CN103623857B - There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and method for hydrogen cracking - Google Patents
There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and method for hydrogen cracking Download PDFInfo
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- CN103623857B CN103623857B CN201210313775.5A CN201210313775A CN103623857B CN 103623857 B CN103623857 B CN 103623857B CN 201210313775 A CN201210313775 A CN 201210313775A CN 103623857 B CN103623857 B CN 103623857B
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Abstract
The invention provides a kind of catalyst and the preparation method and application with hydrogenation catalyst effect, described preparation method comprises: with 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 the porous carrier that the aqueous impregnation of cosolvent is shaping; To the mixture that obtains be flooded in closed reactor at P
0hydrothermal treatment consists is carried out, P under the pressure of+Δ P
0for the pressure that the water in shaping porous carrier, the compound containing group VIII metallic element, the compound containing group vib metallic element, the cosolvent containing or do not contain and the aqueous solution produces in hydrothermal treatment consists, Δ P is 0.05-15MPa; And mixture hydrothermal treatment consists to be obtained carries out Separation of Solid and Liquid, and the solid phase obtained is carried out drying.Present invention also offers a kind of method for hydrogen cracking.Catalyst of the present invention demonstrates higher catalytic activity in the hydrocracking of hydrocarbon ils.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method and the application with hydrogenation catalyst effect, the invention still further relates to a kind of method for hydrogen cracking.
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 high active of hydrogenation catalysis 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 high active of hydrogenation catalysis 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 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 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 element as auxiliary agent, and described shaping porous carrier is containing silica, aluminium oxide and at least one large pore molecular sieve;
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 prepared by method of the present invention.
A third aspect of the present invention provides the application of a kind of catalyst of the present invention in hydrocarbon oil hydrogenation cracking.
A fourth aspect of the present invention provides a kind of method for hydrogen cracking, under the method is included in hydrocracking condition, by hydrocarbon ils and catalyst exposure of the present 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 is when the hydrocracking for hydrocarbon ils, and catalytic activity is significantly improved.
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 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 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 element on described shaping porous carrier as auxiliary agent make, with the total amount of described catalyst for benchmark, the content of described shaping porous carrier can be 30-88.5 % by weight, be preferably 43-88.5 % by weight, be more preferably 52-85 % by weight; With oxide basis, the content of group vib metallic element can be 10-50 % by weight, is preferably 10-45 % by weight, is more preferably 12-40 % by weight; With oxide basis, the content of group VIII metallic element can be 1-10 % by weight, is preferably 1-7 % by weight, is more preferably 2-5 % by weight; In element, the content as the element of auxiliary agent can be 0.5-10 % by weight, is preferably 0.5-5 % by weight, is more preferably 1-3 % 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 elements that can improve the performance of the catalyst with hydrogenation catalyst effect that the element as auxiliary agent can be commonly used for this area, can be selected from metallic element and nonmetalloid.Particularly, the metallic element as auxiliary agent can be selected from IIB race metallic element, IA race metallic element, IIA race metallic element and thulium; Be preferably selected from Zn-ef ficiency, sodium element, potassium element, magnesium elements, calcium constituent, lanthanum element and Ce elements; More preferably Zn-ef ficiency, magnesium elements and lanthanum element is selected from.Nonmetalloid as auxiliary agent can be selected from phosphorus, boron and fluorine; Be preferably selected from boron and fluorine.
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.
The described compound containing group vib metallic element can be selected from the water soluble compound containing group vib metallic element commonly used this area and the compound containing group vib metallic element that can form water soluble compound under the existence of cosolvent in water.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 water soluble compound containing group VIII metallic element commonly used this area and the compound containing group VIII metallic element that can form water soluble compound under the existence of cosolvent in water.Particularly, the described compound containing group VIII metallic element can be selected from 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 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 phosphide of group VIII metal, the sulfide of group VIII metal, the aluminate of group VIII metal, the molybdate of group VIII metal, the tungstates of group VIII metal and the water-soluble oxide of group VIII metal.
Preferably, the described compound containing group VIII metallic element is selected from 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.
