CN103418397B - 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, 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 made up of the raw material containing at least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether.Present invention also offers a kind of method for hydrotreating hydrocarbon oil.Catalyst according to the invention demonstrates higher catalytic activity in hydrocarbon oil hydrogenation process.
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; Further, 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, load is on the carrier substantially in a salt form for described group VIII metallic element and described group vib metallic element, wherein, described carrier is made up of the raw material containing at least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether.
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 described group vib metallic element, wherein, described carrier is made up of the raw material containing at least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether.
A third aspect of the present invention provides a kind of 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 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 is using the article shaped prepared by the raw material containing boehmite, silicon-containing compound and cellulose ether as carrier, and catalytic activity is obviously promoted.
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, with oxide basis, the content of described group VIII metallic element can be 2-15 % by weight, is preferably 4-10 % by weight; The content of described group vib metallic element can be 15-55 % by weight, is preferably 20-50 % by weight; The content of described carrier can be 30-80 % by weight, is preferably 40-75 % 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 substantially in a salt form for described group VIII metallic element and described group vib metallic element.That is, described group VIII metallic element basic (that is, mainly or in fact) in a salt form load on the carrier, load is on the carrier in a salt form for described group vib metallic element basic (that is, mainly or in fact).
Catalyst according to the invention, described carrier is made up of the raw material containing at least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether.
Catalyst according to the invention, described carrier can prepare formed body by the raw material containing at least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether, and described formed body is carried out drying and makes; Also can prepare formed body by the raw material containing at least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether, and described formed body successively carried out drying and roasting and make.
According to the present invention, described raw material contains at least one hydrated alumina, at least one silicon-containing 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 article shaped prepared by described raw material directly can be used as the carrier of catalyst of the present invention without roasting, also can be used as the carrier of catalyst of the present invention after roasting.That is, the carrier in catalyst according to the invention can be siliceous hydrated alumina forming matter, also can be silicon-containing alumina article shaped.
In the present invention, described siliceous hydrated alumina forming matter refers to the hydrated alumina forming matter containing element silicon; Described silicon-containing alumina article shaped refers to the aluminium oxide article shaped containing element silicon.
Catalyst according to the invention, the composition of described raw material can carry out suitable selection according to the application scenario of catalyst, can meet instructions for use be as the criterion with the carrier prepared by this raw material.Usually, with the total amount of described raw material for benchmark, the total content of described cellulose ether can be 0.5-8 % by weight, is preferably 1-6 % by weight, is more preferably 2-5 % by weight; With SiO
2the total content of the described silicon-containing compound of meter can be 0.5-50 % by weight, is preferably 1-45 % by weight, is more preferably 1.5-40 % by weight; With Al
2o
3the total content of the described hydrated alumina of meter can be 47-96 % by weight, is preferably 50-95 % by weight, is more preferably 55-94 % by weight.In the present invention, when calculating the total amount of described raw material, silicon-containing compound is with SiO
2meter, 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 compound containing silicon atom in the various molecular structures that described silicon-containing compound can be commonly used for this area.Such as, described silicon-containing compound can be selected from the compound shown in sodium metasilicate, silica and formula I,
In formula I, R
1, R
2, R
3and R
4can be C separately
1-C
5alkyl or hydrogen; Preferred R
1, R
2, R
3and R
4in at least two be C
1-C
5alkyl; More preferably R
1, R
2, R
3and R
4be C separately
1-C
5alkyl.
Particularly, described silicon-containing compound can be selected from sodium metasilicate, silica, methyl silicate, ethyl orthosilicate, positive n-propyl silicate, positive isopropyl silicate and the positive positive butyl ester of silicic acid.
In the present invention, described silicon-containing compound can be the common silicon-containing compound existed with various form in this area.Such as: sodium metasilicate can be the aqueous solution (that is, waterglass) of sodium metasilicate; Silica can be such as silicon-dioxide powdery (water content is generally lower than 0.1 % by weight, as fumed silica), and also can be Ludox, can also be silica gel.Described Ludox refers to water to be the silica colloid solution of decentralized photo, and wherein, the content of silica can be 10-40 % by weight; Described silica gel refers to the silica dioxide granule (wherein, water content be generally more than 0.1 % by weight and lower than 10 % by weight) containing a small amount of moisture existed in solid form.
