CN106179414A - A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof - Google Patents
A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of sulfurized hydrogenation catalyst for refining and preparation method thereof.This catalyst is body phase Hydrobon catalyst, its composition includes the sulfide of hydrogenation active metals component W, Ni and Mo, aluminium oxide, and its table phase active metallic content is high, active site density is big, active metal disperses evenly, and the cooperation between active metal is good, and active metal utilization rate is high, catalyst pore structure is reasonable simultaneously, mechanical strength is high, has higher hydrodesulfurization and hydrodenitrogeneration reactivity worth, particularly suitable application in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst and preparation method thereof, the most highly active vulcanization type body phase Hydrobon catalyst and preparation method thereof.
Background technology
At present the most worldwide, crude oil heaviness increasingly and in poor quality, the sustainable development of World Economics and the increasingly stringent of environmental regulation, need to produce a large amount of light clean fuel in addition.Exploitation and to use super-low sulfur be even to clean the trend that fuel develops in the range of the world today without sulfur vapour, diesel oil.Traditional Hydrobon catalyst is used such as to improve reaction temperature, hydrogen dividing potential drop by increasing reaction severity or reduce reaction velocity etc., the deep desulfuration even ultra-deep desulfurization of diesel oil can also be realized, but the rising of reaction temperature can cause the variation of product colour and catalyst life to shorten, and reduces air speed and then means the minimizing for the treatment of capacity.For existing hydrogenation plant, its design pressure is the most fixing, and the amplitude improving hydrogen dividing potential drop is limited.Therefore, current is one of the important means of deep desulfuration by using the catalyst of more high desulfurization activity.
Containing various structures and the sulfur-containing compound of different molecular weight in petroleum distillate, but at ultra-deep desulfurization stage (sulfur content is less than 50 g/g), mainly removing 4, the sulfur-containing compound of the substituted bases such as 6-dimethyl Dibenzothiophene class.Owing to the methyl of sulphur atom next-door neighbour makes to create between sulphur atom and the active center of catalyst sterically hindered, the active center of the most accessible reaction of sulphur atom, thus result in reaction rate and significantly decline.
Conventional load type hydrogenation catalyst is limited by carrier hole structure, active metal load capacity is usually no more than 30wt%, the active center quantity that loaded catalyst can be provided by is limited, although the quantity in active center and type distribution can be optimized adjustment, but owing to the limit bottleneck of active center quantity cannot be broken through, increase substantially the limited space of hydrogenation activity, be difficult to the demand meeting refinery to manufacturing country V diesel product.Hydrogenation catalyst major part prepared by body phase method is made up of active metal component, the restriction of tenor can be broken away from, can any ratio of each active component in regulating catalyst, improve the Hydrogenation of catalyst, owing to bulk phase catalyst has the hydrogenation activity of excellence, can be under conditions of not improving device reaction severity, being directly produced the product without sulfur diesel meeting state V standard, original device is without transformation, it is possible to improve the treating capacity of device, reduce the production cost of refinery, it is achieved energy efficiency.
Current industrialized hydrogenation catalyst, its active metal component major part is all to exist in the form of an oxide, and time actually used, need that metal sulfide on catalyst is just had hydrogenation sites, therefore, catalyst needs before use through over cure or claims presulfurization.Conventional catalyst vulcanization process uses " in device " presulfurization, the most first the catalyst of oxidation state is loaded in reactor, then being passed through hydrogen to reactor during constantly heating up and vulcanizing agent carries out presulfurization, this method brings following problem: (1) to set up special and vulcanizing equipment on hydrogenation plant；(2) water and hydrogen sulfide that the vulcanizing agent added in sulfidation and reaction generate easily cause high-pressure reactor and the corrosion about equipment, cause device damage and potential safety hazard；(3) sulfidation is longer, is delayed on-stream time.(4) vulcanizing agent used by is inflammable poisonous, to environment in sulfidation；(5) in-situ presulfurization is relatively costly.
