CN103285939B - There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and hydrofinishing process - Google Patents
There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and hydrofinishing process Download PDFInfo
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Abstract
The present invention relates to the catalyst and preparation method and application with hydrogenation catalyst effect, this preparation method is included on shaping porous carrier and introduces group vib metallic element, group VIII metallic element and the metallic element as auxiliary agent, wherein, the method introducing group vib metallic element and group VIII metallic element comprises with porous carrier shaping described in a kind of aqueous impregnation, the described aqueous solution contain at least one containing the compound of group VIII metallic element and at least one containing the compound of group vib metallic element and containing or not containing cosolvent; The mixture obtained by dipping is in closed reactor and pressure is P
0hydrothermal treatment consists is carried out under the condition of+Δ P; Mixture hydrothermal treatment consists obtained carries out Separation of Solid and Liquid, and by dry for the solid phase obtained.The invention still further relates to a kind of hydrofinishing process.Catalyst of the present invention demonstrates higher catalytic activity in the hydrofinishing of hydrocarbon ils.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method with hydrogenation catalyst effect, and the application of this catalyst in hydrocarbon oil hydrogenation is refined; The invention still further relates to a kind of hydrofinishing process using described catalyst.
Background technology
Along with environmental requirement increasingly stringent in world wide, various countries are day by day harsh to the quality requirement of vehicle fuel.In addition, because petroleum resources reduce, oil property becomes and heavily becomes bad, and refinery has to process crude oil more inferior.Therefore, significantly reduce bavin well cuts and polycyclic aromatic hydrocarbon content, significantly improve diesel quality, become the problem that oil refining enterprise is in the urgent need to address.Hydrogen addition technology reduces one of impurity content, the major technique improving oil quality in oil product, and its core is hydrogenation catalyst.
Therefore, develop the catalyst with higher hydrogenation activity and become study hotspot.
CN101298043B discloses a kind of hydrothermal deposition preparation method of support type monometallic Hydrobon catalyst, and the method comprises:
(1) in the autoclave being added with aluminium oxide, a kind of metal salt solution being selected from group vib active metal is added, take inorganic acid as precipitating reagent, take organic acid as dispersant, the temperature controlling hydro-thermal reaction is 100-200 DEG C, time is 6-48 hour, wherein, the mol ratio of dispersant and active metal is 0.5-3: 1, binary or the tricarboxylic acid of described dispersant to be carbon number be 2-12;
(2) suspension carries out filtering, washing after completing by hydro-thermal reaction, and carries out drying and roasting, thus obtains Hydrobon catalyst.
CN101298047A discloses a kind of preparation method of hydrogenation catalyst, and the supported on carriers of this hydrogenation catalyst has group vib metal and group VIII metal active constituent, and this preparation method comprises:
(1) in autoclave, add carrier and the salting liquid containing group vib metal, being precipitating reagent with inorganic acid, take cationic surfactant as dispersant, and the temperature controlling hydro-thermal reaction is 100-200 DEG C, and the time is 12-36 hour;
(2) suspension carries out filtering, washing after completing by hydro-thermal reaction, and carries out drying, roasting, obtains single-metal reforming catalyst;
(3) single-metal reforming catalyst obtained being placed in autoclave, adding the salting liquid of group VIII metal, take urea as precipitating reagent, after reacting 4-12 hour, temperature is increased to 90-137 DEG C, then reacts 4-12 hour at the temperature of 50-90 DEG C;
(4), after product being carried out filter and wash, carry out drying and roasting, obtain the hydrogenation catalyst of bimetallic component.
When disclosed in employing CN101298043B and CN101298047A, hydrothermal deposition method prepares hydrogenation catalyst, because the compound containing group vib metallic element is different from the dissolubility of the compound containing group VIII metallic element, therefore need to carry out twice hydrothermal deposition reaction and could prepare the hydrogenation catalyst with bimetallic component, complex operation, is difficult to the demand meeting large-scale production.
Li Jun really wait (hydrothermal modification is to NiMO/ γ-Al
2o
3the impact of hydrodenitrogenation catalyst structure and performance, Chinese Journal of Inorganic Chemistry, 20 (6): 739-742,2004) disclose a kind of preparation method of hydrogenation catalyst, the method comprises (NH with step impregnation method
4)
6mo
7o
244H
2o and Ni (NO
3)
26H
2o load is at γ-Al
2o
3on, and the product after dipping is carried out at the temperature of 140-180 DEG C the hydrothermal modification of 2 hours.But find in research process, the hydrogenation activity of the catalyst adopting the method to prepare still awaits further raising.
Summary of the invention
The object of the present invention is to provide a kind of preparation method with the catalyst of hydrogenation catalyst effect, the high active of hydrogenation catalysis of the catalyst prepared by the method is high, and the method is easy and simple to handle, the catalyst with group vib metallic element and group VIII metallic element can be prepared by a step dipping.
The present inventor finds in research process, the aqueous impregnation porous carrier of the compound of group VIII metallic element is contained with the compound and at least one that contain group vib metallic element containing at least one, and the mixture after dipping is carried out in the process of hydrothermal treatment consists, improve the pressure of hydrothermal treatment consists, the catalytic activity of the catalyst of final preparation can be significantly improved.This completes the present invention.
A first aspect of the present invention provides a kind of preparation method with the catalyst of hydrogenation catalyst effect, and this preparation method comprises:
Shaping porous carrier is introduced at least one group vib metallic element, at least one group VIII metallic element and at least one metallic element as auxiliary agent;
Wherein, the method shaping porous carrier being introduced at least one group vib metallic element and at least one group VIII metallic element comprises the following steps:
(1) with porous carrier shaping described in a kind of aqueous impregnation, the described aqueous solution contain at least one containing the compound of group VIII metallic element and at least one containing the compound of group vib metallic element and containing or not containing cosolvent;
(2) in closed reactor, carry out hydrothermal treatment consists by flooding the mixture obtained, described hydrothermal treatment consists is P at pressure
0carry out under the condition of+Δ P, wherein, P
0for described shaping porous carrier, the described compound containing group VIII metallic element, the described pressure containing the water in the compound of group vib metallic element, the described cosolvent containing or do not contain and the described aqueous solution and produce in hydrothermal treatment consists, Δ P is 0.05-15MPa; And
(3) mixture hydrothermal treatment consists obtained carries out Separation of Solid and Liquid, and the solid phase obtained is carried out drying.