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 the aqueous solution described in step (1) 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 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 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 element of auxiliary agent, at least one and at least one simultaneously; The described 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 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 element of auxiliary agent.The various methods that this area can be adopted to commonly use using as the 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 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 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 element of auxiliary agent: using at least one containing in the aqueous solution be dissolved in as the compound of the 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 element of auxiliary agent), and with this aqueous impregnation porous carrier, thus in described shaping porous carrier, introduce the described 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 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 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 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 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 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 element of auxiliary agent that the compound as the 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 containing the compound as the element of auxiliary agent, the water-soluble nitrate of IA race metal, the water-soluble nitrate of IIA race metal, 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, the water soluble hydroxide of rare earth metal, hydrofluoric acid, hydrofluoride, fluosilicic acid, fluosilicate, ammonium fluoride, boric acid, ammonium borate, ammonium metaborate, and tetraboric acid ammonium.Preferably, magnesium nitrate, sodium nitrate, zinc nitrate, cerous nitrate, lanthanum nitrate, magnesium chloride, sodium chloride, zinc chloride, cerium chloride, lanthanum chloride, ammonium fluoride, ammonium fluosilicate, boric acid and tetraboric acid ammonium is selected from containing the compound as the element of auxiliary agent.
According to method of the present invention, described shaping porous carrier is containing silica, aluminium oxide and large pore molecular sieve.In the present invention, in described shaping porous carrier, the content of silica, aluminium oxide and large pore molecular sieve 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 hydrocracking of hydrocarbon ils, with the total amount of described shaping porous carrier for benchmark, the content of described silica can be 2-45 % by weight, is preferably 5-40 % by weight, is more preferably 10-30 % by weight; The content of described large pore molecular sieve can be 2-75 % by weight, is preferably 5-60 % by weight, is more preferably 5-20 % by weight; The content of described aluminium oxide can be 23-96 % by weight, is preferably 35-90 % by weight, is more preferably 50-85 % by weight.
In the present invention, described large pore molecular sieve refers to the zeolite molecular sieve with twelve-ring pore structure.Such as, described large pore molecular sieve can for have faujasite structure zeolite molecular sieve, there is the zeolite structured zeolite molecular sieve of Beta and have in the zeolite molecular sieve of mordenite structure one or more.
Preferably, described large pore molecular sieve is y-type zeolite.
More preferably, described large pore molecular sieve be HY zeolite, rare-earth type Y zeolite (namely, REY zeolite), rare-earth type HY zeolite (namely, REHY zeolite), overstable gamma zeolite (namely, USY zeolite), one or more in rare-earth type overstable gamma zeolite (that is, REUSY zeolite), phosphorous y-type zeolite, phosphorous overstable gamma zeolite, phosphorous HY type zeolite and dealuminium Y type beta stone.
Further preferably, described large pore molecular sieve has B acid and L acid, and the mol ratio of described B acid and described L acid is for being greater than 0.9, and described zeolite molecular sieve is at 3685-3760cm
-1occur that at least one corresponds to the characteristic peak of silicone hydroxyl.
Still more preferably, described B acid is 1-10 with the mol ratio of described L acid, and described large pore molecular sieve is at 3685-3760cm
-1there are two characteristic peaks corresponding to silicone hydroxyl.
The method that this area can be adopted to commonly use is to measure B acid and the L acid of described large pore molecular sieve, and such as can adopt infra-red sepectrometry to measure, concrete method of testing is: be pressed into about 10mg/cm by after large pore molecular sieve porphyrize
2from blade, be placed in the original position pond of infrared spectrometer, in 350 DEG C, 10
-3the vacuum lower surface purified treatment of Pa 2 hours, then cools the temperature to room temperature, introduces pyridine saturated vapor, and after adsorption equilibrium 15 minutes, at 200 DEG C, vacuumize desorption 30 minutes, then cool the temperature to room temperature, carry out infrared scan, sweep limits is 1400cm
-1-1700cm
-1, by 1540cm
-1± 5cm
-1the amount that the absorbance of infrared absorption peak at place and the ratio of the weight of sample strip and area are defined as B acid (is expressed as: A
b(cm
2g)
-1); By 1450cm
-1± 5cm
-1the amount that the absorbance of infrared absorption peak at place and the ratio of the weight of sample strip and area are defined as L acid (is expressed as: A
l(cm
2g)
-1), by A
b/ A
lvalue be defined as large pore molecular sieve B acid and the ratio of L acid.