The catalyst that the presulfurization of catalyst is transferred to carry out on special vulcanization reaction device or make by on-the-spot outer pre-curing technology (or claiming " device is outer " presulfurization) has been the catalyst of sulphided state, and catalyst loads in hydrogenation reactor and can use.This kind of vulcanization process be simple, efficient, pollution-free and low cost, has the most become the development trend of hydrogenation catalyst technology of preparing.
Although active metallic content is high in body phase hydrogenation catalyst, but by mechanical strength, the restriction of the aspects such as active metal easily gathering, need to add a certain amount of adhesive component, generally meet the requirement of mechanical strength, the addition of binding agent will be at more than 30wt%, the most, the most not only reduce the consumption of active metal, in making again amount of activated metal entrance body mutually, make it can not become hydrogenation sites, there is the problem that active metal utilization rate is low, simultaneously, the distribution making different hydrogenation active metals is not easily controlled, thus affect the distribution of different hydrogenation active metals.Therefore, for body phase hydrogenation catalyst, there is the distribution of good hydrogenation active metals, there is mating reaction between suitable hydrogenation active metals component, there is high catalyst surface active bit density, there is high active metal utilization rate, the activity of catalyst can be significantly improved.
CN1951561A discloses the method using co-precipitation to prepare hydrogenation catalyst, and catalyst uses active metal Ni, W component to generate Ni with precipitant co-precipitationxWyOzComposite oxides precursor, in above process, can add aluminum salt solution, it is also possible to be directly added into aluminium hydroxide after plastic, then with MoO3Making beating mixing, filtration, molding, activation are final catalyst.Bulk phase catalyst prepared by the method reaches to meet the use of mechanical strength when requiring, its surface activity bit density is relatively low, it is impossible to give full play to the advantage of high-load active metal component, reduces the utilization rate of active metal, adds the preparation cost of catalyst.
CN101306374A discloses a kind of hydrogenating catalyst composition, this catalyst is prepared by coprecipitation method, the compound of at least one metal component of group VIII, the compound of at least two metal component of group VIB, organic additive and water are mixed with mixed liquor, the pH using acid or alkali to adjust mixed liquor is 7～11, described mixed liquor is placed in reactor, react 1～24 hour under the airtight condition of room temperature to 250 DEG C, filter afterwards and be dried.The catalyst of the method gained is without high-temperature roasting, containing organic additive in final catalyst, the mechanical strength of catalyst to be made meets use requirement, needs to add more adhesive component, so can affect the distribution of different hydrogenation active metals, make catalyst surface active reduce.
CN101255356A discloses the preparation method of a kind of unsupported catalyst, it is to use urea melting reaction technology, the VIIIth race and group VIB active metal precursor will be contained and carbamide will mix and is incorporated under urea melting state reaction, remove unnecessary carbamide, obtain catalyst particles, can be shaped by adding binding agent.In the method, carbamide adds as precipitant, need after reaction to add the carbamide that heat extraction is unnecessary, being subsequently adding binding agent to be shaped, such the method yet suffers from the addition of binding agent and makes the skewness of different hydrogenation active metals, the low density problem of catalyst surface active position simultaneously.
Hydrogenation catalyst prepared by body phase method, its hydrogenation sites be reactant molecule can be close catalyst channel surfaces on, although this type of catalyst activity tenor is higher, but not all active metal can become hydrogenation sites, therefore, how to make more active metal be distributed in channel surfaces and form hydrogenation sites, improve the active center density on bulk phase catalyst surface, the utilization rate improving hydrogenation active metals component is the most important research topic.
