effect 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 hydrotreating method, and the method comprises under hydroprocessing conditions, and by hydrocarbon ils and catalyst exposure, wherein, described catalyst is catalyst provided by the invention.
Catalyst according to the invention demonstrates higher catalytic activity in the hydrotreatment of hydrocarbon ils.
Detailed description of the invention
A first aspect of the present invention provides a kind of catalyst with hydrogenation catalyst effect, and 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, 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, with the total amount of described catalyst for benchmark, the content of described carrier can be 30-80 % by weight, is preferably 40-75 % by weight; With oxide basis, the content of described group VIII metallic element can be 2-15 % by weight, is preferably 4-10 % by weight; With oxide basis, the content of described group vib metallic element can be 15-55 % by weight, is preferably 20-50 % 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, described group VIII metallic element and group vib metallic element existence form are on the carrier not particularly limited, and can be that the routine of this area is selected.From the angle of catalytic activity improving further catalyst according to the invention, load is on the carrier in a salt form for described group VIII metallic element and 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 carrier can prepare formed body by containing at least one hydrated alumina, at least one containing the compound of rare earth element and the raw material of at least one cellulose ether, and described formed body is carried out drying and makes (that is, described carrier is hydrated alumina forming matter); Also formed body can be prepared by containing at least one hydrated alumina, at least one containing the compound of rare earth element and the raw material of at least one cellulose ether, and described formed body successively carried out drying and roasting and make (that is, described carrier is aluminium oxide article shaped).From the further angle improving the catalytic activity of catalyst according to the invention, described carrier is hydrated alumina forming matter.
According to the present invention, described raw material contains at least one hydrated alumina, at least one contains rare earth 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).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 3-7 % by weight; Can be 0.5-12 % by weight with the total content of compound containing rare earth element described in oxide basis, preferably 1-10 % by weight, be more preferably 1-9 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be 78-98 % by weight, is preferably 82-97 % by weight, is more preferably 84-95 % by weight.In the present invention, when calculating the total amount of described raw material, containing the compound of rare earth element with oxide basis, hydrated alumina is with Al
2o
3meter, and do not comprise the water 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 rare earth elements that described rare earth element can be commonly used for this area.In article shaped according to the present invention as when having the carrier of catalyst of hydrogenation catalyst effect, described rare earth element is preferably selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm; More preferably La and Ce is selected from.
According to the present invention, the compound containing rare earth element in the various molecular structures that the described compound containing rare earth element can be commonly used for this area.Preferably, the described compound containing rare earth element is selected from rare earth chloride (that is, RECl
3), nitric acid rare earth (that is, RE (NO
3)
3), nitric acid rare earth ammonium (that is, (NH
4)
2rE (NO
3)
6) and rare earth acetate (that is, RE (Ac)
3, Ac is acetate).Particularly, the described compound containing rare earth element can be selected from RECl
3, La (NO
3)
36H
2o and (NH
4)
2ce (NO
3)
6.Wherein, RE represents rare earth element.
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 consumption of described extrusion aid and kind can be that the routine of this area is selected.Usually, with the total amount of described raw material for benchmark, the content of described extrusion aid can be 0.1-8 % by weight, is preferably 0.5-5 % by weight.According to hydrated alumina forming matter of the present invention, described extrusion aid is preferably starch (that is, described raw material is also containing starch).As the starch in the various sources that the starch of extrusion aid can be commonly used for this area, such as: by vegetable seeds through pulverizing the powder obtained, as sesbania powder.
Catalyst according to the invention, described carrier is made up of described raw material.The conventional various methods in this area can be adopted to prepare formed body by described raw material, and described formed body is carried out drying and optional roasting, to obtain the carrier in catalyst of the present invention.The various methods that this area can be adopted conventional, to prepare described formed body, such as: the compound mixed-forming that directly at least one hydrated alumina, at least one cellulose ether and at least one can be contained rare earth element, thus obtain described formed body; 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 rare earth element, thus obtains described formed body.
One of the present invention preferred embodiment in, described formed body is mixed with water containing the compound of rare earth element and at least one cellulose ether at least one hydrated alumina, at least one, obtain the first mixture, and make shaping for described first mixture.