Preferably, described silicon-containing compound is selected from sodium metasilicate and silica.More preferably, described silicon-containing compound is silica.
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, unformed hydrated alumina 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.Preferably, with the total amount of described raw material for benchmark, the total content of described extrusion aid is 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).The starch in the various sources that described starch 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, can adopt the conventional various methods in this area to prepare formed body by described raw material, and then obtain described carrier.Such as: directly by least one hydrated alumina, at least one cellulose ether and at least one silicon-containing compound mixed-forming, 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 load at least one silicon-containing compound on this preform, thus obtain described formed body.
One of the present invention preferred embodiment in, described formed body is mixed with water at least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether, obtains the first mixture, and make shaping for described first mixture.
In another preferred embodiment of the present invention, described formed body is mixed with water at least one hydrated alumina and at least one cellulose ether, obtain the second mixture, and described second mixture is successively carried out shaping and dehydration, obtain preform, and load at least one silicon-containing compound is made on described preform.
In this embodiment, on described preform, the mode of load at least one silicon-containing compound can be the routine selection of this area, such as: can by described preform is contacted with the solution containing at least one silicon-containing compound, thus by described silicon-containing compound load on described preform.The mode contacted with described solution by described preform can be selected for the routine of this area, such as: by flooding or spraying, described preform can be contacted with the solution containing at least one silicon-containing compound, thus by described silicon-containing compound load on described preform.Adopt dipping mode by described silicon-containing compound load on described preform time, described dipping can be saturated dipping, also can flood for supersaturation.The solvent of the described solution containing at least one silicon-containing compound can be the routine selection of this area, is preferably water.The concentration of the described solution containing at least one silicon-containing compound is not particularly limited, with enable the amount of the silicon-containing compound of load on described preform meet the demands (such as previously described content) be as the criterion.
In this embodiment, the condition of described dehydration is not particularly limited, and can be that the routine of this area is selected, be as the criterion can remove water.Usually, described dehydration can be carried out lower than at the temperature of 350 DEG C more than 60 DEG C, preferably at the temperature of 80-300 DEG C, more preferably carries out at the temperature of 120-250 DEG C.The time of described dehydration can carry out suitable selection according to the temperature of dehydration, is not particularly limited.Usually, the time of described dehydration can be 1-48 hour, is preferably 2-24 hour, is more preferably 2-12 hour.
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, described carrier can also prepare formed body by the raw material containing at least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether, and described formed body is successively carried out drying and roasting and make.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%.
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 15-30N/mm.
In the present invention, described radial crushing strength be 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.
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.Preferably, 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.More preferably, 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 is 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, 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 made up of the raw material containing at least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether.
According to method of the present invention, described 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 load capacity are on the carrier to make in the catalyst of final preparation, and the content of group VIII metallic element and group vib metallic element can meet concrete instructions for use and be as the criterion.When prepared according to the methods of the invention catalyst is used for the hydrotreatment of hydrocarbon ils, 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, with oxide basis, the content of described group VIII metallic element is 2-15 % by weight, is preferably 4-10 % by weight; The content of described group vib metallic element is 15-55 % by weight, is preferably 20-50 % by weight; The content of described carrier is 30-80 % by weight, is preferably 40-75 % 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).The various modes that this area can be adopted conventional by described group VIII metallic element and described group vib metallic element substantially in a salt form load 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.
In one embodiment of the invention, by described group VIII metallic element and described group vib metallic element substantially in a salt form load mode on the carrier comprise: 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 remove the water on the carrier that floods and obtain.
In another embodiment of the invention, by described group VIII metallic element and described group vib metallic element substantially in a salt form load mode on the carrier comprise: with containing at least one containing the salt of group VIII metallic element aqueous impregnation described in carrier, and remove the water flooded on the carrier that obtains, with the carrier having the described salt containing group VIII metallic element containing at least one containing the aqueous impregnation load of compound of group vib metallic element, and remove the water on the carrier that floods and obtain.