Body phase hydrogenation catalyst disclosed in CN102049265A, ammonium hydrogen carbonate is added during coprecipitated, body phase hydrogenation catalyst disclosed in CN102451703A, carbon dioxide is added during coprecipitated, generate carbonate or bicarbonate, said method is all to utilize it to release a certain amount of gas in roasting process, under the percussion of gas, increase the pore volume of catalyst, specific surface area, more metal active position is made to be exposed to the surface of catalyst, but this kind of method can make cell channels collapse, pore size distribution disperse, mechanical strength reduces, and cause active metal localized clusters, the metal active position come out is limited.
Under distillate ultra-deep hydrodesulfuration reaction environment, present in distillate, nitrogen-containing organic compound produces obvious inhibitory action to hydrodesulfurization reaction, hydrodesulfurization activity increases along with the nitrogen content in raw material and reduces, this is because there is competitive Adsorption on catalyst activity position in nitrogen-containing compound and sulfide in distillate, the absorbability of nitride is stronger, occupy the active sites on catalyst, sulfide is made to be difficult to close, inhibit hydrodesulfurization reaction, so when processing the high heavy diesel of nitrogen content and producing super-low sulfur product, catalyst needs the hydrodenitrogenationactivity activity with excellence, the hydrodenitrogenationactivity activity of catalyst improves, after nitrogen content reduces, reduce with the nitride of sulfide generation competitive Adsorption, sulfide is easier to, adsorb the most more on catalyst activity position, promote hydrodesulfurization reaction.Therefore the hydrodenitrogenationactivity activity improving catalyst has extremely important effect to the ultra-deep hydrodesulfuration activity improving bulk phase catalyst.
Coprecipitation method prepares bulk phase catalyst technology, use different coprecipitation mode, Gelation Conditions etc., all can to active metallic content on channel surfaces in catalyst and between active center density, the distribution of different hydrogenation active metals and different hydrogenation active metals interaction relationship have a great impact.The coprecipitation method of above-mentioned employing can make the distribution of different hydrogenation active metals be not easily controlled, thus affect the distribution of different hydrogenation active metals, reduce the effect of cooperating between active metal, simultaneously, in catalyst, table phase active metallic content is less and active center density is relatively low, finally affects the ultra-deep hydrodesulfuration performance of catalyst.Therefore, how to regulate and control the distribution of hydrogenation active metals, make to have between hydrogenation active metals component suitable mating reaction, how to increase table phase active metallic content and active center density in catalyst, improve the utilization rate of hydrogenation active metals component, be the key improving body phase Hydrobon catalyst Hydrogenation.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of sulfurized hydrogenation catalyst for refining and preparation method thereof.This catalyst table phase active site density is big, hydrogenation active metals utilization rate is high, improve the distribution of hydrogenation active metals in catalyst, improve mating reaction between hydrogenation active metals, catalyst pore structure is reasonable simultaneously, active metal disperses evenly, and mechanical strength is high, particularly suitable application in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.
Sulfurized hydrogenation catalyst for refining of the present invention is vulcanization type body phase Hydrobon catalyst, and its composition includes the sulfide of hydrogenation active metals component W, Ni, Mo, aluminium oxide；Wherein the sulfide of table phase active metal component W is with WS2The sulfide of the weight content of meter and body middle active metal component W mutually is with WS2The ratio of the weight content of meter is 2.0:1 ~ 7.0:1, it is preferably 3.0:1 ~ 6.0:1, the ratio of the weight content that the sulfide of the weight content that the sulfide of table phase active metal component Ni is counted with NiS and body phase active metal component Ni is counted with NiS as 1.5:1 ~ 5.5:1, it is preferably: 1.8 ~ 4.5:1, the sulfide of table phase active metal component Mo is with MoS2The weight content of meter and the sulfide of body phase active metal component Mo are with MoS2The ratio of the weight content of meter is 1.8:1 ~ 6:1, preferably 2.5:1 ~ 4.5:1.
Sulfurized hydrogenation catalyst for refining of the present invention, hydrogenation active metals W therein, Ni, Mo
It is to be present in catalyst with sulphided form, is usually with WS2、NiS、MoS2Presented in.