In another preferred embodiment of the present invention, described formed body is mixed with water at least one hydrated alumina and at least one cellulose ether, obtain the second mixture, and described second mixture is successively carried out shaping and dehydration, obtain preform, and load at least one is made containing the compound of rare earth element on described preform.
In this embodiment, on described preform, load at least one contains the routine selection that the mode of the compound of rare earth element can be this area, such as: by being contacted with containing the solution of at least one containing the compound of rare earth element by described preform, thus the compound loaded on described preform of rare earth 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 rare earth element, thus contain the compound loaded on described preform of rare earth element by described.Adopting the mode of dipping by described containing when rare earth element compound loaded is on described preform, described dipping can be saturated dipping, also can flood for supersaturation.The described solvent containing the solution of the compound of rare earth 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 rare earth element, with enable the amount of the compound containing rare earth 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 the temperature of 80-300 DEG C, more preferably carries out at the temperature of 120-250 DEG C.The time of described dehydration can carry out suitable selection according to the temperature of dehydration, is not particularly limited.Usually, the time of described dehydration can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
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.
The temperature of described formed body drying can be that the routine of this area is selected by catalyst according to the invention.Usually, the temperature of described drying can be more than 60 DEG C and lower than 350 DEG C, be preferably 80-300 DEG C, be more preferably 120-250 DEG C.The time of described drying can carry out suitable selection according to the temperature of drying, meets instructions for use be as the criterion can make volatile matter content in the article shaped that finally obtains.Usually, the time of described drying can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.According to the present invention, described drying can be carried out at ambient pressure, also can carry out at reduced pressure.
Catalyst according to the invention, when described carrier is aluminium oxide article shaped, the present invention is not particularly limited for the condition of described roasting, can be that the routine of this area is selected.Particularly, the temperature of described roasting can be 450-950 DEG C, is preferably 500-900 DEG C; The time of described roasting can be 2-8 hour, is preferably 3-6 hour.
Catalyst according to the invention, described carrier has good intensity and absorbent properties.
Particularly, described carrier radial crushing strength loss late (that is, δ value) is after steeping less than 10%, can be even less than 5% (as less than 4%).
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.
Radial crushing strength (that is, the Q of described carrier
1) can be more than 12N/mm, be even more than 15N/mm.Generally, the radial crushing strength of described carrier is that 15-30N/mm(is as 15-25N/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 RIPP 25-90 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 0.6-1.2.
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.
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, wherein, described carrier is hydrated alumina forming matter or aluminium oxide article shaped, makes containing the compound of rare earth element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one; 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.
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.When the hydrotreatment of catalyst prepared by method of the present invention for hydrocarbon ils, described group vib metallic element and the load capacity of group VIII metallic element on carrier make, with the total amount of the catalyst finally prepared for benchmark, the content of described carrier can be 30-80 % by weight, is preferably 40-75 % by weight; With oxide basis, the content of described group VIII metallic element can be 2-15 % by weight, is preferably 4-10 % by weight; With oxide basis, the content of described group vib metallic element can be 15-55 % by weight, is preferably 20-50 % by weight.
The present invention is not particularly limited for the method at supported on carriers at least one group VIII metallic element and at least one group vib metallic element, can adopt the various methods that this area is conventional.Such as, can by dipping by described group VIII metallic element and the load of group vib metallic element on the carrier.Described dipping can be saturated dipping, also can be excessive dipping.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.
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 the carrier after dipping is carried out drying.
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 compound water solution dip loading 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.
The present invention is 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).
Drying is carried out by flooding the carrier obtained under the condition can commonly used in this area.Usually, 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 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 salt 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, the various water soluble compounds containing group vib metallic element can commonly used for 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 contact with molybdenum oxide the water soluble compound formed in water 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 salt of described para-molybdic acid comprises water-soluble metal salt and the ammonium paramolybdate of para-molybdic acid.Preferably, the described compound 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 the present invention, load has the carrier of described group VIII metallic element and group vib metallic element can carry out roasting (namely, in the catalyst of preparation, load is on the carrier in the form of the oxide separately for group VIII metallic element and group vib metal), also roasting can not be carried out (namely, in the catalyst of preparation, load is on the carrier substantially in a salt form for described group VIII metallic element and group vib metallic element; Also namely, in the catalyst of preparation, described group VIII metallic element and group vib metallic element are substantially with the form load of non-oxidized substance on the carrier).From the further angle improving the catalytic activity of catalyst according to the invention, described group VIII metallic element and the preferred load substantially in a salt form of group vib metallic element are on the carrier.That is, load has the carrier of described group VIII metallic element and group vib metallic element preferably not carry out roasting.
