CN103071508B - Catalyst and preparation method and application thereof, and hydrorefining method - Google Patents
Catalyst and preparation method and application thereof, and hydrorefining method Download PDFInfo
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- CN103071508B CN103071508B CN201110328381.2A CN201110328381A CN103071508B CN 103071508 B CN103071508 B CN 103071508B CN 201110328381 A CN201110328381 A CN 201110328381A CN 103071508 B CN103071508 B CN 103071508B
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Abstract
The invention discloses a catalyst and a preparation method and an application thereof. According to the method, a shaped porous carrier is impregnated by using a water solution; the mixture obtained by impregnation is subjected to a hydrothermal treatment in a sealed reactor; and a solid product obtained by the hydrothermal treatment is dried. The water solution comprises at least one compound comprising VIII-family metal, and at least one compound comprising VIB-family metal. The water solution contains or does not contain a cosolvent. A pressure of the hydrothermal treatment is P0+deltaP, wherein P0 is the pressure produced in the hydrothermal treatment of the porous carrier, the compound comprising VIII-family metal, the compound comprising VIB-family metal, the cosolvent or not, and water. DeltaP is 0.05-15MPa. The invention also relates to a hydrorefining method. According to the invention, under a hydrorefining condition, hydrocarbon oil contacts the catalyst provided by the invention. The catalyst provided by the invention shows higher catalytic activity in hydrocarbon oil hydrorefining.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, and the application of this catalyst in hydrofinishing; 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 oil product impurity content, the major technique improving oil quality, 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 metal is different from the dissolubility of the compound containing group VIII metal, 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 catalytic 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, the catalytic activity of the catalyst prepared by the method is high, and the method is easy and simple to handle, the catalyst with group vib metal and group VIII metal 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 metal is contained with the compound and at least one that contain group vib metal 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 of catalyst, the method comprises with the shaping porous carrier of a kind of aqueous impregnation, in closed reactor, hydrothermal treatment consists is carried out by flooding the mixture obtained, and solid product hydrothermal treatment consists obtained carries out drying, described porous carrier is containing silica and aluminium oxide, the described aqueous solution contain at least one containing the compound of group VIII metal and at least one containing the compound of group vib metal and containing or the cosolvent that do not contain, described hydrothermal treatment consists is P at pressure
0carry out under the condition of+Δ P, wherein, P
0for described porous carrier, described compound containing group VIII metal, described contain group vib metal compound, containing or the described cosolvent that do not contain and the described aqueous solution in the pressure that produces in hydrothermal treatment consists of water, Δ P is 0.05-15MPa.
A second aspect of the present invention provides a kind of catalyst prepared by 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 impregnation fluid porous carrier, except described porous carrier, described compound containing group VIII metal, described contain group vib metal compound, containing or the described cosolvent that do not contain and the described aqueous solution in the pressure P that produces of water
0outward, also apply pressure Δ P in addition, the catalyst prepared thus is when the hydrofinishing for hydrocarbon ils, and catalytic activity is significantly improved.
Detailed description of the invention
The invention provides a kind of preparation method of catalyst, the method comprises with the shaping porous carrier of a kind of aqueous impregnation, in closed reactor, hydrothermal treatment consists is carried out by flooding the mixture obtained, and solid product hydrothermal treatment consists obtained carries out drying, described porous carrier containing silica and aluminium oxide, the described aqueous solution contain at least one containing the compound of group VIII metal and at least one containing the compound of group vib metal and containing or not containing cosolvent.
Method according to the present invention comprises and uses a kind of aqueous solution to carry out the porous carrier of dip forming, the described aqueous solution contain at least one containing the compound of group vib metal and at least one containing the compound of group VIII metal and containing or not containing cosolvent.