A second aspect of the present invention provides a kind of catalyst obtained by preparation method of the present invention.
A third aspect of the present invention provides the application of catalyst according to the invention in hydrocarbon oil hydrogenation is refined.
A fourth aspect of the present invention provides a kind of hydrofinishing process, under the method is included in Hydrofinishing conditions, is contacted by hydrocarbon ils with catalyst according to the invention.
Method according to the present invention to when carrying out hydrothermal treatment consists with the mixture obtained after the shaping porous carrier of impregnation fluid, except shaping porous carrier, the compound containing group VIII metallic element, the compound containing group vib metallic element, containing or the described cosolvent that do not contain and the aqueous solution in the pressure P that produces of water
0outward, also apply pressure Δ P in addition, the catalyst prepared thus demonstrates higher catalytic activity in the hydrofinishing of hydrocarbon ils.
Detailed description of the invention
A first aspect of the present invention provides a kind of preparation method with the catalyst of hydrogenation catalyst effect, and this preparation method is included on shaping porous carrier and introduces at least one group vib metallic element, at least one group VIII metallic element and at least one metallic element as auxiliary agent.
In the present invention, term " at least one " represents one or more.
In the catalyst that preparation in accordance with the present invention obtains, described group vib metallic element, group VIII metallic element and the content as the metallic element of auxiliary agent can carry out suitable selection according to the embody rule occasion of described catalyst.Usually, described group vib metallic element, described group VIII metallic element and the introduction volume of described metallic element on described shaping porous carrier as auxiliary agent make, with the total amount of described catalyst for benchmark, with oxide basis, the content of group vib metallic element can be 10-50 % by weight, is preferably 15-45 % by weight; The content of group VIII metallic element can be 1-10 % by weight, is preferably 1-7 % by weight; Content as the described metallic element of auxiliary agent can be 0.5-10 % by weight, is preferably 0.5-5 % by weight; The content of described shaping porous carrier can be 30-88.5 % by weight, is preferably 43-83.5 % by weight.
Preparation in accordance with the present invention, described group vib metallic element and described group VIII metallic element can be that the routine of this area is selected.Usually, described group vib metallic element is preferably molybdenum element and/or W elements, and described group VIII metallic element is preferably cobalt element and/or nickel element.
Preparation in accordance with the present invention, the various metallic elements that can improve the performance of the catalyst with hydrogenation catalyst effect that the described metallic element as auxiliary agent can be commonly used for this area, can select according to the application scenario of catalyst.Preferably, the described metallic element as auxiliary agent can be selected from IIB race metallic element, IA race metallic element, IIA race metallic element and thulium.More preferably, the described metallic element as auxiliary agent is selected from Zn-ef ficiency, sodium element, potassium element, magnesium elements, calcium constituent, lanthanum element and Ce elements.
Preparation in accordance with the present invention, the method that shaping porous carrier is introduced at least one group vib metallic element and at least one group VIII metallic element comprises the following steps:
(1) with porous carrier shaping described in a kind of aqueous impregnation, wherein, the described aqueous solution contain at least one containing the compound of group vib metallic element and at least one containing the compound of group VIII metallic element and containing or not containing cosolvent;
(2) in closed reactor, carry out hydrothermal treatment consists by flooding the mixture obtained, described hydrothermal treatment consists is P at pressure
0carry out under the condition of+Δ P; And
(3) mixture hydrothermal treatment consists obtained carries out Separation of Solid and Liquid, and the solid phase obtained is carried out drying.
Preparation in accordance with the present invention, in step (1) the described aqueous solution, the described concentration containing the compound of group vib metallic element and the compound containing group VIII metallic element, meets concrete instructions for use (such as previously described content requirement) can make the content of group vib metallic element and group VIII metallic element in the catalyst of final preparation and is as the criterion.
According to the present invention, can be dissolved in water containing the compound of group vib metallic element and at least one containing the compound of group VIII metallic element by least one that this area is commonly used, thus prepare the described aqueous solution.
Such as, the water soluble compound containing group vib metallic element that the described compound containing group vib metallic element can be commonly used for this area, the water soluble compound containing group VIII metallic element that the described compound containing group VIII metallic element can be commonly used for this area.
Particularly, the described compound containing group vib metallic element can be selected from ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide and tungsten oxide.
The described compound containing group VIII metallic element can be selected from the nitrate of group VIII metallic element, the chloride of group VIII metallic element, the sulfate of group VIII metallic element, the formates of group VIII metallic element, the acetate of group VIII metallic element, the phosphate of group VIII metallic element, the citrate of group VIII metallic element, the oxalates of group VIII metallic element, the carbonate of group VIII metallic element, the subcarbonate of group VIII metallic element, the hydroxide of group VIII metallic element, the phosphate of group VIII metallic element, the phosphide of group VIII metallic element, the sulfide of group VIII metallic element, the aluminate of group VIII metallic element, the molybdate of group VIII metallic element, the tungstates of group VIII metallic element and the water-soluble oxide of group VIII metallic element.
Preferably, the described compound containing group VIII metallic element is selected from the oxalates of group VIII metallic element, the nitrate of group VIII metallic element, the sulfate of group VIII metallic element, the acetate of group VIII metallic element, the chloride of group VIII metallic element, the carbonate of group VIII metallic element, the subcarbonate of group VIII metallic element, the hydroxide of group VIII metallic element, the phosphate of group VIII metallic element, the molybdate of group VIII metallic element, the tungstates of group VIII metallic element and the water-soluble oxide of group VIII metallic element.