According to method of the present invention, described carrier can be hydrated alumina forming matter, also can be aluminium oxide article shaped, makes containing the compound of rare earth element and the raw material of at least one cellulose ether by containing at least one hydrated alumina, at least one.From the further angle improving the activity of prepared according to the methods of the invention catalyst, described carrier is preferably hydrated alumina forming matter.The preparation method of described carrier is described above, is not described in detail in this.
According to method of the present invention, the radial crushing strength of described carrier can be more than 12N/mm, is even more than 15N/mm, is generally 15-30N/mm(as 15-25N/mm).The δ value of described carrier is less than 10%, can be even less than 5% (as less than 4%).The water absorption rate of described carrier is 0.4-1.5, is generally 0.6-1.2.
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 component introduction volume on the carrier can improving 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 is 0.1-10 % by weight, is preferably 0.5-5 % by weight.
The catalyst that prepared according to the methods of the invention has a hydrogenation catalyst effect has the catalytic activity of raising.
Thus, a third aspect of the present invention provides a kind of catalyst with hydrogenation catalyst effect prepared by method of the present invention.
The catalyst with hydrogenation catalyst effect provided by the invention is suitable for the hydroprocessing processes of all kinds of hydrocarbon oil crude material.
Thus, a fourth aspect of the present invention provides a kind of according to the application of catalyst in hydrocarbon oil hydrogenation process with hydrogenation catalyst effect of the present invention.
A fifth aspect of the present invention provides a kind of hydrotreating method, under the method is included in hydrocarbon oil hydrogenation treatment conditions, by hydrocarbon ils and catalyst exposure of the present invention.
Hydrotreating method of the present invention is that the catalyst that the application of the invention provides obtains higher hydrogenation activity, is not particularly limited for the kind of hydrocarbon ils and hydroprocessing condition, can be that the routine of this area is selected.
Particularly, described hydrocarbon ils can be the mixed fraction oil of various heavy mineral oil, artificial oil or heavy mineral oil and artificial oil, such as: described hydrocarbon ils can one or more for being selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and heavy deasphalted oil.The condition of described hydrotreatment comprises: temperature can be 300-380 DEG C; In gauge pressure, pressure can be 4-8MPa; During the liquid of hydrocarbon ils, volume space velocity can be 1-3 hour
-1; Hydrogen to oil volume ratio can be 200-1000.
According to hydrotreating method 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 RIPP 25-90 is adopted to measure the radial crushing strength of the carrier of preparation.
In following examples and comparative example, following methods is adopted to measure the δ value of the article shaped of preparation: to adopt the method mensuration that specifies in RIPP 25-90 (to be designated as Q without the radial crushing strength of the carrier of water soaking
1); The carrier of preparation is placed in 50g deionized water, soaks 30 minutes, then filter, by the solid that obtains at the temperature of 120 DEG C dry 4 hours, the radial crushing strength measuring dry solid according to the method specified in RIPP 25-90 (was designated as Q
2), adopt following formulae discovery δ value,
In following examples and comparative example, following methods is adopted to measure the water absorption rate of the carrier of preparation: 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, contents on dry basis is testing sample in the percent value of the weight of the weight of 600 DEG C of roastings after 4 hours and unfired sample.
Embodiment 1-10 is for illustration of the Catalysts and its preparation method with hydrogenation 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, 20.0mL rare earth chloride (that is, RECl
3) aqueous solution is (with RE
2o
3meter, content of rare earth is 85.0g/L, in its total amount of rare earth: Ce
2o
363 % by weight, La
2o
325 % by weight, Pr
6o
112.1 % by weight, Nd
2o
35.0 % by weight, Sm
2o
30.5 % by weight, other rare earth 4.4 % by weight) and 80g deionized water mix.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven, 150 DEG C of dryings 12 hours, thus obtains the carrier in catalyst according to the invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(2) 4.71 grams of basic nickel carbonates (NiO content is 51 % by weight), 12.0 grams of molybdenum oxides and 2.24 grams of 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 71.3 % 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.Adopt XRF to measure the composition of catalyst, result illustrates in table 2.