In another embodiment of the present invention, by described group VIII metallic element and described group vib metallic element substantially in a salt form load mode on the carrier comprise: with containing at least one containing the compound of group vib metallic element aqueous impregnation described in carrier, and remove the water flooded on the carrier that obtains, with the carrier having the described compound containing group vib metallic element containing at least one containing the aqueous impregnation load of salt of group VIII metallic element, and remove the water on the carrier that floods and obtain.
According to the present invention, the described salt containing group VIII metallic element can be the conventional various water soluble salts containing group VIII metallic element of 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 water soluble compound 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, concentration for the described aqueous solution is also not particularly limited, 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, remove the water on carrier, such as: temperature can be 100-200 DEG C, be 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 is made up of the raw material containing at least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether, can be siliceous hydrated alumina forming matter, also can be silicon-containing alumina article shaped.The composition of described raw material and the preparation method of carrier are described above, are 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.Generally, the radial crushing strength of described carrier is 15-30N/mm.
According to method of the present invention, the δ value of described carrier is less than 10%, can be even less than 5%.
According to method of the present invention, 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 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 can be 0.1-10 % by weight.Preferably, the described content that can improve the component of the performance of catalyst is 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, and the method comprises under hydroprocessing conditions, by hydrocarbon ils and catalyst exposure of the present invention.
Hydrotreating method according to 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 various heavy mineral oil, artificial oil or their mixed fraction 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.
Usually, described hydroprocessing condition 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, and at the temperature of 140-370 DEG C, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, 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 carrier 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 by measuring testing sample 600 DEG C of roastings 4 hours.
Embodiment 1-10 is for illustration of the Catalysts and its preparation method with hydrogenation catalyst effect of the present invention.
Embodiment 1
(1) measure 12mL water glass solution (purchased from Sinopec catalyst Chang Ling branch company, SiO
2content is 280g/L, modulus is 3.26) be dissolved in deionized water and be mixed with 95mL waterglass weak solution.100g boehmite powder (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 4.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder and the above-mentioned waterglass weak solution of 95mL are mixed.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven, drying 12 hours at the temperature of 150 DEG C, 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) 4.71g 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 nickel-molybdenum-phosphorus solution; The carrier (average diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 69.6 % by weight) the solution impregnation 20.5g step (1) obtained prepared, dip time is 4 hours.After filtration, by the solid product that obtains at the temperature of 120 DEG C dry 4 hours, obtain catalyst according to the invention B1.Adopt XRF to analyze catalyst, result illustrates in table 2.
Comparative example 1
(1) measure 12mL water glass solution (with embodiment 1) to be dissolved in deionized water and to be mixed with 95mL waterglass weak solution.100g boehmite powder (with embodiment 1), 2.5mL red fuming nitric acid (RFNA), 4.0g sesbania powder and the above-mentioned waterglass weak solution of 95mL 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 150 DEG C dry 12 hours, then at the roasting temperature 4 hours of 600 DEG C, thus obtains carrier.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in Table 1.
(2) 2.03g basic nickel carbonate (NiO content is 51 % by weight), 5.18g molybdenum oxide and 1.32g phosphoric acid are dissolved in the water, are mixed with 12.0mL nickel-molybdenum-phosphorus solution.The carrier (average 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 obtain catalyst A 1 at 400 DEG C of roasting 3h.Adopt XRF to analyze 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 structural breakdown 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, thus obtain catalyst A 2.Adopt XRF to analyze 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 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 unformed hydrated alumina, wherein, Al
2o
3content is 63 % by weight, is defined as amorphous state through XRD analysis.
(2) take 50.0g alkaline silica sol (purchased from Red Star spacious mansion chemical building material Co., Ltd of Beijing, SiO
2content is 25 % by weight, Na
2o<0.3 % by weight, pH is 8.5), in deionized water, prepare 95mL silica aqueous solution with stirring and dissolving.Unformed hydrated alumina, 2.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g HEMC (purchased from Shanghai Hui Guang Fine Chemical Co., Ltd) and the above-mentioned silica aqueous solution of 95mL 50.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 50.0g step (1) prepared stir.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, drying 6 hours at the temperature of 220 DEG C, 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.