According to method of the present invention, in the described aqueous solution, the described concentration containing the compound of group vib metal and the compound containing group VIII metal, can meet concrete instructions for use can make the content of group vib metal and group VIII metal in the catalyst of final preparation and be as the criterion.Usually, when prepared according to the methods of the invention catalyst is used for the hydrofinishing of hydrocarbon ils, contain the total amount of the compound of group vib metal in the described aqueous solution and make containing the total amount of the compound of group VIII metal in the catalyst of preparation, with oxide basis, the content of group vib metal is 10-50 % by weight, is preferably 10-45 % by weight; The content of group VIII metal is 1-10 % by weight, is preferably 1-7 % by weight; The content of porous carrier is 40-89 % by weight, is preferably 48-89 % by weight.
According to method of the present invention, described group vib metal and described group VIII metal can be that the routine of this area is selected.When prepared according to the methods of the invention catalyst is used for the hydrofinishing of hydrocarbon ils, described group vib metal is preferably molybdenum and/or tungsten, and described group VIII metal is preferably cobalt and/or nickel.
According to the present invention, and can be dissolved in water containing the compound of group VIII metal by the compound containing group vib metal that this area is commonly used, thus prepare the described aqueous solution.
The water soluble compound containing group vib metal that the described compound containing group vib metal can be commonly used for this area, the water soluble compound containing group VIII metal that the described compound containing group VIII metal can be commonly used for this area.
Particularly, the described compound containing group vib metal can be one or more in ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide and tungsten oxide.
The described compound containing group VIII metal can be the nitrate of group VIII metal, the chloride of group VIII metal, the sulfate of group VIII metal, the formates of group VIII metal, the acetate of group VIII metal, the phosphate of group VIII metal, the citrate of group VIII metal, the oxalates of group VIII, the carbonate of group VIII metal, the subcarbonate of group VIII metal, the hydroxide of group VIII metal, the phosphate of group VIII metal, the phosphide of group VIII metal, the sulfide of group VIII metal, the aluminate of group VIII metal, the molybdate of group VIII metal, one or more in the tungstates of group VIII metal and the water-soluble oxide of group VIII metal, be preferably in the water-soluble oxide of the oxalates of group VIII metal, the nitrate of group VIII metal, the sulfate of group VIII metal, the acetate of group VIII metal, the chloride of group VIII metal, the carbonate of group VIII metal, the subcarbonate of group VIII metal, the hydroxide of group VIII metal, the phosphate of group VIII metal, the molybdate of group VIII metal, the tungstates of group VIII metal and group VIII metal one or more.
Particularly, the described compound containing group VIII metal can for but be not limited to: one or more in nickel nitrate, nickelous sulfate, nickel acetate, basic nickel carbonate, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chloride.
According to method of the present invention, the various cosolvents that the described aqueous solution can also be commonly used containing this area, to improve the described compound containing group vib metal and the described dissolubility of compound in water containing group VIII metal; 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 kind of multiple 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.
According to method of the present invention, described porous carrier is containing silica and aluminium oxide.In the present invention, in described porous carrier, the content of silica and aluminium oxide can carry out suitable selection according to the application scenario of the catalyst of final preparation.When prepared according to the methods of the invention catalyst is used for the hydrofinishing of hydrocarbon ils, with the total amount of described porous carrier for benchmark, the content of described silica can be 2-45 % by weight, is preferably 5-40 % by weight, more preferably 5-30 % by weight; The content of described aluminium oxide can be 55-98 % by weight, is preferably 60-95 % by weight, more preferably 70-95 % by weight.
According to method of the present invention, described porous carrier is shaping porous carrier, the method preparation that this area can be adopted conventional, such as: the precursor of aluminium oxide and/or aluminium oxide can be mixed with the precursor of silica and/or silica, by shaping for the mixture obtained, the formed body obtained carried out roasting and obtains.The various methods that this area can be adopted conventional by shaping for described mixture, such as: the precursor of institute's aluminium oxide and/or aluminium oxide can be mixed with the precursor of silica and/or silica, by the mixture extrusion molding in an extruder obtained.