Particularly, the described compound containing group VIII metallic element can be selected from but be not limited to: nickel nitrate, nickelous sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chloride.
Preparation in accordance with the present invention, the various cosolvents that step (1) the described aqueous solution can also be commonly used containing this area, to improve the described compound containing group vib metallic element and the described dissolubility of compound in water containing group VIII metallic element; Or stablize the described aqueous solution, prevent precipitation.The various materials that can realize above-mentioned functions that described cosolvent can be commonly used for this area, are not particularly limited.Such as, described cosolvent can be one or more in phosphoric acid, citric acid and ammoniacal liquor.The present invention is not particularly limited for the concentration of described ammoniacal liquor, can be that the routine of this area is selected.The consumption of described cosolvent can be the routine selection of this area, and usually, in the described aqueous solution, the content of described cosolvent can be 1-10 % by weight.
Preparation in accordance with the present invention, the various methods that this area can be adopted to commonly use introduce the metallic element of at least one as auxiliary agent on described shaping porous carrier.Such as: before the described group vib metallic element of introducing and described group VIII metallic element, the described metallic element as auxiliary agent can be introduced on described shaping porous carrier; Also can introduce on described shaping porous carrier described at least one as group VIII metallic element described in group vib metallic element described in the metallic element of auxiliary agent, at least one and at least one simultaneously; The described metallic element as auxiliary agent can also be introduced in the process of the described shaping porous carrier of preparation.
In the first embodiment of the present invention, described shaping porous carrier is introduced at least one comprise as the mode of the metallic element of auxiliary agent: in step (1), before with porous carrier shaping described in described aqueous impregnation, on described shaping porous carrier, load at least one is as the described metallic element of auxiliary agent.The various methods that this area can be adopted to commonly use using as the described metallic element load of auxiliary agent on described shaping porous carrier.Such as: can by contacting with described shaping porous carrier containing the aqueous solution as the compound of the metallic element of auxiliary agent with containing at least one, and load had the shaping porous carrier of described compound successively to carry out drying and roasting, thus using as the described metallic element load of auxiliary agent on described shaping porous carrier.The method of described contact can be the routine selection of this area, such as: dipping and spraying.
In the second embodiment of the present invention, described shaping porous carrier is introduced at least one comprise as the mode of the metallic element of auxiliary agent: using at least one containing in the aqueous solution be dissolved in as the compound of the described metallic element of auxiliary agent described in step (1) (namely, containing at least one containing the compound of group VIII metallic element and at least one containing the compound of group vib metallic element and containing or not containing cosolvent the described aqueous solution also containing at least one containing the compound as the described metallic element of auxiliary agent), and with this aqueous impregnation porous carrier, thus in described shaping porous carrier, introduce the described metallic element as auxiliary agent simultaneously, described group vib metallic element and described group VIII metallic element.In this embodiment, P
0for described shaping porous carrier, described compound containing group VIII metallic element, described contain group vib metallic element compound, containing or the described cosolvent do not contained, the described pressure containing producing in hydrothermal treatment consists as the water in the compound of the described metallic element of auxiliary agent and the described aqueous solution.
In the third embodiment of the present invention, described shaping porous carrier is introduced at least one comprise as the mode of the metallic element of auxiliary agent: at least one is mixed with the raw material for the preparation of described shaping porous carrier containing the compound as the described metallic element of auxiliary agent, and by shaping for the mixture obtained.
Preparation in accordance with the present invention, above-mentioned three kinds of embodiments can be used alone, also can combinationally use, be not particularly limited, as long as can guarantee that in the final catalyst obtained, the content as the metallic element of auxiliary agent can meet concrete instructions for use (such as previously described content range).From the angle of simple process, preferably adopt the second embodiment on described shaping porous carrier, be introduced as the described metallic element of auxiliary agent according to method of the present invention.
According to the present invention, containing the various water soluble compounds contained as the described metallic element of auxiliary agent that the compound as the described metallic element of auxiliary agent can be commonly used for this area, such as: the water-soluble nitrate that can be selected from IIB race metal, the water-soluble nitrate of IA race metal, the water-soluble nitrate of IIA race metal and the water-soluble nitrate of rare earth metal, the water soluble chloride of IIB race metal, the water soluble chloride of IA race metal, the water soluble chloride of IIA race metal, the water soluble chloride of rare earth metal, the water soluble hydroxide of IIB race metal, the water soluble hydroxide of IA race metal, the water soluble hydroxide of IIA race metal and the water soluble hydroxide of rare earth metal.Particularly, magnesium nitrate, sodium nitrate, zinc nitrate, cerous nitrate, lanthanum nitrate, magnesium chloride, sodium chloride, zinc chloride, cerium chloride and lanthanum chloride can be selected from containing the compound as the described metallic element of auxiliary agent.
Preparation in accordance with the present invention, the various shaping porous carrier that described shaping porous carrier can be commonly used for this area, is not particularly limited.Preferably, described shaping porous carrier is shaping heat-resistant inorganic oxide.In the present invention, term " heat-resistant inorganic oxide " refers in oxygen or oxygen-containing atmosphere, and decomposition temperature is not less than the inorganic oxygen-containing compound of 300 DEG C (such as: decomposition temperature is 300-1000 DEG C).In the present invention, described shaping porous carrier can be formed by a kind of heat-resistant inorganic oxide, also can be formed by two or more heat-resistant inorganic oxide.
According to the present invention, described heat-resistant inorganic oxide can for this area commonly use can as the various heat-resistant inorganic oxides of the carrier of catalyst.Usually, described heat-resistant inorganic oxide can be one or more in aluminium oxide, silica, titanium oxide, magnesia, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia and silica-alumina, zirconia.
Preferably, described heat-resistant inorganic oxide is aluminium oxide.