(3) 3.43g basic cobaltous carbonate (CoO content is 70 % by weight), 12.00g molybdenum oxide and 2.24g phosphoric acid are dissolved in the water, are mixed with 60mL nickel-molybdenum-phosphorus solution.By the carrier (average diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 71.5 % by weight) obtaining solution impregnation 20.0g 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 according to the invention B2.Adopt XRF to analyze catalyst, result is listed in table 2.
Embodiment 3
(1) take 5.0g acidic silicasol (purchased from the long-range Science and Technology Ltd. in Chinese and Western, Beijing, SiO
2content is 30 % by weight, Na
2o<0.006 % by weight, pH is 2-6), with stirring and dissolving in deionized water, prepare the 95mL acidic silicasol aqueous solution.By 60.0g boehmite (purchased from Sinopec catalyst Chang Ling branch company, contents on dry basis is 69.5 % by weight), 40.0g gibbsite (purchased from Pingguo Aluminium Industry Co., Guangxi, contents on dry basis is 64.5 % by weight), 1.0g methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 2.0g hydroxypropyl methylcellulose (purchased from Zhejiang Hai Shen Chemical Co., Ltd.), 3.0g sesbania powder and the above-mentioned acidic silicasol aqueous solution of 95mL stirs.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, drying 12 hours at the temperature of 80 DEG C, 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 3.85g nickel nitrate (Ni (NO
3)
26H
2o), 5.65g ammonium metatungstate ((NH
4)
6w
7o
244H
2o) be dissolved in the water, be mixed with 17.9mL nickel tungsten solution.The carrier (average diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 69.4 % by weight) the solution impregnation 20.6g 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 analyze 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), 95.0g acidic silicasol (purchased from the long-range Science and Technology Ltd. in Chinese and Western, Beijing, SiO
2content is 30 % by weight, Na
2o<0.006 % by weight, pH is 2-6) stir.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, drying 12 hours at the temperature of 150 DEG C, 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) 1.18g basic nickel carbonate (NiO content is 51 % by weight), 3.00g molybdenum oxide and 0.68g phosphoric acid are dissolved in the water, are mixed with 60mL nickel-molybdenum-phosphorus solution.The carrier (average diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 68.6 % by weight) the solution impregnation 20.9g 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, thus obtain catalyst according to the invention B4.Adopt XRF to analyze catalyst, result is listed in table 2.
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), 3.0g sesbania powder and 65.0g fumed silica (purchased from Shenyang Chemical Co., Ltd.) are mixed with 150mL deionized water.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, drying 4 hours at the temperature of 250 DEG C, 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) 3.53g basic nickel carbonate (NiO content is 51 % by weight), 9.00g molybdenum oxide and 1.38g phosphoric acid are dissolved in the water, are mixed with 60mL nickel-molybdenum-phosphorus solution.The carrier (average diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 75.4 % by weight) the solution impregnation 19.0g step (1) obtained prepared, dip time is 4 hours.After filtration, by the solid that obtains in 150 DEG C of dryings 3 hours, thus obtain catalyst according to the invention B5.Adopt XRF to analyze catalyst, result is listed in table 2.
Embodiment 6
(1) 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, 45.0g fumed silica (purchased from Shenyang Chemical Co., Ltd.) are mixed with 135mL deionized water.The mixture obtained is sent in extruder and extrudes, obtain wet bar.The wet bar obtained is placed in baking oven, drying 4 hours at the temperature of 180 DEG C, 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) 14.12g basic nickel carbonate (NiO content is 51 % by weight), 36.00g molybdenum oxide and 6.70g phosphoric acid are dissolved in the water, are mixed with 60mL nickel-molybdenum-phosphorus solution.The carrier (average diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 65.2 % by weight) the solution impregnation 21.9g 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 analyze catalyst, result is listed in table 2.