According to the present invention, the method that this area can be adopted to commonly use to measure the silicone hydroxyl of large pore molecular sieve, such as: infra-red sepectrometry.Particularly, the method adopting infra-red sepectrometry to measure the silicone hydroxyl of large pore molecular sieve can be: be pressed into about 10mg/cm by after zeolite molecular sieve sample porphyrize
2from blade, be placed in the original position pond of infrared spectrometer, at 350 DEG C, 10
-3the vacuum lower surface purified treatment of Pa 2 hours, cools the temperature to room temperature and carries out infrared scan, and sweep limits is 3400cm
-1-4000cm
-1.
According to method of the present invention, the method preparation that described shaping porous carrier can adopt this area conventional, such as: the precursor of the precursor of aluminium oxide and/or aluminium oxide, silica and/or silica can be mixed with large pore molecular sieve, 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 its precursor, silica and/or silica can be mixed with large pore molecular sieve, 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 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 and adhesive 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 described formed body 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 shaping porous carrier can have various shape according to concrete use occasion, such as: spherical, sheet shape, bar shaped or cloverleaf pattern.
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 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.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 preferably 0.1-10MPa, is more preferably 0.2-8MPa, 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: ethanol, 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 metallic element, compound containing group VIII metallic element, cosolvent, there is chemically interactive gas, the various non-active gas can commonly used for this area containing as the compound of the 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 prepared by method of the present invention.
Catalyst according to the invention, when the hydrocracking for hydrocarbon ils, has higher catalytic activity.Catalyst according to the invention is particularly suitable for the hydrocracking catalyst as heavy distillate and inferior distillate oil, to produce boiling range for 149-371 DEG C, particularly boiling range for the intermediate oil of 180-370 DEG C.
Thus, a third aspect of the present invention provides the application of a kind of catalyst according to the invention in hydrocarbon oil hydrogenation cracking.
A fourth aspect of the present invention provides a kind of method for hydrogen cracking, under the method is included in hydrocracking condition, by hydrocarbon ils and catalyst exposure provided by the invention.
According to method for hydrogen cracking of the present invention, described hydrocarbon ils can be various heavy mineral oil, artificial oil or their mixture.Particularly, the example of described hydrocarbon ils can include but not limited to: vacuum gas oil (VGO), metal removal oil, reduced crude, de-asphalted vacuum residue, decompression residuum, coker distillate, shale oil, asphalt sand oil and liquefied coal coil.
The present invention is that all the other conditions for hydrocracking are not particularly limited, and can be the normal condition of this area by using catalyst according to the invention to improve the activity of catalyst in hydrocracking.Preferably, described hydrocracking condition comprises: temperature can be 200-650 DEG C, is preferably 300-510 DEG C; In gauge pressure, pressure can be 3-24MPa, is preferably 4-15MPa; Hydrogen to oil volume ratio can be 100-5000, is preferably 200-1000; During the liquid of hydrocarbon ils, volume space velocity can be 0.1-10 hour
-1, be preferably 0.2-5 hour
-1.
According to method for hydrogen cracking of the present invention, described catalyst preferably carries out presulfurization before use.The condition of described presulfurization can be the normal condition of this area.Such as, the condition of described presulfurization can comprise: in presence of hydrogen, at the temperature of 360-400 DEG C, carries out presulfurization with one or more in sulphur, hydrogen sulfide, carbon disulfide, DMDS or polysulfide.According to method for hydrogen cracking 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 and comparative example.
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, Bio-RadIFS-3000 infrared spectrometer measures the B acid on large pore molecular sieve surface and the mol ratio of L acid and the silicone hydroxyl on large pore molecular sieve surface.
In following examples and comparative example, be on the X-ray diffractometer of X ' pert being purchased from the model of Philips company, measure the degree of crystallinity of molecular sieve, wherein, degree of crystallinity is relative crystallinity, is measure according to the method specified in RIPP139-90.
In following examples and comparative example, contents on dry basis is by measuring sample 600 DEG C of roastings 4 hours.
Preparation example 1-3 is for the preparation of shaping porous carrier.
Preparation example 1
(1) (be purchased from Chang Ling refinery company of China Petrochemical Industry catalyst plant, lattice constant is to get 200g (in butt) NaY molecular sieve
relative crystallinity is 100%, and specific area is 720m2/g, and sodium oxide content is 13.1 % by weight) be placed in reactor, add 200g ammonium sulfate and 2000mL water, with stirring, temperature is increased to 90 DEG C, and keeps 2 hours at such a temperature.After reaction terminates, product is filtered, and washes filter cake with water three times, obtain molecular sieve NY-1.