According to the present invention, the various materials that can form aluminium oxide under roasting condition that the precursor of described aluminium oxide can be commonly used for this area, such as: hydrated alumina (as boehmite), Alumina gel.The various materials that can form silica under roasting condition that the precursor of described silica can be commonly used for this area, such as: water-soluble silicon-containing compound; And the silicon-containing compound forming Silica hydrogel or Ludox can be hydrolyzed in aqueous medium.The instantiation of the precursor of described silica can be: waterglass, Ludox and esters of silicon acis.
According to method of the present invention, described porous carrier can also contain the auxiliary agent that can improve the performance of the catalyst of final preparation further of effective dose, as P elements.The conventional various methods in this area can be adopted in described porous carrier to introduce described auxiliary agent, repeat no more herein.
According to the present invention, when adopting the method extruded to come shaping, described mixture can also contain extrusion aid and/or adhesive.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, are not repeated herein.
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.
Method according to the present invention is not particularly limited for the method for dipping, 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).According to method of the present invention, described dipping is preferably excessive dipping.The saturated infusion process in described hole and excessive infusion process are known in the field, repeat no more herein.
Also comprise according to method of the present invention and 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.
In the present invention, P
0for described porous carrier, the described compound containing group VIII metal, the described pressure containing the generation of water in hydrothermal treatment consists in the compound of group vib metal, the described cosolvent containing or do not contain and the described aqueous solution.
According to method of the present invention, in described hydrothermal treatment process, for carry out pressure in the closed container of hydrothermal treatment consists except described porous carrier, the described compound containing group VIII metal, described contain group vib metal compound, containing or the described cosolvent that do not contain and the described aqueous solution in except the pressure that produces of water, also comprising 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 (such as: 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 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 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 decompose the material producing gas under hydrothermal conditions for various under hydrothermal conditions.Such as, described volatile organic matter can be one or more organic matters in the polyethylene glycol of 200-1500 for being selected from alcohol, acid, amine and number-average molecular weight.Preferably, described volatile organic matter is for being 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 one or more in the polyethylene glycol of 200-1500.More preferably, described volatile organic matter is for being 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 one or more in 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 in one or more.
Particularly, described volatile organic matter can be one or more in the polyethylene glycol being selected from normal propyl alcohol, isopropyl alcohol, ethylene glycol, glycerine, triethylene glycol, number-average molecular weight are 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 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, there is chemically interactive gas containing the compound of group vib metal, compound, cosolvent and the water containing group VIII metal, can be the conventional various non-active gas in this area.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.
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 volatile organic matter and 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 of the catalyst improving final preparation, but from improving the activity of catalyst and the angle of ease-to-operate prepared by method of the present invention further, under the existence of non-active gas, preferably carry out described hydrothermal treatment consists according to method of the present invention 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
0carry out under the condition of+Δ P.More preferably, described hydrothermal treatment consists is carried out under the existence of non-active gas.
According to method of 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.
Also comprise after mixture hydrothermal treatment consists obtained filters according to method of the present invention and carry out drying.The present invention is 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.
Can also comprise according to method of the present invention 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 prepared by method of the present invention.Catalyst according to the invention demonstrates higher catalytic activity when the hydrofinishing for hydrocarbon ils.
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 gasoline, diesel oil, lubricating oil, kerosene and naphtha; Also can be 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 liquid, 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 sulfuration before use.Usually, the condition of described sulfuration 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 reactor, also can be In-situ sulphiding in 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.
Embodiment 1-9 is for illustration of catalyst according to the invention and preparation method thereof.
Embodiment 1
2000 grams of aluminium hydrate powders (dry glue powder that Chang Ling refinery company catalyst plant is produced, butt 71 % by weight) and 1039 grams of Ludox (Haiyang Chemical Plant, Qingdao's product, dioxide-containing silica is 30 % by weight) are mixed.The mixture banded extruder obtained is extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, and by the wet bar extruded 120 DEG C of dryings 4 hours, then 600 DEG C of roastings 3 hours, obtained carrier S 1, in carrier S 1, silica content is 18.0 % by weight, and alumina content is 82.0 % by weight.