Comparative example 1
(1) method identical with embodiment 1 is adopted to prepare carrier, unlike, do not use methylcellulose, but use 2.5mL red fuming nitric acid (RFNA), and the wet bar extruded after 12 hours, then 600 DEG C of roastings 4 hours, thus is obtained carrier 150 DEG C of dryings.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(2) 2.03 grams of basic nickel carbonates (NiO content is 51 % by weight), 5.18 grams of molybdenum oxides and 0.62 gram of phosphoric acid are dissolved in the water, are mixed with 12.3mL 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.By the solid product that obtains in 120 DEG C of dryings 4 hours, then at 400 DEG C of roasting 3h, obtain catalyst A 1.Adopt XRF to measure the composition of catalyst, result is listed in table 2.
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.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(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 structure collapses appears in carrier, and result cannot obtain shaping catalyst.
Comparative example 3
(1) method identical with comparative example 1 is adopted to prepare carrier.
(2) the method Kaolinite Preparation of Catalyst identical with comparative example 1 is adopted, unlike, do not carry out roasting at 400 DEG C, obtain catalyst A 2.Adopt XRF to measure the composition of catalyst, result is listed in table 2.
Embodiment 2
(1) in the retort of a 2L with and the mode of flowing adds the aluminum sulfate solution and sodium aluminate solution (Al that 2000mL concentration is 48g/L
2o
3content is 200g/L, and causticity coefficient is 1.58) carry out precipitation reaction, reaction temperature is 50 DEG C, and pH value is 6.0, and reaction time is 15 minutes; The slurries vacuum filter obtained is filtered, to be filtered complete after, on filter cake supplement add 20L deionized water (temperature is 40 ± 5 DEG C) flush cake about 60 minutes.Filter cake after washing is joined 1.5L deionized water for stirring and becomes slurries, slurries are carried out drying with being pumped in spray dryer, control the outlet temperature of spray dryer within the scope of 100-110 DEG C, the dry materials time is 2 minutes, obtain hydrated alumina, wherein, Al
2o
3content is 63 % by weight, is defined as amorphous state through XRD analysis.
(2) amorphous hydrated alumina powder 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), 20.0mL rare earth chloride solution are (with RE
2o
3meter, content of rare earth is 170.0g/L, in its total amount of rare earth: Ce
2o
363 % by weight, La
2o
325 % by weight, Pr
6o
112.1 % by weight, Nd
2o
35.0 % by weight, Sm
2o
30.5 % by weight, other rare earth 4.4 % 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 according to the invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(3) 3.43 grams of basic cobaltous carbonates (CoO content is 70 % by weight), 12.00 grams of molybdenum oxides and 2.24 grams of phosphoric acid are dissolved in the water, be mixed with 60mL solution, (diameter is 1.1mm to the carrier prepared by this solution impregnation 20.3g step (2), particle length is 2-5mm, contents on dry basis is 70.5 % by weight), the time is 4 hours.After filtration, by the solid that obtains in 150 DEG C of dryings 3 hours, obtain catalyst according to the invention B2.Adopt XRF to measure the composition of catalyst, result is listed in table 2.
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 be dissolved with 20gLa (NO
3)
36H
2the 90mL deionized water and stirring of O is even.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 80 DEG C of dryings 12 hours, thus obtains the carrier in catalyst according to the invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(2) by 3.85 grams of nickel nitrate (Ni (NO
3)
26H
2o), 5.65 grams of ammonium metatungstate ((NH
4)
6w
7o
244H
2o) be dissolved in the water, be mixed with 14.6mL solution.The carrier (diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 66.8 % by weight) the solution impregnation 20.3g step (1) obtained prepared, dip time is 1 hour.By the carrier that obtains in 120 DEG C of dryings 4 hours, thus obtain catalyst according to the invention B3.Adopt XRF to measure the composition of catalyst, result is listed in table 2.