(2) get the molecular sieve NY-1 that 100 grams of steps (1) obtain, be placed in Muffle furnace, intensification limit, limit passes into steam, temperature is increased to 550 DEG C, and constant temperature, after 2 hours, cools the temperature to room temperature, takes out.The product obtained is placed in reactor, adds the aqueous solution that 1000mL contains sulfuric acid and ammonium sulfate, wherein, the concentration of sulfuric acid is 0.1 % by weight, and the content of ammonium sulfate is 100 grams.With stirring, temperature is increased to 90 DEG C, constant temperature 2 hours.Product is filtered, the filter cake obtained is repeated the process secondary of step (2).
(3) filter cake that step (2) obtains is placed in reactor, add the aqueous solution of the fluorine-containing ammonium silicate of 500mL and ammonium sulfate, wherein, in the described aqueous solution, the content of ammonium fluosilicate (being purchased from Yunnan Fu Ye Chemical Co., Ltd.) is 2 grams, the content of ammonium sulfate is 100 grams, with stirring, temperature is increased to 90 DEG C, constant temperature filtered after 2 hours, the filter cake obtained is dried to constant weight at 120 DEG C, obtains large pore molecular sieve CZ-1.Infrared spectrum measurement, this large pore molecular sieve is at 3685-3760cm
-1occur two hydroxyl peak, absworption peak position is respectively 3740cm
-1and 3710cm
-1, B acid/L acid=8.3 (mol ratios).
(4) the CZ-1 zeolite 225 grams of steps (3) obtained, 850 grams of (in butt) boehmites (are purchased from Shandong Aluminum Plant, commodity are called SD powder, contents on dry basis is 69 % by weight), 430 grams of Ludox (are purchased from Haiyang Chemical Plant, Qingdao, dioxide-containing silica is 30 % by weight) and 45 grams of sesbania powder mixing, be extruded into extruder the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.By the formed body extruded 120 DEG C of dryings 5 hours, then 550 DEG C of roastings 3 hours, obtained carrier S 1.In carrier S 1, the content of large pore molecular sieve is 15.0 % by weight, and the content of silica is 18.0 % by weight, and the content of aluminium oxide is 67.0 % by weight.
Preparation example 2
By 75 grams of REY molecular sieves, (be purchased from Chang Ling refinery company of China Petrochemical Industry catalyst plant, commodity are called REHY, and lattice constant is
the content of rare earth element is 3 % by weight), 1050 grams of (in butt) boehmites (are purchased from Shandong Aluminum Plant, commodity are called SD powder, contents on dry basis is 69 % by weight), 1250 grams of Ludox (are purchased from Haiyang Chemical Plant, Qingdao, dioxide-containing silica is 30 % by weight) and 45 grams of sesbania powder mixing, be extruded into extruder the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.By the formed body extruded 120 DEG C of dryings 5 hours, then 550 DEG C of roastings 3 hours, obtained carrier S 2.In carrier S 2, the content of large pore molecular sieve is 5.0 % by weight, and the content of silica is 25.0 % by weight, and the content of aluminium oxide is 70.0 % by weight.
Preparation example 3
By 150 grams of phosphorous y-type zeolites, (be purchased from Chang Ling refinery company of China Petrochemical Industry catalyst plant, commodity are called PSRY, and lattice constant is
phosphorus content is 5 % by weight), 1125 grams of (in butt) boehmites (are purchased from Shandong Aluminum Plant, commodity are called SD powder, contents on dry basis is 69 % by weight), 750 grams of Ludox (are purchased from Haiyang Chemical Plant, Qingdao, dioxide-containing silica is 30 % by weight) and 45 grams of sesbania powder mixing, be extruded into extruder the cloverleaf pattern bar that circumscribed circle diameter is 1.6 millimeters.By the formed body extruded 120 DEG C of dryings 5 hours, then 550 DEG C of roastings 3 hours, obtained carrier S 3.In carrier S 3, the content of large pore molecular sieve is 10.0 % by weight, and the content of silica is 15.0 % by weight, and the content of aluminium oxide is 75.0 % by weight.
Embodiment 1-11 is for illustration of catalyst according to the invention and preparation method thereof.