50 grams of ammonium molybdates (be purchased and tie up Science and Technology Ltd. from Beijing Kang Puhui) are joined in 120 ml waters, drip under adding thermal agitation concentration be 25 % by weight ammoniacal liquor dissolve to ammonium molybdate, then 30 grams of cobalt nitrates (being purchased from Beijing Yili Fine Chemicals Co., Ltd.) are added, after stirring and dissolving, add 20 milliliters of ethanol, then add water and be settled to 200 milliliters.The aqueous solution adopting excessive infusion process to prepare 100 grams of carrier S 1 0.1 hours.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, and pressure is 0.7MPa, wherein, and P
0=0.5MPa, Δ P=0.2MPa.Mixture hydrothermal treatment consists obtained is cooled to room temperature and filters, and the solid obtained, 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 illustrates in Table 1.
Embodiment 2
Joining in 120 ml waters by 15 grams of basic cobaltous carbonates and 30 grams of molybdenum trioxides, adding 10 grams of phosphoric acid (85 % by weight) with stirring, heating stirring and dissolving, then adds water and is settled to 200 milliliters.Adopt the above-mentioned aqueous impregnation of excessive infusion process 100 grams of carrier S 1 0.2 hours.Be placed in autoclave by flooding the mixture obtained, and in autoclave, add 15 milliliters of isopropyl alcohols, carry out hydrothermal treatment consists, the condition of hydrothermal treatment consists comprises: temperature is 200 DEG C, and the time is 10 hours, and 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, obtain catalyst according to the invention B-2.The composition of catalyst B-2 illustrates in Table 1.
Embodiment 3
20 grams of basic nickel carbonates being joined in 150 ml waters, adding 8 grams of phosphoric acid with stirring, heating stirring and dissolving; Then add 12 grams of ammonium molybdates and 110 grams of ammonium metatungstates respectively with stirring, add water after dissolving and be settled to 200 milliliters.Adopt the above-mentioned aqueous impregnation of excessive infusion process 100 grams of carrier S 1 0.1 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 24 hours, in hydrothermal treatment process, in autoclave, pass into nitrogen 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 in Table 1 shown in.
Embodiment 4
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 3, unlike, the intake of nitrogen makes the pressure in autoclave be 10.2MPa, wherein, and Δ P=10.0MPa, thus obtain catalyst according to the invention B-4, its composition illustrates in Table 1.
Comparative example 1
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 3, unlike, in hydrothermal treatment process, do not pass into nitrogen in autoclave, the pressure of hydrothermal treatment consists is 0.2MPa (that is, Δ P=0), obtains catalyst D-1, and its composition illustrates in Table 1.
Embodiment 5
30 grams of ammonium molybdates are joined 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, 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 carrier S 12 hours.The mixture obtained is placed in autoclave, carries out hydrothermal treatment consists, the condition of hydrothermal treatment consists comprises: temperature is 100 DEG C, time is 12 hours, in hydrothermal treatment process, passes into nitrogen and make the pressure in autoclave be 3.2MPa 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 450 DEG C of roastings 3 hours.Obtain catalyst according to the invention B-5, its composition is in table 1.
Comparative example 2
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 5, unlike, in the process of hydrothermal treatment consists, do not pass into nitrogen in autoclave, the pressure of hydrothermal treatment consists is 0.2MPa (that is, Δ P=0).Obtain catalyst D-2, its composition illustrates in Table 1.
Embodiment 6
2000 grams of aluminium hydrate powders (dry glue powder that Chang Ling refinery company catalyst plant is produced, butt 71 % by weight) and 250 grams of Ludox (Haiyang Chemical Plant, Qingdao's product, dioxide-containing silica is 30 % by weight) are mixed.The mixture banded extruder obtained is extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, and by the wet bar extruded 120 DEG C of dryings 4 hours, then 600 DEG C of roastings 3 hours, obtained carrier S 2, in carrier S 2, silica content is 5.0 % by weight, and alumina content is 95.0 % by weight.