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) and be dissolved with 9.5g (NH
4)
2ce (NO
3)
685g deionized water and stirring even.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 150 DEG C of dryings 12 hours, thus obtains the carrier in catalyst according to the invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(2) 1.18 grams of basic nickel carbonates (NiO content is 51 % by weight), 3.00 grams of molybdenum oxides and 0.68 gram of phosphoric acid are dissolved in the water, be mixed with 60mL solution, (diameter is 1.1mm to the carrier prepared by this solution impregnation 18.3g step (1), particle length is 2-5mm, contents on dry basis is 78.2 % by weight), dip time is 4 hours.After filtration, by the solid product that obtains in 120 DEG C of dryings 4 hours, obtain catalyst B 4 of the present invention.Adopt XRF to measure the composition of catalyst, result is listed in table 2.
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, 10gLa
2(CO
3)
38H
2o and 95g deionized water mixes.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 250 DEG C of dryings 4 hours, thus obtains the carrier in catalyst according to the invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(2) 3.53 grams of basic nickel carbonates (NiO content is 51 % by weight), 9.00 grams of molybdenum oxides and 1.38 grams of 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, obtain catalyst B 5 of the present invention.Adopt XRF to measure the composition of catalyst, result is listed in table 2.
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 and be dissolved with 5.0g La (Ac)
3105g deionized water mix.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, 180 DEG C of dryings 4 hours, thus obtains the carrier in catalyst according to the invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(2) 14.12 grams of basic nickel carbonates (NiO content is 51 % by weight), 36.00 grams of molybdenum oxides and 3.35 grams of 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 74.1 % by weight) the solution impregnation 19.3g step (1) obtained obtained, dip time is 4 hours.After filtration, by the solid product that obtains in 120 DEG C of dryings 4 hours, thus obtain catalyst according to the invention B6.Adopt XRF to measure the composition of catalyst, result is listed in table 2.
Embodiment 7
(1) method identical with embodiment 1 is adopted to prepare hydrated alumina forming matter, unlike, the content of methylcellulose is 5.83g, thus obtains the carrier in catalyst according to the invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(2) the method Kaolinite Preparation of Catalyst identical with embodiment 1 is adopted, be that (diameter is 1.1mm to the carrier prepared of embodiment 7 step (1), and particle length is 2-5mm unlike, carrier, contents on dry basis is 70.4 % by weight), thus obtain catalyst according to the invention B7.Adopt XRF to measure the composition of catalyst, result is listed in table 2.
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 Zhejiang Hai Shen Chemical Co., Ltd.) and 3.0g sesbania powder are mixed.The mixture obtained is sent in banded extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven, 150 DEG C of dryings 12 hours.Take 50.0g shaping and drying bar, put into 100.0mL rare earth chloride solution (with RE
2o
3meter, content of rare earth is 85.0g/L, in total amount of rare earth: Ce
2o
363 % by weight, La
2o
325 % by weight, Pr
6o
112.1 % by weight, Nd
2o
35.0 % by weight, Sm
2o
30.5 % by weight, other rare earth 4.4 % by weight) in, soak after 4 hours and filter, 120 DEG C of dryings 6 hours, thus obtain the carrier in catalyst according to the invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(2) the method Kaolinite Preparation of Catalyst identical with embodiment 1 is adopted, be that (diameter is 1.1mm to the carrier prepared of embodiment 8 step (1), and particle length is 2-5mm unlike, carrier, contents on dry basis is 68.1 % by weight), thus obtain catalyst according to the invention B8.Adopt XRF to measure the composition of catalyst, result is listed in table 2.
Embodiment 9
(1) method identical with embodiment 3 is adopted to prepare carrier, unlike, the wet bar obtained is placed in baking oven, 120 DEG C of dryings 12 hours, thus obtains the carrier in catalyst according to the invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(2) the method Kaolinite Preparation of Catalyst identical with embodiment 3 is adopted, be that (diameter is 1.1mm to the carrier prepared of embodiment 9 step (1), and particle length is 2-5mm unlike, carrier, contents on dry basis is 67.9 % by weight), thus obtain catalyst according to the invention B9.Adopt XRF to measure the composition of catalyst, result is listed in table 2.
Embodiment 10
(1) method identical with embodiment 5 is adopted to prepare carrier, unlike, the wet bar obtained is placed in baking oven, 300 DEG C of dryings 4 hours, thus obtains the carrier in catalyst according to the invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(2) the method Kaolinite Preparation of Catalyst identical with embodiment 5 is adopted, unlike, (diameter is 1.1mm to the carrier adopting embodiment 10 step (1) to prepare, and particle length is 2-5mm, contents on dry basis is 75.3 % by weight), thus obtain catalyst according to the invention B10.Adopt XRF to measure the composition of catalyst, result is listed in table 2.