Embodiment 1
50 grams of ammonium molybdates are joined in 120 ml waters, drip under adding thermal agitation concentration be 25% ammoniacal liquor until ammonium molybdate dissolve, then add 30 grams of cobalt nitrates and 10 grams of ammonium fluorides, after stirring and dissolving, 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, 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; 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-1.The composition of catalyst B-1 is table 1 illustrate.
Embodiment 2
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, 110 grams of ammonium metatungstates and 22 grams of boric acid 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 2, dip time is 0.1 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 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-2, its composition illustrates in Table 1.
Comparative example 1
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, unlike, do not use ammonium fluoride and isopropyl alcohol, in hydrothermal treatment process, the pressure in autoclave is 1.5MPa (that is, Δ P=0), obtains catalyst D-1, and its composition illustrates in Table 1.
Comparative example 2
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 2, unlike, in hydrothermal treatment process, in autoclave, do not pass into nitrogen, in hydrothermal treatment process, the pressure in autoclave be 0.2MPa (namely, Δ P=0), obtain catalyst D-2, its composition illustrates in Table 1.
Embodiment 3
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 2, unlike, 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-3, and its composition illustrates in Table 1.
Embodiment 4
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 1, unlike, not 15 milliliters of isopropyl alcohols are added in the autoclave of mixture that has and flood and obtain, but add in the aqueous solution for impregnated carrier S1, obtain catalyst according to the invention B-4, its composition illustrates in Table 1.
Embodiment 5
30 grams of ammonium molybdates are added in 65 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, 5 grams of ammonium fluorides and 10 milliliters of ethanol, 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 3, 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, its composition illustrates in Table 1.
Embodiment 6
50 grams of ammonium molybdates are added 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, 10 grams of ammonium fluorides and 20 milliliters of ethanol are added, add water after stirring and dissolving and be settled to 200 milliliters, adopt the above-mentioned aqueous impregnation of excessive infusion process 100 grams of carrier S 3, 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 2.1MPa in hydrothermal treatment process in autoclave, wherein, 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 200 DEG C dry 3 hours again, obtain catalyst according to the invention B-6, its composition illustrates in Table 1.
Comparative example 3
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 6, unlike, do not use ethanol and nitrogen, in hydrothermal treatment process, the pressure in autoclave is 1.5MPa (that is, Δ P=0), thus obtains catalyst D-3, and its composition illustrates in Table 1.
Table 1
Embodiment 7
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 and 20 grams of zinc nitrates are added, 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 infusion process 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, 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-7, and its composition illustrates in table 2.
Embodiment 8
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, 110 grams of ammonium metatungstates and 35 grams of magnesium nitrates 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 2, dip time is 0.1 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 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-8, its composition illustrates in table 2.
Comparative example 4
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 7, unlike, do not use zinc nitrate and ethanol, in hydrothermal treatment process, the pressure in autoclave is 0.5MPa (that is, Δ P=0), obtains catalyst D-4, and its composition illustrates in table 2.
Comparative example 5
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 8, unlike, do not use magnesium nitrate and nitrogen, in hydrothermal treatment process, the pressure in autoclave is 0.2MPa (that is, Δ P=0), obtains catalyst D-5, and its composition illustrates in table 2.
Embodiment 9
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 8, unlike, 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-9, and its composition illustrates in table 2.
Embodiment 10
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 4.5 grams of lanthanum 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 3, dip time is 2 hours.Autoclave is placed in by flooding the mixture obtained, and add 15 milliliters of isopropyl alcohols and carry out hydrothermal treatment consists, the condition of hydrothermal treatment consists comprises: temperature is 100 DEG C, time is 12 hours, in autoclave, pass into argon gas in hydrothermal treatment process makes the pressure in autoclave be 3.2MPa, 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-10, its composition illustrates in table 2.
Embodiment 11
50 grams of ammonium molybdates are added in 150 ml waters, drip under adding thermal agitation concentration be 25 % by weight ammoniacal liquor dissolve to ammonium molybdate, then 30 grams of cobalt nitrates and 8 grams of lanthanum nitrates are added, add water after stirring and dissolving and be settled to 200 milliliters, adopt the above-mentioned aqueous impregnation of excessive infusion process 100 grams of carrier S 3, dip time is 2 hours.Autoclave is placed in by flooding the mixture obtained, and add 15 milliliters of isopropyl alcohols and carry out hydrothermal treatment consists, the condition of hydrothermal treatment consists comprises: temperature is 200 DEG C, time is 12 hours, in autoclave, pass into argon gas in hydrothermal treatment process makes the pressure in autoclave be 2.1MPa, wherein, 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 200 DEG C dry 3 hours again, obtain catalyst according to the invention B-11, its composition illustrates in table 2.