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 6, unlike, do not pass into argon gas in hydrothermal treatment process, the pressure of hydrothermal treatment consists is 0.7MPa, wherein, and P
0=0.5MPa, Δ P=0.2MPa, obtains catalyst according to the invention B-7, and its composition illustrates in Table 1.
Embodiment 8
1000 grams of aluminium hydrate powders (dry glue powder that Chang Ling refinery company catalyst plant is produced, butt 71 % by weight) and 1014 grams of Ludox (Haiyang Chemical Plant, Qingdao's product, dioxide-containing silica is 30 % by weight) are mixed.The mixture banded extruder obtained is extruded into the butterfly bar that circumscribed circle diameter is 1.4 millimeters, and the wet bar extruded was 120 DEG C of dryings 4 hours, then 600 DEG C of roastings 3 hours, obtained carrier S 3, in carrier S 3, silica content is 30.0 % by weight, and alumina content is 70.0 % by weight.
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 respectively with stirring, after dissolving, 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 3, dip time is 0.5 hour.Autoclave is placed in by flooding the mixture obtained, and add 15 milliliters of isopropyl alcohols, 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 argon gas in hydrothermal treatment process makes the pressure in autoclave be 3.3MPa, wherein, and P
0=0.3MPa, 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, and 200 DEG C dry 3 hours again, obtain catalyst according to the invention B-8, the composition of catalyst B-8 illustrates in Table 1.
Embodiment 9
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, unlike, the consumption of ethanol is 10mL, makes the pressure in autoclave be 0.6MPa, wherein, and P
0=0.5MPa, Δ P=0.1MPa, obtains catalyst according to the invention B-9, and its composition 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, in hydrothermal treatment process, the pressure in autoclave is 0.5MPa (that is, Δ P=0), obtain catalyst D-3, its composition illustrates in Table 1.
Table 1
| Embodiment is numbered | Catalyst is numbered | WO 3(% by weight) | MoO 3(% by weight) | NiO (% by weight) | CoO (% by weight) |
| Embodiment 1 | B-1 | - | 18.3 | - | 4.1 |
| Embodiment 2 | B-2 | - | 18.7 | - | 4.3 |
| Embodiment 3 | B-3 | 30.5 | 3.2 | 4.2 | - |
| Comparative example 1 | D-1 | 30.1 | 3.0 | 4.0 | - |
| Embodiment 4 | B-4 | 30.6 | 3.2 | 4.3 | - |
| Embodiment 5 | B-5 | - | 18.0 | - | 4.0 |
| Comparative example 2 | D-2 | - | 18.0 | - | 4.0 |
| Embodiment 6 | B-6 | - | 18.4 | - | 4.2 |
| Embodiment 7 | B-7 | - | 18.3 | - | 4.1 |
| Embodiment 8 | B-8 | 30.4 | 3.1 | 4.2 | - |
| Embodiment 9 | B-9 | - | 18.3 | - | 4.1 |
| Comparative example 3 | D-3 | - | 18.2 | - | 4.1 |
Embodiment 10-18 is for illustration of the application of catalyst according to the invention and hydrofinishing process.
Embodiment 10-18
The catalyst that on 30 milliliters of diesel hydrotreating units prepared by Evaluation operation example 1-9.
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
Hydrogen dividing potential drop: 3.2MPa
Reaction temperature: 330 DEG C
Hydrodesulfurization activity is by 1.65 order reaction process, and hydrodenitrogenationactivity activity is by 1 order reaction process, and computing formula is as follows:
Result illustrates in table 2.
Comparative example 4-6
The activity of the catalyst adopting the method evaluation comparative example 1-3 identical with embodiment 10-18 to prepare, result illustrates in table 2.
Table 2
The result display of table 2, prepared according to the methods of the invention catalyst, when the hydrofinishing for hydrocarbon ils, demonstrates higher catalytic activity.