Preparation in accordance with the present invention, the method that this area can be adopted to commonly use prepares described shaping porous carrier.Such as: the precursor that at least one heat-resistant inorganic oxide and/or at least one can be formed under roasting condition heat-resistant inorganic oxide is shaping, the formed body obtained is carried out roasting and obtains.Described shaping method can be that the routine of this area is selected, such as: the precursor extrusion molding in an extruder that at least one heat-resistant inorganic oxide and/or at least one can be formed under roasting condition heat-resistant inorganic oxide.
In the present invention, the described precursor that can form heat-resistant inorganic oxide under roasting condition can carry out suitable selection according to the kind of the heat-resistant inorganic oxide of expection, is as the criterion can form described heat-resistant inorganic oxide by roasting.
Such as, when described heat-resistant inorganic oxide is aluminium oxide, the various materials that can form aluminium oxide under roasting condition that the described precursor that can form heat-resistant inorganic oxide under roasting condition can be commonly used for this area, such as: hydrated alumina (as boehmite), Alumina gel.
One of the present invention preferred embodiment in, will can form the precursor extrusion molding of aluminium oxide under roasting condition, then the formed body extruded be carried out drying and roasting, thus obtain described porous carrier.
According to the present invention, when adopting the method extruded to come shaping, extrusion aid and/or adhesive can also be added in described heat-resistant inorganic oxide and/or the precursor that can form heat-resistant inorganic oxide under roasting condition.The kind of described extrusion aid and peptizing agent and consumption are conventionally known to one of skill in the art, do not repeat them here.
According to the present invention, the condition of the formed body extruded being carried out roasting can be selected for the routine of this area.Such as, the temperature of described roasting can be 350-650 DEG C, is preferably 400-600 DEG C; The time of described roasting can be 2-6 hour, is preferably 3-5 hour.
According to the present invention, described porous carrier can have various shape according to concrete use occasion, such as: spherical, sheet shape or bar shaped.
Preparation in accordance with the present invention, in step (1), the method for dipping is not particularly limited, and can be that the routine of this area is selected, such as: the saturated infusion process in hole and excessive dipping method (that is, supersaturation infusion process).Preferably, according to method of the present invention, described dipping is excessive dipping.The saturated infusion process in described hole and excessive infusion process are known in the field, repeat no more herein.Preparation in accordance with the present invention, in step (1), number of times for dipping is also not particularly limited, it can be single-steeping, also can for repeatedly to flood, with in the catalyst finally obtained, the content of group VIII metallic element and group vib metallic element can meet instructions for use (such as previously described content range) and be as the criterion.
Preparation in accordance with the present invention, in step (2), described hydrothermal treatment consists is P at pressure
0carry out under the condition of+Δ P.
In the present invention, P
0for described shaping porous carrier, described compound containing group VIII metallic element, described contain group vib metallic element compound, containing or do not contain described cosolvent, containing or do not contain containing the pressure produced in hydrothermal treatment consists as the water in the compound of the described metallic element of auxiliary agent and the described aqueous solution.
According to method of the present invention, in described hydrothermal treatment process, remove P for the pressure carried out in the closed container of hydrothermal treatment consists
0, also comprise Δ P outward, wherein, Δ P is 0.05-15MPa.Preferably, Δ P is 0.1-10MPa.From the angle of pressure in the catalytic activity of the catalyst of the final preparation of balance and described closed container are born, Δ P is more preferably 0.2-7MPa, Δ P more preferably 0.2-5MPa.
In the present invention, pressure is all in gauge pressure.
The various methods that this area can be adopted conventional are to make described hydrothermal treatment consists at pressure for P
0carry out under the condition of+Δ P.
In one embodiment of the invention, described hydrothermal treatment consists is made to be P at pressure
0the mode of carrying out under the condition of+Δ P comprises: under the existence of at least one volatile organic matter, carry out described hydrothermal treatment consists, and the pressure that the addition of described volatile organic matter makes described volatile organic matter produce in hydrothermal treatment consists is Δ P.
Can adopt and make described hydrothermal treatment consists carry out under the existence of described volatile organic matter (that is, carrying out having described volatile organic matter in the closed container of hydrothermal treatment consists) in various manners.Such as, described volatile organic matter can be added in the mixture that the aqueous solution or dipping for flooding described porous carrier obtains, thus described hydrothermal treatment consists is carried out under the existence of volatile organic matter.From the angle of the catalytic activity of the catalyst of raising preparation further, preferably volatile organic matter is added in the mixture flooding and obtain according to method of the present invention, thus described hydrothermal treatment consists is carried out under the existence of volatile organic matter.
In this embodiment, can conventional various volatile organic matters be added in closed container, as long as described volatile organic matter can improve the pressure in the closed container carrying out described hydrothermal treatment consists under hydrothermal conditions, the pressure in described closed container is within scope mentioned above.
In the present invention, described volatile organic matter can become the material of gaseous state by liquid state and/or can produce the material of gas under hydrothermal conditions for various under hydrothermal conditions.Such as, described volatile organic matter can be selected from the polyethylene glycol that alcohol, acid, amine and number-average molecular weight are 200-1500.Preferably, described volatile organic matter is selected from C
1-C
30fatty alcohol, C
2-C
30aliphatic acid, C
2-C
30fatty amine, C
6-C
30alkane and number-average molecular weight be the polyethylene glycol of 200-1500.More preferably, described volatile organic matter is selected from C
1-C
12fatty alcohol, C
2-C
10aliphatic acid, C
2-C
12fatty amine, C
6-C
12alkane and number-average molecular weight be the polyethylene glycol of 200-1500.Further preferably, described volatile organic matter is selected from C
1-C
8fatty alcohol, C
2-C
5aliphatic acid, C
2-C
7fatty amine and C
6-C
11alkane.
Particularly, described volatile organic matter can be selected from but be not limited to: normal propyl alcohol, isopropyl alcohol, ethylene glycol, glycerine, triethylene glycol, number-average molecular weight are the polyethylene glycol of 200-1500, diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-CDTA, tartaric acid, malic acid, ethylenediamine, hexane and isomers, heptane and isomers thereof, octane and isomers thereof and decane and isomers thereof.