In the present invention, the weight content of the sulfide of table phase active metal component W is that the sulfide of table middle W mutually is with WS2Meter weight content, the weight content of the sulfide of body phase active metal component W be in catalyst the sulfide of W with WS2The weight content of meter；The weight content of the sulfide of table phase active metal component Ni is the sulfide of table middle Ni mutually weight content in terms of NiS, and the weight content of the sulfide of body phase active metal component Ni is the sulfide of Ni weight content in terms of NiS in catalyst；The sulfide of table phase active metal component Mo is with MoS2The weight content of meter is that the sulfide of table middle Mo mutually is with MoS2The weight content of meter, the sulfide of body phase active metal component Mo is with MoS2Meter weight content be in catalyst the sulfide of Mo with MoS2The weight content of meter.
The Hydrobon catalyst of the present invention, on the basis of the weight of Hydrobon catalyst, the sulfide of Ni, W and Mo is (with NiS, WS2、MoS2Meter) gross weight content is 40% ~ 95%, preferably 50% ~ 85%, alumina content is 5% ~ 60%, preferably 15% ~ 50%.In the Hydrobon catalyst of the present invention, the mol ratio of Ni/W is 1:8 ~ 8:1, preferably 1:4 ~ 4:1, and (Ni+W)/Mo mol ratio is 1:10 ~ 10:1, preferably 1:5 ~ 5:1.
Hydrobon catalyst of the present invention can contain adjuvant component as required, adjuvant component is one or more in silicon, phosphorus, titanium, zirconium, boron etc., preferably titanium and/or zirconium, in terms of element, adjuvant component weight content in Hydrobon catalyst is 0 ~ 20%, preferably 1% ~ 15%.
The preparation method of Hydrobon catalyst of the present invention, including:
(1), prepare the component saline mixed solution A Han Ni and Al, precipitant is added dropwise to solution A and carries out plastic reaction, generate nickeliferous, aluminum precipitation thing serosity I；
(2), prepare the component saline mixed solution B Han W, Mo and Al, solution B and precipitant carried out and flows plastic reaction, generating tungstenic, molybdenum, aluminum precipitation thing serosity II；
(3), by the serosity I of step (1) gained and the serosity II mix homogeneously of step (2) gained, the most aging, after aging end, filter, the material water vapour obtained carries out hydrothermal treatment consists, wherein adds carbamide during hydrothermal treatment consists；
(4), step (3) gained material add Ammonium hyposulfite. and adjuvant kneading, molding after drying, be dried, carry out heat treatment the most in the presence of an inert gas, obtain sulfurized hydrogenation catalyst for refining.
In the inventive method, can add required catalyst promoter according to a conventional method, adjuvant component is one or more in silicon, phosphorus, titanium, zirconium, boron etc..
Precipitant described in step (1) or step (2) is one or more in sodium carbonate, sodium bicarbonate, ammonia, sodium hydroxide, potassium hydroxide, potassium carbonate, potassium bicarbonate, preferably ammonia, and weights of ammonia concentration is 5%～15%.
In step (1) mixed solution A, Ni weight concentration in terms of NiO is 5～80g/L, and preferably 10～60g/L, Al is with Al2O3The weight concentration of meter is 2～60g/L, preferably 8～40g/L.In step (2) mixed solution B, W is with WO3The weight concentration of meter is 10～100g/L, and preferably 20～90g/L, Mo is with MoO3The weight concentration 5～80g/L of meter, preferably 10～60g/L, Al is with Al2O3The weight concentration of meter is 2～60g/L, preferably 8～40g/L.When preparing mixed solution A, the general nickel source used can be one or more in nickel sulfate, nickel nitrate, basic nickel carbonate, Nickel dichloride., and aluminum source can be one or more in aluminum nitrate, aluminum sulfate, aluminum chloride or aluminium acetate etc..When preparing mixed solution B, the general tungsten source used can be one or more in ethyl ammonium metatungstate, ammonium metatungstate；Molybdenum source is ammonium molybdate；Aluminum source can be one or more in aluminum nitrate, aluminum sulfate, aluminum chloride or aluminium acetate etc..