Embodiment 7
(1) method identical with embodiment 1 is adopted to prepare siliceous 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 B7 identical with embodiment 1 is adopted, unlike, carrier is carrier (average diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 70.2 % by weight) prepared by embodiment 7 step (1).Adopt XRF to analyze 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 extruder and extrudes, obtain wet bar.The wet bar extruded is placed in baking oven at the temperature of 150 DEG C dry 12 hours.Take 50.0g shaping and drying bar, be placed in 100.0g acidic silicasol (purchased from the long-range Science and Technology Ltd. in Chinese and Western, Beijing, SiO
2content is 10 % by weight, Na
2o<0.006 % by weight, pH is 2-6) in, soak after 4 hours and filter, drying 6 hours at the temperature of 120 DEG C, 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 B8 identical with embodiment 1 is adopted, unlike, carrier is carrier (average diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 68.5 % by weight) prepared by embodiment 8 step (1).Adopt XRF to analyze catalyst, result is listed in table 2.
Embodiment 9
(1) method identical with embodiment 3 is adopted to prepare article shaped, unlike, the wet bar obtained is placed in baking oven, drying 12 hours at the temperature of 120 DEG C, 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 B9 identical with embodiment 3 is adopted, unlike, carrier is carrier (average diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 71.6 % by weight) prepared by embodiment 9 step (1).Adopt XRF to analyze catalyst, result is listed in table 2.
Embodiment 10
(1) method identical with embodiment 5 is adopted to prepare article shaped, unlike, the wet bar obtained is placed in baking oven, drying 4 hours at the temperature of 300 DEG C, 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 B10 identical with embodiment 5 is adopted, unlike, carrier is carrier (average diameter is 1.1mm, and particle length is 2-5mm, and contents on dry basis is 77.8 % by weight) prepared by embodiment 10 step (1).Adopt XRF to analyze catalyst, result is listed in table 2.
Table 1
| Numbering | Crushing strength (N/mm) | Water absorption rate | δ value (%) |
| Embodiment 1 | 21.6 | 0.83 | 3.1 |
| Comparative example 1 | 26.3 | 0.84 | 3.4 |
| Comparative example 2 | 15.6 | 0.65 | 65.3 |
| Comparative example 3 | 26.3 | 0.84 | 3.4 |
| Embodiment 2 | 18.9 | 0.69 | 2.4 |
| Embodiment 3 | 14.2 | 0.87 | 3.2 |
| Embodiment 4 | 20.3 | 0.71 | 2.4 |
| Embodiment 5 | 21.2 | 0.68 | 3.1 |
| Embodiment 6 | 19.1 | 0.79 | 3.2 |
| Embodiment 7 | 21.8 | 0.81 | 2.8 |
| Embodiment 8 | 20.2 | 0.72 | 3.5 |
| Embodiment 9 | 15.5 | 0.88 | 2.8 |
| Embodiment 10 | 23.3 | 0.69 | 3.6 |
The result display of table 1, the carrier in catalyst according to the invention has good strength retention, even if still have higher crushing strength after soaking in water.
Table 2
Embodiment 11-20 is for illustration of the catalyst having a hydrogenation catalyst effect according to of the present invention and application thereof and hydrotreating method.
Embodiment 11-20
With 4,6-dimethyl Dibenzothiophene (4,6-DMDBT) as model compound, the hydrodesulfurization 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: temperature is 360 DEG C, in gauge pressure, pressure is 4.2MPa, H
2flow velocity is 400mL/min, and sulfurized oil adopts CS
2mass fraction is the cyclohexane solution of 5%, 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, in gauge pressure, pressure is 4.2MPa, H
2flow velocity is 400mL/min, and the feed rate of reaction raw materials is 0.2mL/min, stable reaction after 3 hours sampling gas-chromatography analyze.
According to following formulae discovery desulfurization degree, thus the hydrodesulfurization activity of evaluate catalysts, result is listed in table 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 4-5
Adopt the method identical with embodiment 11-20 to evaluate the hydrodesulfurization 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 | 97 |
| Comparative example 4 | A1 | 76 |
| Comparative example 5 | A2 | 85 |
| Embodiment 12 | B2 | 93 |
| Embodiment 13 | B3 | 86 |
| Embodiment 14 | B4 | 89 |
| Embodiment 15 | B5 | 96 |
| Embodiment 16 | B6 | 99 |
| Embodiment 17 | B7 | 96 |
| Embodiment 18 | B8 | 97 |
| Embodiment 19 | B9 | 95 |
| Embodiment 20 | B10 | 94 |
Embodiment 21-28 is for illustration of the Catalysts and its preparation method with hydrogenation catalyst effect according to the present invention.