According to method of the present invention, the consumption of described volatile organic matter is not particularly limited, and can carry out suitable selection, repeat no more herein according to the kind of the Δ P value of expection and the volatile organic matter used.
In another embodiment of the invention, described hydrothermal treatment consists is made to be P at pressure
0the mode of carrying out under the condition of+Δ P comprises: under the existence of at least one non-active gas, carry out described hydrothermal treatment consists, and the pressure that the addition of described non-active gas makes described non-active gas produce in hydrothermal treatment consists is Δ P.
In the present invention, described non-active gas refers in hydrothermal treatment process can not with porous carrier, containing the compound of group vib metal, compound containing group VIII metal, cosolvent, there is chemically interactive gas, the various non-active gas can commonly used for this area containing as the compound of the described metallic element of auxiliary agent and water.Preferably, described non-active gas is selected from nitrogen, group 0 element gas (such as: argon gas), carbon dioxide, sulfur hexafluoride and C
1-C
5hydrocarbon.Further preferably, described non-active gas is selected from nitrogen and group 0 element gas.
According to this embodiment, can in the process of hydrothermal treatment consists, in the closed container carrying out hydrothermal treatment consists, pass into non-active gas, make the pressure in described closed container be P
0+ Δ P; Also can before carrying out hydrothermal treatment consists, in the closed container carrying out described hydrothermal treatment consists, pass into described non-active gas, then close described container and carry out hydrothermal treatment consists.
According to another embodiment of the present invention, described post processing is made to be P at pressure
0the mode of carrying out under the condition of+Δ P comprises: under the existence of at least one volatile organic matter and at least one non-active gas, carry out described hydrothermal treatment consists, the gross pressure that total addition of described volatile organic matter and non-active gas makes described volatile organic matter and non-active gas produce in hydrothermal treatment consists is Δ P.
In this embodiment, the kind of described volatile organic matter and described non-active gas and using method as mentioned before, do not repeat them here.
According to method of the present invention, although adopt above-mentioned three kinds of modes all can realize the object of the catalytic activity improving the final catalyst obtained, but from improving the activity of catalyst and the angle of ease-to-operate that are obtained by preparation method of the present invention further, preparation in accordance with the present invention is preferably carried out described hydrothermal treatment consists or carry out described hydrothermal treatment consists, to make described hydrothermal treatment consists at pressure for P under the existence of volatile organic matter and non-active gas under the existence of non-active gas
0carry out under the condition of+Δ P.More preferably, described hydrothermal treatment consists is carried out under the existence of non-active gas.
Preparation in accordance with the present invention, the time of described hydrothermal treatment consists and temperature can be that the routine of this area is selected, as long as the pressure of described hydrothermal treatment consists meets previously described requirement.Preferably, the temperature of described hydrothermal treatment consists can be 100-200 DEG C; The time of described hydrothermal treatment consists can be 0.5-36 hour, is preferably 1-24 hour.
Preparation in accordance with the present invention also comprises step (3): mixture hydrothermal treatment consists obtained carries out Separation of Solid and Liquid, and the solid phase obtained is carried out drying.Preparation method of the present invention is not particularly limited for the method for Separation of Solid and Liquid, can be that the routine of this area is selected, such as: can be filtration, standing separation or centrifugation.The present invention is also not particularly limited for the condition of described drying, can be that the routine of this area is selected.Usually, the condition of described drying comprises: temperature can be 100-300 DEG C, is preferably 100-280 DEG C, is more preferably 100-250 DEG C; Time can be 1-12 hour, is preferably 2-8 hour.
Preparation in accordance with the present invention can also comprise solid matter drying obtained and carry out roasting.The condition of described roasting can be the routine selection of this area.Usually, the condition of described roasting comprises: temperature can be 350-550 DEG C, is preferably 400-500 DEG C; Time can be 1-8 hour, is preferably 2-6 hour.
A second aspect of the present invention provides a kind of catalyst obtained by preparation method of the present invention.Catalyst according to the invention, when the hydrofinishing for hydrocarbon ils, has higher catalytic activity.
Thus, a third aspect of the present invention provides the application of a kind of catalyst according to the invention in hydrocarbon oil hydrogenation is refined.
A fourth aspect of the present invention provides a kind of hydrofinishing process, under the method is included in Hydrofinishing conditions, by hydrocarbon ils and catalyst exposure provided by the invention.
Hydrofinishing process according to the present invention is applicable to the subtractive process such as hydrodesulfurization, hydrodenitrogeneration of various hydrocarbon oil crude material.Described hydrocarbon oil crude material can be such as one or more in gasoline, diesel oil, lubricating oil, kerosene and naphtha; Also can be one or more in reduced crude, decompression residuum, pertroleum wax and Fischer-Tropsch synthesis oil.
The present invention be the catalyst of the application of the invention to improve the activity of the catalyst in unifining process, all the other conditions for hydrofinishing process are not particularly limited, can be this area routine select.Usually, described hydrorefined condition comprises: temperature can be 300-400 DEG C; In gauge pressure, pressure can be 1.0-8.0MPa; During the liquid of hydrocarbon ils, volume space velocity can be 0.5-3.0 hour
-1; Hydrogen to oil volume ratio can be 100-700.
According to hydrofinishing process of the present invention, described catalyst preferably adopts the conventional method of this area to carry out presulfurization before use.Usually, the condition of described presulfurization can comprise: in presence of hydrogen, at the temperature of 360-400 DEG C, carries out the presulfurization of 2-4 hour with one or more in sulphur, hydrogen sulfide, carbon disulfide, DMDS or polysulfide.According to hydrofinishing process of the present invention, described presulfurization can be carried out outside hydrogenation reactor, also can be In-situ sulphiding in hydrogenation reactor.
The present invention is described in detail below in conjunction with embodiment.
In following examples and comparative example, adopt the 3271E type Xray fluorescence spectrometer be purchased from Rigaku electric machine industry Co., Ltd., analysiss mensuration is carried out to the content of element each in catalyst.