Table 1
| Numbering | Crushing strength (N/mm) | Water absorption rate | δ value (%) |
| Embodiment 1 | 22.2 | 0.85 | 3.4 |
| Comparative example 1 | 19.1 | 0.86 | 3.3 |
| Comparative example 2 | 16.5 | 0.64 | 64.2 |
| Comparative example 3 | 19.1 | 0.86 | 3.3 |
| Embodiment 2 | 19.8 | 0.71 | 2.8 |
| Embodiment 3 | 15.1 | 0.85 | 3.9 |
| Embodiment 4 | 19.7 | 0.70 | 3.1 |
| Embodiment 5 | 20.6 | 0.67 | 2.5 |
| Embodiment 6 | 19.7 | 0.78 | 2.8 |
| Embodiment 7 | 21.8 | 0.83 | 2.9 |
| Embodiment 8 | 20.3 | 0.71 | 3.3 |
| Embodiment 9 | 15.5 | 0.86 | 2.7 |
| Embodiment 10 | 22.6 | 0.68 | 3.7 |
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.
Table 2
Embodiment 11-20 is for illustration of the application of catalyst according to the invention and hydrotreating method.
Embodiment 11-20
With 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) as model compound, the catalytic activity of catalyst prepared of Evaluation operation example 1-10 respectively on high-pressure hydrogenation micro-reactor, actual conditions is as follows.
The n-decane solution of reaction raw materials: 4,6-DMDBT, wherein, concentration is 0.45 % by weight;
The conditions of vulcanization of catalyst: the useful load of catalyst is 0.15g, and temperature is 360 DEG C, and pressure is 4.2MPa, H
2flow velocity is 400mL/min, and sulfurized oil adopts CS
2mass fraction is the cyclohexane solution of 5 % by weight, and sulfurized oil feed rate is 0.4mL/min, and sulfuration carries out 3 hours altogether.
Hydrodesulfurization reaction condition: reaction temperature is 280 DEG C, pressure is 4.2MPa, H
2flow velocity is 400mL/min, and reaction oil feed rate is 0.2mL/min, stable reaction after 3 hours sampling gas-chromatography analyze.
According to following formulae discovery desulfurization degree, result is listed in table 3.
Conversion ratio × (the S of desulfurization degree (%)=4,6-DMDBT
dMBCH+ S
dMCHB+ S
dMBP) × 100%
Wherein, S
dMBCH, S
dMCHBand S
dMBPin the product that obtains of 4,6-DMDBT hydrodesulfurization respectively, dimethyl connection cyclohexane, Dimethylcyclohexyl benzene and dimethyl diphenyl selective.
Comparative example 4 and 5
Adopt the method identical with embodiment 11-20 to evaluate the catalytic activity of catalyst prepared by comparative example 1 and 3 respectively, result is listed in table 3.
Table 3
| Numbering | Catalyst is numbered | Desulfurization degree (%) |
| Embodiment 11 | B1 | 96 |
| Comparative example 4 | A1 | 75 |
| Comparative example 5 | A2 | 77 |
| Embodiment 12 | B2 | 87 |
| Embodiment 13 | B3 | 85 |
| Embodiment 14 | B4 | 87 |
| Embodiment 15 | B5 | 94 |
| Embodiment 16 | B6 | 97 |
| Embodiment 17 | B7 | 94 |
| Embodiment 18 | B8 | 95 |
| Embodiment 19 | B9 | 86 |
| Embodiment 20 | B10 | 88 |
Embodiment 21-27 is for illustration of Catalysts and its preparation method of the present invention.
Embodiment 21
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, unlike, carry out roasting under the condition that carrier embodiment 1 step (1) prepared is listed at table 4, to obtain the carrier used in catalyst according to the invention, and then obtain catalyst according to the invention B11.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in table 4.Adopt XRF to measure the composition of catalyst, result is listed in table 5.
Embodiment 22
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 2, unlike, carry out roasting under the condition that carrier embodiment 2 step (1) prepared is listed at table 4, to obtain the carrier used in catalyst according to the invention, and then obtain catalyst according to the invention B12.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in table 4.Adopt XRF to measure the composition of catalyst, result is listed in table 5.