In step (1), reaction temperature is 20～90 DEG C, preferably 30～70 DEG C.During cemented into bundles, pH value controls is 6.0 ~ 11.0, preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.
In step (2), reaction temperature is 30～90 DEG C, preferably 40～80 DEG C.And pH value control is 6.0 ~ 11.0 when flowing plastic, preferably 7.0 ~ 9.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.
In step (1) and step (2), gelling temperature and time can be the same or different.Step (1) and step (2) can carry out can also carrying out during difference simultaneously.
In step (3), aging temperature is 40～90 DEG C, preferably 50～80 DEG C.Time aging, pH value controls is 6.0 ~ 10.0, preferably 6.5 ~ 9.0.Ageing time is 0.5 ~ 6.0 hour, preferably 1.0 ~ 4.0 hours.
Hydrothermal conditions described in step (3) is as follows: carry out under airtight container, and temperature is 200 ~ 300 DEG C, preferably 210 ~ 260 DEG C, and pressure is 1.0 ~ 8.0 MPa, preferably 3.0 ~ 6.0MPa, and the process time is 0.5 ~ 10.0 hour, preferably 1.0 ~ 6.0 hours.During hydrothermal treatment consists, the addition of carbamide is 0.5:1 ~ 10.0:1, preferably 2.0:1 ~ 8.0:1 with the mol ratio of active metal (tungsten, molybdenum, nickel) atom total amount in catalyst.
The addition of the Ammonium hyposulfite. described in step (4) is calculated as catalyst theory with element sulphur and needs the 100%～200% of sulfur content, preferably 105%～160%.Described adjuvant is unsaturated hydro carbons, including one or more in alkene, alkadienes, alkynes, can also be for the mixture (concentration of unsaturated hydro carbons is 30v%～60v%) containing unsaturated hydro carbons, including one or more in coker gasoline, coker gas oil, catalytically cracked gasoline, catalytic cracking diesel oil, the boiling point of adjuvant is 110～370 DEG C, and the addition of adjuvant is calculated as the 3%～50% of step (3) gained material gained dried material weight after drying with unsaturated hydro carbons.
Molding described in step (4), it is dried this area conventional method can be used to carry out.In forming process, the shaping assistant of routine, one or more in such as peptizer, extrusion aid etc. can be added as required.Described peptizer is one or more in hydrochloric acid, nitric acid, sulphuric acid, acetic acid, oxalic acid etc., described extrusion aid refers to the most extruded material, such as one or more in sesbania powder, white carbon black, graphite powder, citric acid etc., the consumption of extrusion aid accounts for 1wt%～10wt% of total material butt.Drying condition after molding is as follows: being dried 1 ~ 48 hour at 50 ~ 250 DEG C, preferably 80 ~ 180 DEG C are dried 4 ~ 36 hours.
Heat treatment described in step (4) is to carry out in the presence of noble gas, at least one gas of hydrogen, and treatment temperature is 200～600 DEG C, preferably 350～500 DEG C, and the process time is 2～12 hours, preferably 4～10 hours.
In the inventive method, the shape of catalyst can be as needed for lamellar, spherical, cylindrical bars and irregular bar (Herba Trifolii Pratentis, Herba Galii Bungei), preferably cylindrical bars and irregular bar (Herba Trifolii Pratentis, Herba Galii Bungei).The diameter of carrier can be slice and the thick bar of ＞ 2.5mm of 0.8 ~ 2.0mm.
In Hydrobon catalyst of the present invention, surface activity bit density is big, active metal disperses evenly, cooperation between active metal is good, active metal utilization rate is high, and catalyst pore structure is reasonable simultaneously, and mechanical strength is high, there is higher hydrodesulfurization and hydrodenitrogeneration reactivity worth, particularly suitable application in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.