In following examples and comparative example, gas chromatography is adopted to measure the sulfur content and nitrogen content of carrying out in the raw material of hydrodesulfurization reaction and the product of acquisition.
In following examples and comparative example, adopt relative hydrodesulfurization activity to carry out the hydrodesulfurization activity of evaluate catalysts, computational methods be using hydrodesulfurization reaction as 1.65 order reaction process, be calculated as follows the reaction rate constant k (X) of catalyst X
hDS:
In formula, volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction,
(k (D-3) is designated as with the hydrodesulfurization activity of catalyst D-3
hDS) be benchmark, be calculated as follows the relative hydrodesulfurization activity of catalyst X:
In following examples and comparative example, adopt relative hydrodenitrogenationactivity activity to carry out the hydrodenitrogenationactivity activity of evaluate catalysts, computational methods be using hydrodenitrogeneration reaction as 1 order reaction process, be calculated as follows the reaction rate constant k (X) of catalyst X
hDN:
In formula, volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction,
(k (D-3) is designated as with the hydrodenitrogenationactivity activity of catalyst D-3
hDN) be benchmark, be calculated as follows the relative hydrodenitrogenationactivity activity of catalyst X:
Embodiment 1-7 is for illustration of the Catalysts and its preparation method with hydrogenation catalyst effect of the present invention.
Embodiment 1
(1) by 1000 grams of aluminium hydrate powders (purchased from Chang Ling branch company of China Petrochemical Industry catalyst plant, contents on dry basis is 72 % by weight) be extruded into banded extruder the butterfly bar that circumscribed circle diameter is 1.3 millimeters, by the wet bar extruded in 120 DEG C of dryings 4 hours, then at the roasting temperature 3 hours of 600 DEG C, thus carrier S 1 is obtained.
(2) 50 grams of ammonium molybdates are joined in 120 ml waters, drip under adding thermal agitation concentration be 25 % by weight ammoniacal liquor until ammonium molybdate dissolve, then add 30 grams of cobalt nitrates and 15 grams of zinc nitrates, after stirring and dissolving, add 20 milliliters of ethanol, then add water and be settled to 200 milliliters.Adopt the above-mentioned aqueous impregnation of excessive dipping method 100 grams of carrier S 1, dip time is 0.1 hour.Be placed in autoclave by flooding the mixture obtained, carry out hydrothermal treatment consists, the condition of hydrothermal treatment consists comprises: temperature is 150 DEG C, and the time is 4 hours; Pressure is 0.7MPa, wherein, and P
0=0.5MPa, Δ P=0.2MPa.Mixture hydrothermal treatment consists obtained is cooled to room temperature, after filtration, by the solid that obtains 120 DEG C of dryings 2 hours, then 450 DEG C of roastings 3 hours, obtains catalyst according to the invention B-1.The composition of catalyst B-1 is in table 1.
Embodiment 2
Joining in 120 ml waters by 15 grams of basic cobaltous carbonates, 30 grams of molybdenum trioxides, adding 10 grams of phosphoric acid and 25 grams of magnesium nitrates with stirring, heating stirring and dissolving, adds 15 milliliters of isopropyl alcohols, then adds water and be settled to 200 milliliters.Adopt the above-mentioned aqueous impregnation of the method for excessive dipping 100 grams of carrier S 1, dip time is 0.2 hour.The mixture that dipping obtains is placed in autoclave and carries out hydrothermal treatment consists, the condition of hydrothermal treatment consists comprises: temperature is 200 DEG C; Time is 10 hours; Pressure is 2.1MPa, wherein, and P
0=1.5MPa, Δ P=0.6MPa.Mixture hydrothermal treatment consists obtained is cooled to room temperature, after filtration, by the solid that obtains 120 DEG C of dryings 2 hours, then 250 DEG C dry 3 hours again, thus obtain catalyst according to the invention B-2.The composition of catalyst B-2 is in table 1.
Embodiment 3
Joining in 150 ml waters by 20 grams of basic nickel carbonates, adding 8 grams of phosphoric acid with stirring, heating stirring and dissolving, adds 12 grams of ammonium molybdates, 110 grams of ammonium metatungstates and 9 grams of lanthanum nitrates respectively with stirring, adds water and be settled to 200 milliliters after dissolving.Adopt the above-mentioned aqueous impregnation of the method for excessive dipping 100 grams of carrier S 1, dip time is 0.5 hour.Be placed in autoclave by flooding the mixture obtained, carry out hydrothermal treatment consists, the condition of hydrothermal treatment consists comprises: temperature is 100 DEG C; Time is 24 hours; In autoclave, pass into nitrogen in hydrothermal treatment process makes the pressure in autoclave be 5.2MPa, wherein, and P
0=0.2MPa, Δ P=5.0MPa.Mixture hydrothermal treatment consists obtained is cooled to room temperature, after filtration, by the solid that obtains 120 DEG C of dryings 2 hours, then 200 DEG C dry 3 hours again, obtain catalyst according to the invention B-3, the composition of catalyst B-3 is in table 1.
Embodiment 4
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 3, unlike, in hydrothermal treatment process, the intake of nitrogen makes the pressure in autoclave be 10.2MPa, wherein, and P
0=0.2MPa, Δ P=10.0MPa, obtains catalyst according to the invention B-4, and the composition of catalyst B-4 illustrates in Table 1.
Comparative example 1
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 3, unlike, in autoclave, do not pass into nitrogen in hydrothermal treatment process, pressure in autoclave be 0.2MPa (namely, Δ P=0), obtain catalyst D-1, its composition illustrates in Table 1.