Embodiment 23
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 3, unlike, carry out roasting under the condition that carrier embodiment 3 step (1) prepared is listed at table 4, to obtain the carrier used in catalyst according to the invention, and then obtain catalyst according to the invention B13.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in table 4.Adopt XRF to measure the composition of catalyst, result is listed in table 5.
Embodiment 24
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 4, unlike, carry out roasting under the condition that carrier embodiment 4 step (1) prepared is listed at table 4, to obtain the carrier used in catalyst according to the invention, and then obtain catalyst according to the invention B14.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in table 4.Adopt XRF to measure the composition of catalyst, result is listed in table 5.
Embodiment 25
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 5, unlike, carry out roasting under the condition that carrier embodiment 5 step (1) prepared is listed at table 4, to obtain the carrier used in catalyst according to the invention, and then obtain catalyst B 15 of the present invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in table 4.Adopt XRF to measure the composition of catalyst, result is listed in table 5.
Embodiment 26
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 6, unlike, carry out roasting under the condition that carrier embodiment 6 step (1) prepared is listed at table 4, to obtain the carrier used in catalyst according to the invention, and then obtain catalyst B 16 of the present invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in table 4.Adopt XRF to measure the composition of catalyst, result is listed in table 5.
Embodiment 27
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 7, unlike, carry out roasting under the condition that carrier embodiment 7 step (1) prepared is listed at table 4, to obtain the carrier used in catalyst according to the invention, and then obtain catalyst according to the invention.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in table 4.Adopt XRF to measure the composition of catalyst, result is listed in table 5.
Embodiment 28
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 8, unlike, carry out roasting under the condition listed at table 4 by the carrier prepared according to embodiment 8 step (1), to obtain the carrier used in catalyst according to the invention, and then obtain catalyst according to the invention B18.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in table 4.Adopt XRF to measure the composition of catalyst, result is listed in table 5.
Table 4
Table 5
Embodiment 29-36 is for illustration of the application of catalyst according to the invention and hydrotreating method.
Adopt the catalytic activity of catalyst that the method identical with embodiment 11-20 is prepared in Evaluation operation example 21-28 respectively, result is listed in table 6.
Table 6
| Numbering | Catalyst is numbered | Desulfurization degree (%) |
| Embodiment 29 | B11 | 92 |
| Embodiment 30 | B12 | 83 |
| Embodiment 31 | B13 | 79 |
| Embodiment 32 | B14 | 81 |
| Embodiment 33 | B15 | 86 |
| Embodiment 34 | B16 | 90 |
| Embodiment 35 | B17 | 88 |
| Embodiment 36 | B18 | 89 |
As can be seen from table 3 and table 6, the catalyst with hydrogenation catalyst effect according to the present invention demonstrates higher catalytic activity in the hydrotreatment of hydrocarbon ils.
Claims (36)
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, it is characterized in that, described carrier is hydrated alumina forming matter or aluminium oxide article shaped, be made up of a kind of raw material, described raw material by least one hydrated alumina, at least one containing the compound of rare earth element, at least one cellulose ether and containing or at least one extrusion aid that do not contain form.
2. catalyst according to claim 1, wherein, with the total amount of this catalyst for benchmark, the content of described carrier is 30-80 % by weight, with oxide basis, the content of described group VIII metallic element is 2-15 % by weight, and the content of described group vib metallic element is 15-55 % by weight.
3. catalyst according to claim 1, wherein, 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 rare earth element described in oxide basis for 0.5-12 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 78-98 % by weight.
4. catalyst according to claim 3, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 3-7 % by weight, to contain the total content of the compound of rare earth element described in oxide basis for 1-9 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 84-95 % by weight.
5. according to the catalyst in claim 1,3 and 4 described in any one, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
6. according to the catalyst in claim 1,3 and 4 described in any one, wherein, described rare earth element is selected from La, Ce, Pm, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm.
7. according to the catalyst in claim 1,3 and 4 described in any one, wherein, the described compound containing rare earth element is selected from rare earth chloride, nitric acid rare earth, nitric acid rare earth ammonium and rare earth acetate;
Described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
8. catalyst according to claim 1 and 2, 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.
9. catalyst according to claim 8, wherein, the radial crushing strength of described carrier is 15-30N/mm, and water absorption rate is 0.6-1.2, δ value is less than 5%.