Claims (18)
1. the preparation method of a catalyst, the method comprises with the shaping porous carrier of a kind of aqueous impregnation, in closed reactor, hydrothermal treatment consists is carried out by flooding the mixture obtained, and solid product hydrothermal treatment consists obtained carries out drying, described porous carrier is containing silica and aluminium oxide, the described aqueous solution by least one containing the compound of group VIII metal, at least one containing group vib metal compound, containing or do not contain cosolvent, containing or the volatile organic matter that do not contain and water form, it is characterized in that, described hydrothermal treatment consists is P at pressure
0carry out under the condition of+Δ P, wherein, P
0for described porous carrier, described compound containing group VIII metal, described contain group vib metal compound, containing or the described cosolvent that do not contain and the described aqueous solution in the pressure that produces in hydrothermal treatment consists of water, Δ P is 0.05-15MPa,
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 the 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 for being selected from C
1-C
12fatty alcohol, C
2-C
12fatty amine, C
6-C
12alkane and number-average molecular weight be one or more in the polyethylene glycol of 200-1500;
Under the existence of 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 the second volatile organic matter and 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. method according to claim 1, wherein, Δ P is 0.1-10MPa.
3. method according to claim 2, wherein, Δ P is 0.2-7MPa.
4. method according to claim 1, wherein, described second volatile organic matter is for being 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 one or more in the polyethylene glycol of 200-1500.
5. method according to claim 4, wherein, described second volatile organic matter is for being selected from C
1-C
8fatty alcohol, C
2-C
5aliphatic acid, C
2-C
7fatty amine and C
6-C
11alkane in one or more.
6. method according to claim 1, wherein, described first volatile organic matter is for being selected from C
1-C
8fatty alcohol, C
2-C
7fatty amine and C
6-C
11alkane in one or more.
7. method according to claim 1, wherein, described dipping is excessive dipping.
8. method according to claim 1, wherein, contain the total amount of the compound of group vib metal in the described aqueous solution and make containing the total amount of the compound of group VIII metal in the catalyst of preparation, with oxide basis, the content of group vib metal is 10-50 % by weight, the content of group VIII metal is 1-10 % by weight, and the content of porous carrier is 40-89 % by weight.
9. the method according to claim 1 or 8, wherein, described group vib metal is molybdenum and/or tungsten, and described group VIII metal is cobalt and/or nickel.
10. method according to claim 1, wherein, with the total amount of described porous carrier for benchmark, the content of described silica is 2-45 weight, and the content of described aluminium oxide is 55-98 % by weight.
11. 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.
12. methods according to claim 1, wherein, the method also comprises solid matter drying obtained and carries out roasting.
13. methods according to claim 12, wherein, the condition of described roasting comprises: temperature is 350-550 DEG C, and the time is 1-8 hour.
14. methods according to claim 1 or 12, wherein, the condition of described drying comprises: temperature is 100-300 DEG C, and the time is 1-12 hour.
15. catalyst prepared according to the method in claim 1-14 described in any one.
16. application of catalyst according to claim 15 in hydrocarbon oil hydrogenation is refined.
17. 1 kinds of hydrofinishing process, under the method is included in Hydrofinishing conditions, by hydrocarbon ils and catalyst exposure according to claim 15.
18. methods according to claim 17, wherein, described Hydrofinishing conditions comprises: temperature is 300-400 DEG C; In gauge pressure, pressure is 1.0-8.0MPa; During liquid, volume space velocity is 0.5-3.0 hour
-1; Hydrogen to oil volume ratio is 100-700.
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| CN104560156B (en) * | 2013-10-29 | 2016-10-05 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking |
| CN104560160A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical materials |
| CN105080556B (en) * | 2014-05-14 | 2018-02-13 | 中国石油化工股份有限公司 | Hydrobon catalyst and catalytic cracking light cycle oil process for purification |
| CN105080557B (en) * | 2014-05-14 | 2018-09-14 | 中国石油化工股份有限公司 | Catalytic cracking light cycle oil Hydrobon catalyst |
| CN105727974B (en) * | 2014-12-06 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of method for preparing catalyst for synthesis gas methanation |
| CN105727973B (en) * | 2014-12-06 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of preparation method of synthesis gas preparing natural gas by methanation catalyst |
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