Embodiment 5
30 grams of ammonium molybdates are added in 70 ml waters, drip under adding thermal agitation concentration be 25 % by weight ammoniacal liquor dissolve to ammonium molybdate, then add 20 grams of cobalt nitrates and 15 grams of zinc nitrates, add water after stirring and dissolving and be settled to 85 milliliters.Adopt the above-mentioned aqueous impregnation of saturated infusion process 100 grams of S1 carriers, dip time is 2 hours.The mixture that dipping obtains is placed in autoclave and carries out hydrothermal treatment consists, the condition of hydrothermal treatment consists comprises: temperature is 100 DEG C, and the time is 12 hours, passes into nitrogen and make the pressure in autoclave be 3.2MPa in hydrothermal treatment process in autoclave, wherein, P
0=0.2MPa, Δ P=3.0MPa.Mixture hydrothermal treatment consists obtained is cooled to room temperature, after filtration, by the solid that obtains 120 DEG C of dryings 2 hours, then 200 DEG C dry 3 hours again, obtain catalyst according to the invention B-5, the composition of catalyst B-5 illustrates in Table 1.
Comparative example 2
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 5, unlike, in hydrothermal treatment process, in autoclave, do not pass into nitrogen, the pressure in autoclave is 0.2MPa (that is, Δ P=0), obtain catalyst D-2, the composition of this catalyst illustrates in Table 1.
Embodiment 6
(1) by 1000 grams of aluminium hydrate powders (purchased from Chang Ling branch company of China Petrochemical Industry catalyst plant, contents on dry basis is 72 % by weight) mix with 40 grams of magnesium nitrates, mix rear banded extruder and be extruded into the butterfly bar that circumscribed circle diameter is 1.3 millimeters, by the wet bar extruded in 120 DEG C of dryings 4 hours, then at the roasting temperature 3 hours of 600 DEG C, thus carrier S 2 is obtained.
(2) 50 grams of ammonium molybdates are joined in 120 ml waters, drip under adding thermal agitation concentration be 25 % by weight ammoniacal liquor dissolve to ammonium molybdate, then add 30 grams of cobalt nitrates, after stirring and dissolving, add 20 milliliters of ethanol, then add water and be settled to 200 milliliters.Adopt the above-mentioned aqueous impregnation of excessive dipping method 100 grams of carrier S 2, dip time is 0.1 hour.Be placed in autoclave by flooding the mixture obtained, carry out hydrothermal treatment consists, the condition of hydrothermal treatment consists comprises: temperature is 150 DEG C, time is 4 hours, in autoclave, pass into argon gas in hydrothermal treatment process makes the pressure in autoclave be 2.5MPa, wherein, and P
0=0.5MPa, Δ P=2.0MPa (wherein, the pressure that ethanol produces is 0.2MPa, and the pressure that argon gas produces is 1.8MPa).Mixture hydrothermal treatment consists obtained is cooled to room temperature, after filtration, by the solid that obtains 120 DEG C of dryings 2 hours, then 450 DEG C of roastings 3 hours, obtains catalyst according to the invention B-6.The composition of catalyst B-6 illustrates in Table 1.
Embodiment 7
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, unlike, not that 20 milliliters of ethanol are added in the aqueous solution, but 20 milliliters of ethanol are added in the autoclave having and flood the mixture obtained, thus obtain catalyst according to the invention B-7.The composition of catalyst B-7 illustrates in Table 1.
Comparative example 3
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, unlike, in autoclave, do not add ethanol and zinc nitrate, in hydrothermal treatment process, the pressure in autoclave is 0.5MPa (wherein, Δ P=0), obtain catalyst D-3, its composition illustrates in Table 1.
Table 1
Embodiment 8-14 is for illustration of the application of catalyst according to the invention and hydrofinishing process.
Embodiment 8-14
The catalyst prepared of Evaluation operation example 1-7 respectively on 30 milliliters of diesel hydrotreating units.
Raw materials used as follows:
Raw material: Middle East straight-run diesel oil
S content: 9700wppm
N content: 97wppm
Density (20 DEG C): 0.8321g/cm
3
Refraction index (20 DEG C): 1.4658
Use following process condition:
Volume space velocity during liquid: 2.0h
-1
Hydrogen to oil volume ratio: 300
Pressure: 3.2MPa
Reaction temperature: 330 DEG C
Wherein, the relative hydrodesulfurization activity of catalyst illustrates in table 2 with relative hydrodenitrogenationactivity activity.
Comparative example 4-6
The method identical with embodiment 8-14 is adopted to carry out hydrofinishing, unlike, catalyst is catalyst prepared by comparative example 1-3, and wherein, the relative hydrodesulfurization activity of catalyst illustrates in table 2 with relative hydrodenitrogenationactivity activity.
Table 2
The result display of table 2, prepared according to the methods of the invention catalyst demonstrates higher catalytic activity in the hydrofinishing of hydrocarbon ils.
Claims (22)
1. have a preparation method for the catalyst of hydrogenation catalyst effect, this preparation method comprises:
Shaping porous carrier is introduced at least one group vib metallic element, at least one group VIII metallic element and at least one metallic element as auxiliary agent;
It is characterized in that, the method that shaping porous carrier is introduced at least one group vib metallic element and at least one group VIII metallic element comprises the following steps:
(1) with porous carrier shaping described in a kind of aqueous impregnation, the described aqueous solution by least one containing the compound of group VIII metallic element, at least one containing group vib metallic element compound, containing or do not contain cosolvent, containing or do not contain volatile organic matter, containing or at least one that do not contain form containing as the compound of the described metallic element of auxiliary agent and water;
(2) in closed reactor, carry out hydrothermal treatment consists by flooding the mixture obtained, described hydrothermal treatment consists is P at pressure
0carry out under the condition of+Δ P, wherein, P
0for described shaping porous carrier, described compound containing group VIII metallic element, described contain group vib metallic element compound, containing or do not contain described cosolvent, containing or do not contain containing the pressure produced in hydrothermal treatment consists as the water in the compound of the described metallic element of auxiliary agent and the described aqueous solution, Δ P is 0.05-15MPa; And
(3) mixture hydrothermal treatment consists obtained carries out Separation of Solid and Liquid, and the solid phase obtained is carried out drying;
One of in the following ways described hydrothermal treatment consists is made to be P at pressure
0carry out under the condition of+Δ P:
Under the existence of at least one first volatile organic matter, carry out described hydrothermal treatment consists, the pressure that the addition of described first volatile organic matter makes described first volatile organic matter produce in hydrothermal treatment consists is Δ P, and described first volatile organic matter is selected from C
1-C
12fatty alcohol, C
2-C
12fatty amine, C
6-C
12alkane and number-average molecular weight be the polyethylene glycol of 200-1500;
Under the existence of at least one non-active gas, carry out described hydrothermal treatment consists, the pressure that the addition of described non-active gas makes described non-active gas produce in hydrothermal treatment consists is Δ P;
Under the existence of at least one second volatile organic matter and at least one non-active gas, carry out described hydrothermal treatment consists, the gross pressure that total addition of described second volatile organic matter and non-active gas makes described second volatile organic matter and non-active gas produce in hydrothermal treatment consists is Δ P.