10. catalyst according to claim 1, wherein, load is on the carrier substantially in a salt form for described group vib metallic element and group VIII metallic element.
11. according to the catalyst in claim 1,2 and 10 described in any one, and wherein, described group VIII metallic element is cobalt and/or nickel, and described group vib metallic element 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 0.1-8 % by weight.
13. catalyst according to claim 12, wherein, with the total amount of described raw material for benchmark, the content of described extrusion aid is 0.5-5 % by weight.
14. according to the catalyst in claim 1,12 and 13 described in any one, and wherein, described extrusion aid is starch.
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, it is characterized in that, described carrier is hydrated alumina forming matter or aluminium oxide article shaped, be made up of a kind of raw material, described raw material by least one hydrated alumina, at least one containing the compound of rare earth element, at least one cellulose ether and containing or at least one extrusion aid that do not contain form; 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.
16. methods according to claim 15, wherein, by being immersed in supported on carriers at least one group VIII metallic element and at least one group vib metallic element.
17. methods according to claim 15 or 16, 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 30-80 % by weight, with oxide basis, the content of described group VIII metallic element is 2-15 % by weight, and the content of described group vib metallic element is 15-55 % by weight.
18. methods according to claim 15 or 16, wherein, described group VIII metallic element is cobalt and/or nickel, and described group vib metal is molybdenum and/or tungsten.
19. methods according to claim 15 or 16, wherein, load is on the carrier substantially in a salt form for described group VIII metallic element and group vib metallic element.
20. methods according to claim 15, wherein, described carrier is hydrated alumina forming matter, and the mode being prepared described carrier by described raw material comprises: prepare formed body by described raw material, and described formed body is carried out drying; Or
Described carrier is aluminium oxide article shaped, and the mode being prepared described carrier by described raw material comprises: prepare formed body by described raw material, and described formed body is successively carried out drying and roasting.
21. methods according to claim 20, wherein, the mode 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 rare earth 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, the preform obtained, on described preform, load at least one is containing the compound of rare earth element.
22. methods according to claim 20, wherein, the temperature of described drying is more than 60 DEG C and lower than 350 DEG C.
23. methods according to claim 22, wherein, the temperature of described drying is 80-300 DEG C.
24. methods according to claim 20, wherein, the condition of described roasting comprises: temperature is 450-950 DEG C, and the time is 2-8 hour.
25. according to the method in claim 15,20 and 21 described in any one, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-10 % by weight, to contain the total content of the compound of rare earth element described in oxide basis for 0.5-12 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 78-98 % by weight.
26. methods according to claim 25, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 3-7 % by weight, to contain the total content of the compound of rare earth element described in oxide basis for 1-9 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 84-95 % by weight.
27. according to the method in claim 15,20 and 21 described in any one, and wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
28. according to the method in claim 15,20 and 21 described in any one, and wherein, described rare earth element is selected from La, Ce, Pm, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Tm.
29. according to the method in claim 15,20 and 21 described in any one, and wherein, the described compound containing rare earth element is selected from rare earth chloride, nitric acid rare earth, nitric acid rare earth ammonium and rare earth acetate;
Described hydrated alumina is selected from boehmite, gibbsite, amorphous hydrated aluminium oxide and boehmite.
30. according to the method in claim 15,16 and 20 described in any one, and wherein, the water absorption rate of described carrier is 0.6-1.2, δ value is less than 5%, Q
1for 15-30N/mm.
31. methods according to claim 15, wherein, with the total amount of described raw material for benchmark, the content of described extrusion aid is 0.1-8 % by weight.
32. methods according to claim 31, wherein, with the total amount of described raw material for benchmark, the content of described extrusion aid is 0.5-5 % by weight.
33. according to the method in claim 15,31 and 32 described in any one, and wherein, described extrusion aid is starch.
The catalyst of hydrogenation catalyst effect that prepared by the method in 34. claim 15-33 described in any one have.
The application of catalyst in 35. claim 1-14 and 34 described in any one in hydrocarbon oil hydrogenation process.
36. 1 kinds of hydrotreating methods, the method comprises under hydroprocessing conditions, by hydrocarbon ils and catalyst exposure, it is characterized in that, described catalyst is the catalyst in claim 1-14 and 34 described in any one.
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