Embodiment 21
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, unlike, carry out roasting under the condition listed at table 4 by the carrier prepared according to embodiment 1 step (1), 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 analyze 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 listed at table 4 by the carrier prepared according to embodiment 2 step (2), 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 analyze 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 listed at table 4 by the carrier prepared according to embodiment 3 step (1), 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 analyze 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 listed at table 4 by the carrier prepared according to embodiment 4 step (1), 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 analyze 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 listed at table 4 by the carrier prepared according to embodiment 5 step (1), to obtain the carrier used in catalyst according to the invention, and then obtain catalyst according to the invention B15.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in table 4.Adopt XRF to analyze 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 listed at table 4 by the carrier prepared according to embodiment 6 step (1), to obtain the carrier used in catalyst according to the invention, and then obtain catalyst according to the invention B16.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in table 4.Adopt XRF to analyze 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 listed at table 4 by the carrier prepared according to embodiment 7 step (1), to obtain the carrier used in catalyst according to the invention, and then obtain catalyst according to the invention B17.Measure the radial crushing strength of the carrier obtained, water absorption rate and δ value, result is listed in table 4.Adopt XRF to analyze 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 analyze catalyst, result is listed in table 5.
Table 4
Table 5
Embodiment 29-36 is for illustration of the catalyst having a hydrogenation catalyst effect according to of the present invention and application thereof and hydrotreating method.
Embodiment 29-36
Adopt the hydrodesulfurization 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 | 91 |
| Embodiment 30 | B12 | 86 |
| Embodiment 31 | B13 | 83 |
| Embodiment 32 | B14 | 85 |
| Embodiment 33 | B15 | 90 |
| Embodiment 34 | B16 | 96 |
| Embodiment 35 | B17 | 93 |
| Embodiment 36 | B18 | 92 |
Shown by the result of table 3 and table 6, catalyst according to the invention demonstrates higher catalytic activity in the hydrotreatment of hydrocarbon ils.
Claims (27)
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, load is on the carrier substantially in a salt form for described group VIII metallic element and described group vib metallic element, it is characterized in that, described carrier is siliceous hydrated alumina forming matter or silicon-containing alumina article shaped, by containing at least one hydrated alumina, the raw material of at least one silicon-containing compound and at least one cellulose ether is made, described raw material is not containing peptizing agent.
2. catalyst according to claim 1, wherein, with the total amount of this catalyst for benchmark, 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, and the content of described carrier is 30-80 % by weight.
3. catalyst according to claim 1, wherein, described carrier prepares formed body by described raw material, and described formed body is carried out drying make; Or
Described carrier prepares formed body by described raw material, and described formed body is successively carried out dry and roasting and make.
4. the catalyst according to claim 1 or 3, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-8 % by weight, with SiO
2the total content of the described silicon-containing compound of meter is 0.5-50 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 47-96 % by weight.
5. catalyst according to claim 4, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 1-6 % by weight, with SiO
2the total content of the described silicon-containing compound of meter is 1-45 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 50-95 % by weight.
6. the catalyst according to claim 1 or 3, wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
7. the catalyst according to claim 1 or 3, wherein, described silicon-containing compound is selected from the compound shown in sodium metasilicate, silica and formula I,
In formula I, R
1, R
2, R
3and R
4be C separately
1-C
5alkyl or hydrogen;
Described hydrated alumina is selected from boehmite, gibbsite, unformed hydrated alumina and boehmite.
8. according to the catalyst in claim 1-3 described in any one, 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 water absorption rate of described carrier is 0.6-1, δ value is less than 5%, Q
1for 15-30N/mm.
10. catalyst according to claim 1 and 2, wherein, described group VIII metallic element is cobalt and/or nickel, and described group vib metallic element is molybdenum and/or tungsten.