2. preparation method according to claim 1, wherein, described group vib metallic element, described group VIII metallic element and the introduction volume of described metallic element on described shaping porous carrier as auxiliary agent make, with the total amount of catalyst for benchmark, with oxide basis, the content of group vib metallic element is 10-50 % by weight, the content of group VIII metallic element is 1-10 % by weight, content as the described metallic element of auxiliary agent is 0.5-10 % by weight, and the content of described shaping porous carrier is 30-88.5 % by weight.
3. preparation method according to claim 1, wherein, described second volatile organic matter is selected from C
1-C
12fatty alcohol, C
2-C
10aliphatic acid, C
2-C
12fatty amine, C
6-C
12alkane and number-average molecular weight be the polyethylene glycol of 200-1500.
4. preparation method according to claim 3, wherein, described second volatile organic matter is selected from C
1-C
8fatty alcohol, C
2-C
5aliphatic acid, C
2-C
7fatty amine and C
6-C
11alkane.
5. preparation method according to claim 1, wherein, described first volatile organic matter is selected from C
1-C
8fatty alcohol, C
2-C
7fatty amine and C
6-C
11alkane.
6. preparation method according to claim 1, wherein, Δ P is 0.1-10MPa.
7. preparation method according to claim 6, wherein, Δ P is 0.2-7MPa.
8. preparation method according to claim 1, wherein, described shaping porous carrier is introduced at least one and comprises as the mode of the metallic element of auxiliary agent:
In step (1), at least one is dissolved in the described aqueous solution for flooding described shaping porous carrier containing the compound as the described metallic element of auxiliary agent, P
0for described shaping porous carrier, described compound containing group VIII metallic element, described contain group vib metallic element compound, containing or do not contain described cosolvent, containing the pressure produced in hydrothermal treatment consists as the water in the compound of the described metallic element of auxiliary agent and the described aqueous solution;
In step (1), before porous carrier shaping described in described aqueous impregnation, on described shaping porous carrier, load at least one is as the described metallic element of auxiliary agent; And/or
At least one is mixed with the raw material for the preparation of described shaping porous carrier containing the compound as the described metallic element of auxiliary agent, and by shaping for the mixture obtained, contains the described metallic element of at least one as auxiliary agent to make shaping porous carrier.
9. the preparation method according to claim 1 or 8, wherein, described dipping is excessive dipping.
10. according to the preparation method in claim 1,2 and 8 described in any one, wherein, described group vib metallic element is molybdenum element and/or W elements, and described group VIII metallic element is cobalt element and/or nickel element.
11. according to the preparation method in claim 1,2 and 8 described in any one, and wherein, the described metallic element as auxiliary agent is selected from IIB race metallic element, IA race metallic element, IIA race metallic element and thulium.
12. preparation methods according to claim 11, wherein, the described metallic element as auxiliary agent is selected from Zn-ef ficiency, sodium element, potassium element, magnesium elements, calcium constituent, lanthanum element and Ce elements.
13. according to the preparation method in claim 1,2 and 8 described in any one, and wherein, described shaping porous carrier is shaping heat-resistant inorganic oxide.
14. preparation methods according to claim 13, wherein, described heat-resistant inorganic oxide be selected from aluminium oxide, silica, titanium oxide, magnesia, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia and silica-alumina, zirconia one or more.
15. preparation methods according to claim 1, wherein, the temperature of described hydrothermal treatment consists is 100-200 DEG C, and the time of described hydrothermal treatment consists is 0.5-36 hour.
16. preparation methods according to claim 1, wherein, this preparation method also comprises the solid phase of drying is carried out roasting.
17. preparation methods according to claim 16, wherein, the condition of described roasting comprises: temperature is 350-550 DEG C, and the time is 1-8 hour.
18. preparation methods according to claim 1 or 16, wherein, the condition of described drying comprises: temperature is 100-300 DEG C, and the time is 1-12 hour.
19. catalyst obtained according to the preparation method in claim 1-18 described in any one.
20. application of catalyst according to claim 19 in hydrocarbon oil hydrogenation is refined.
21. 1 kinds of hydrofinishing process, under the method is included in Hydrofinishing conditions, by hydrocarbon ils and catalyst exposure according to claim 19.
22. methods according to claim 21, wherein, described Hydrofinishing conditions comprises: temperature is 300-400 DEG C; In gauge pressure, pressure is 1.0-8.0MPa; During the liquid of hydrocarbon ils, volume space velocity is 0.5-3.0 hour
-1; Hydrogen to oil volume ratio is 100-700.
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| CN101530807A (en) * | 2009-04-28 | 2009-09-16 | 中国石油大学(北京) | Preparation method of phosphoric hydrogenation catalyst for realizing deep desulfurization and denitrification |
| CN102309971A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for hydro-treating catalyst |
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| CN101530807A (en) * | 2009-04-28 | 2009-09-16 | 中国石油大学(北京) | Preparation method of phosphoric hydrogenation catalyst for realizing deep desulfurization and denitrification |
| CN102309971A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Preparation method for hydro-treating catalyst |
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