Comparative example 6
Adopt the method Kaolinite Preparation of Catalyst identical with embodiment 11, unlike, do not use isopropyl alcohol and argon gas, in hydrothermal treatment process, the pressure in autoclave is 1.5MPa (that is, Δ P=0), thus obtaining catalyst D-6, its composition illustrates in table 2.
Table 2
Embodiment 12-22 is for illustration of the application of catalyst according to the invention and method for hydrogen cracking.
Embodiment 12-22
High-pressure hydrogenation micro-reactor comes using naphthane as model compound the catalytic performance of catalyst prepared by Evaluation operation example 1-11 respectively.
Become by catalyst breakage diameter to be the particle of 0.3-0.45 millimeter, load this catalyst 0.2 milliliter in fixed bed reactors, before logical oil, first catalyst carries out sulfuration, and conditions of vulcanization is:
Be under the condition of 2.0MPa in hydrogen dividing potential drop, be warming up to 60 DEG C, then pass into the hexane solution that CS2 content is 6 % by weight, be warming up to 300 DEG C, and constant temperature 4 hours;
After sulfuration completes, pass into feedstock oil (for naphthane content is the normal octane solution of 5.61 % by weight), react, reaction condition is: temperature is 390 DEG C, and pressure is 4.0MPa, and hydrogen to oil volume ratio is 5000, and during liquid, volume space velocity is 30 hours
-1.
Adopt the catalytic activity of following formulae discovery catalyst, result illustrates in table 3.
Comparative example 7-12
Adopt the identical method of embodiment 12-22 to evaluate the catalytic activity of catalyst prepared by comparative example 1-6 respectively, result illustrates in table 3.
Table 3
| Embodiment is numbered | Catalyst is numbered | Catalytic activity (%) |
| Embodiment 12 | B-1 | 65.4 |
| Embodiment 13 | B-2 | 86.1 |
| Comparative example 7 | D-1 | 46.4 |
| Comparative example 8 | D-2 | 69.7 |
| Embodiment 14 | B-3 | 89.4 |
| Embodiment 15 | B-4 | 64.9 |
| Embodiment 16 | B-5 | 60.5 |
| Embodiment 17 | B-6 | 63.8 |
| Comparative example 9 | D-3 | 49.6 |
| Embodiment 18 | B-7 | 64.9 |
| Embodiment 19 | B-8 | 88.0 |
| Comparative example 10 | D-4 | 49.5 |
| Comparative example 11 | D-5 | 67.4 |
| Embodiment 20 | B-9 | 90.2 |
| Embodiment 21 | B-10 | 62.7 |
| Embodiment 22 | B-11 | 65.9 |
| Comparative example 12 | D-6 | 51.4 |
The result display of table 3, prepared according to the methods of the invention catalyst demonstrates higher catalytic activity in the hydrocracking of hydrocarbon ils.
Claims (24)
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 are as the element of auxiliary agent, described shaping porous carrier is containing silica, aluminium oxide and at least one large pore molecular sieve, element as auxiliary agent is selected from the nonmetalloid as auxiliary agent and the metallic element as auxiliary agent, nonmetalloid as auxiliary agent is selected from boron and fluorine, described group vib metallic element, described group VIII metallic element and making as the introduction volume of element on described shaping porous carrier of auxiliary agent, with the total amount of catalyst for benchmark, the content of described shaping porous carrier is 30-88.5 % by weight, with oxide basis, the content of described group vib metallic element is 10-50 % by weight, with oxide basis, the content of described group VIII metallic element is 1-10 % by weight, in element, the content of the described element as auxiliary agent is 0.5-10 % by weight,
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 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.