11. 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 described group vib metallic element, it is characterized in that, described carrier is siliceous hydrated alumina forming matter or silicon-containing alumina article shaped, be made up of the raw material containing at least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether, described raw material is not containing peptizing agent.
12. method according to claim 11, wherein, by being immersed in supported on carriers at least one group VIII metallic element and at least one group vib metallic element.
13. methods according to claim 11 or 12, wherein, 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, 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, and the content of described carrier is 30-80 % by weight.
14. methods according to claim 11 or 12, wherein, described group VIII metallic element is cobalt and/or nickel, and described group vib metallic element is molybdenum and/or tungsten.
15. methods according to claim 11, wherein, 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
Prepare formed body by described raw material, and described formed body is successively carried out drying and roasting.
16. method according to claim 15, wherein, the mode being prepared formed body by described raw material comprises:
At least one hydrated alumina, at least one silicon-containing compound and at least one cellulose ether are mixed with water, 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, obtains the second mixture, and described second mixture is successively carried out shaping and dehydration, obtain preform, load at least one silicon-containing compound on described preform.
17. methods according to claim 15, wherein, the condition of described roasting comprises: temperature is 450-950 DEG C, and the time is 2-8 hour;
The temperature of described drying is more than 60 DEG C and lower than 350 DEG C.
18. methods according to claim 17, wherein, the temperature of described drying is 80-300 DEG C.
19. according to the method in claim 11,15 and 16 described in any one, and wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 0.5-8 % by weight, with SiO
2the total content of the described silicon-containing compound of meter is 0.5-50 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 47-96 % by weight.
20. methods according to claim 19, wherein, with the total amount of described raw material for benchmark, the total content of described cellulose ether is 1-6 % by weight, with SiO
2the total content of the described silicon-containing compound of meter is 1-45 % by weight, with Al
2o
3the total content of the described hydrated alumina of meter is 50-95 % by weight.
21. according to the method in claim 11,15 and 16 described in any one, and wherein, described cellulose ether is selected from methylcellulose, HEMC and hydroxypropyl methylcellulose.
22. according to the method in claim 11,15 and 16 described in any one, and wherein, described silicon-containing compound is selected from the compound shown in sodium metasilicate, silica and formula I,
In formula I, R
1, R
2, R
3and R
4be C separately
1-C
5alkyl or hydrogen;
Described hydrated alumina is selected from boehmite, gibbsite, unformed hydrated alumina and boehmite.
23. according to the method in claim 11,12 and 15 described in any one, and 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.
24. methods according to claim 23, wherein, the radial crushing strength of described carrier is 15-30N/mm, and water absorption rate is 0.6-1, δ value is less than 5%.
Catalyst prepared by the method in 25. claim 11-24 described in any one.
The application of catalyst in 26. claim 1-10 and 25 described in any one in hydrocarbon oil hydrogenation process.
27. 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 1-10 and 25 described in any one.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101574659A (en) * | 2009-06-15 | 2009-11-11 | 中国科学院山西煤炭化学研究所 | Catalyst for using coal tar to prepare clean fuel oil by catalytic hydrogenation, preparation method and applications |
| CN102259033A (en) * | 2010-05-24 | 2011-11-30 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof as well as hydrogenation catalyst and preparation method thereof |
| CN102319579A (en) * | 2011-07-08 | 2012-01-18 | 中国石油天然气股份有限公司 | Hydrofining catalyst and preparation method thereof |
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| US7390766B1 (en) * | 2003-11-20 | 2008-06-24 | Klein Darryl P | Hydroconversion catalysts and methods of making and using same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101574659A (en) * | 2009-06-15 | 2009-11-11 | 中国科学院山西煤炭化学研究所 | Catalyst for using coal tar to prepare clean fuel oil by catalytic hydrogenation, preparation method and applications |
| CN102259033A (en) * | 2010-05-24 | 2011-11-30 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof as well as hydrogenation catalyst and preparation method thereof |
| CN102319579A (en) * | 2011-07-08 | 2012-01-18 | 中国石油天然气股份有限公司 | Hydrofining catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 朱洪法等.成型助剂的类别.《催化剂制备及应用技术》.中国石化出版社,2011,第248-252页. * |
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