2. preparation method according to claim 1, wherein, described group vib metallic element, described group VIII metallic element and the introduction volume of element on described shaping porous carrier as auxiliary agent make, with the total amount of catalyst for benchmark, the content of described shaping porous carrier is 52-85 % by weight; With oxide basis, the content of described group vib metallic element is 12-40 % by weight; With oxide basis, the content of described group VIII metallic element is 2-5 % by weight; In element, the content of the described element as auxiliary agent is 1-3 % by weight.
3. preparation method according to claim 1, wherein, one or more in the following manner introduce the element of at least one as auxiliary agent on described shaping porous carrier:
Mode one: at least one is dissolved in the aqueous solution described in step (1) containing the compound as the 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 element of auxiliary agent and the described aqueous solution;
Mode two: before porous carrier shaping described in the aqueous impregnation described in step (1), load at least one is as the element of auxiliary agent on described shaping porous carrier;
Mode three: at least one is mixed with the raw material for the preparation of described shaping porous carrier containing the compound as the element of auxiliary agent, and by shaping for the mixture obtained, contains the element of at least one as auxiliary agent to make shaping porous carrier.
4. according to the method in claim 1-3 described in any one, wherein, described group vib metallic element is molybdenum and/or tungsten, and described group VIII metallic element is cobalt and/or nickel.
5. according to the method in claim 1-3 described in any one, 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.
6. method according to claim 5, wherein, the metallic element as auxiliary agent is selected from Zn-ef ficiency, sodium element, potassium element, magnesium elements, calcium constituent, lanthanum element and Ce elements.
7. method according to claim 1, wherein, with the total amount of described porous carrier for benchmark, the content of described silica is 2-45 % by weight, and the content of described large pore molecular sieve is 2-75 % by weight, and the content of described aluminium oxide is 23-96 % by weight.
8. the method according to claim 1 or 7, wherein, described large pore molecular sieve is the zeolite molecular sieve with twelve-ring pore structure.
9. method according to claim 8, wherein, described large pore molecular sieve be have faujasite structure zeolite molecular sieve, there is the zeolite structured zeolite molecular sieve of Beta and have in the zeolite molecular sieve of mordenite structure one or more.
10. method according to claim 8, wherein, the surface of described large pore molecular sieve has B acid and L acid, and the mol ratio of described B acid and described L acid is for being greater than 0.9, and described large pore molecular sieve is at 3685-3760cm
-1occur that at least one corresponds to the characteristic peak of silicone hydroxyl.
11. methods according to claim 1, wherein, described dipping is excessive dipping.
12. methods according to claim 1, wherein, make described hydrothermal treatment consists be P at pressure by the one in following three kinds of modes
0carry out under the condition of+Δ P:
Mode one: carry out described hydrothermal treatment consists under the existence of at least one volatile organic matter, the pressure that the addition of described volatile organic matter makes described volatile organic matter produce in hydrothermal treatment consists is Δ P;
Mode two: carry out described hydrothermal treatment consists under the existence of at least one non-active gas, the pressure that the addition of described non-active gas makes described non-active gas produce in hydrothermal treatment consists is Δ P;
Mode three: carry out described hydrothermal treatment consists under the existence of at least one volatile organic matter and at least one non-active gas, 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.
13. methods according to claim 12, wherein, 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.
14. methods according to claim 13, wherein, 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.
15. methods according to claim 1 or 12, wherein, Δ P is 0.1-10MPa.
16. methods according to claim 15, wherein, Δ P is 0.2-8MPa.
17. methods according to claim 1 or 12, 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.
18. methods according to claim 1, wherein, the method also comprises solid matter drying obtained and carries out roasting.
19. methods according to claim 18, wherein, the condition of described roasting comprises: temperature is 350-550 DEG C, and the time is 1-8 hour.
20. methods according to claim 1 or 18, wherein, the condition of described drying comprises: temperature is 100-300 DEG C, and the time is 1-12 hour.
21. catalyst prepared according to the method in claim 1-20 described in any one.
22. application of catalyst according to claim 21 in hydrocarbon oil hydrogenation cracking.
23. 1 kinds of method for hydrogen cracking, under the method is included in hydrocracking condition, by hydrocarbon ils and catalyst exposure according to claim 21.
24. methods according to claim 23, wherein, described hydrocracking condition comprises: temperature is 200-650 DEG C; In gauge pressure, pressure is 3-24MPa; Hydrogen to oil volume ratio is 100-5000; During the liquid of hydrocarbon ils, volume space velocity is 0.1-10 hour
-1.
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