Hydrobon catalyst of the present invention is complete cure type catalyst, and heating up the most in presence of hydrogen goes into operation, and empty calory and hydrogen sulfide gas are released, and the outer pre-sulfide catalyst bed of effective preventer is prone to temperature runaway and the problem such as intensification initial stage device is airtight.
The inventive method uses positive addition (the acid sedimentation method i.e. alkaline precipitating agent is added in the metal salt solution of acidity precipitate) to prepare nickel aluminum mixed sediment, uses parallel flow precipitation to prepare tungsten, molybdenum and aluminum mixed sediment, then by aging after both mixing.The present invention prepares the relatively large nickel of crystal grain, aluminum precipitation thing by using positive addition, cocurrent process prepares the relatively small tungsten of crystal grain, molybdenum and aluminum precipitation thing, above two precipitate is mixed, the distribution of different hydrogenation active metals can be controlled, be conducive to being formed between active metal tungsten, molybdenum, nickel high activity phase, and improve the interaction between active metal, improve the ultra-deep hydrodesulfuration performance of body phase Hydrobon catalyst.
In the preparation method of catalyst of the present invention, the material steam treatment under appropriate conditions that obtains add carbamide after the co-precipitation of W, Ni, Mo, Al component, carbamide is decomposed into NH in high temperature environments3And CO2, NH3And CO2NH is generated in the presence of water vapour4 +And HCO3 -Ion, NH4 +And HCO3 -The microscopic pattern of material is had a significant impact by ion at high temperature under high pressure, before hydrothermal treatment consists, material phase structure is cylinder, after hydrothermal treatment consists, material phase structure is changed into, from cylinder, the irregular body that irregular lamellar is piled into, the transformation of this structure make active metal table mutually in distribution substantially increase, and disperse evenly, be conducive to improving the density of Adsorption.Additionally, add carbamide when steam treatment, make the transformation of material form that the pore size distribution of catalyst can also be made more to concentrate, more uniformly, be conducive to improving the mechanical strength of catalyst.The Hydrobon catalyst of the present invention is in deeply desulfurizing fractional oil and denitrification process, there is the hydrodenitrogenationactivity activity of excellence, the reduction of nitrogen content, it is more beneficial for the carrying out of hydrodesulfurization reaction, so Hydrobon catalyst is when the heavy distillate that processed nitrogen content is high, there is the ultra-deep hydrodesulfuration activity of excellence.
Detailed description of the invention
In the present invention, specific surface area and pore volume use low temperature liquid nitrogen determination of adsorption method, and mechanical strength uses side pressure method to measure.Catalyst table phase active metallic content uses x-ray photoelectron spectroscopy (XPS) to measure, and caltalyst phase active metallic content uses inductively coupled plasma atomic emission spectrum (ICP-AES) to measure, transmissioning electric mirror determining catalyst surface WS2/MoS2Density i.e. WS2And MoS2Density.In the present invention, wt% is mass fraction, and v% is volume fraction.
Embodiment 1
Respectively Nickel dichloride. and liquor alumini chloridi being dissolved in water purification, be configured to mixed solution A, in mixed solution A, the weight concentration of NiO is 21g/L, Al2O3Weight concentration be 15g/L.Respectively ammonium metatungstate, ammonium molybdate and liquor alumini chloridi are dissolved in water purification, are configured to mixed solution B, WO in mixed solution B3Weight concentration be 36g/L, MoO3Weight concentration is 18g/L, Al2O3Weight concentration be 13g/L.Being that 10wt% ammonia under agitation adds solution A by concentration, gelling temperature is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I.1000mL water purification is added in retort, being 10wt% ammonia and solution B by concentration and flow in addition retort, gelling temperature is maintained at 60 DEG C, and flows pH value in plastic course of reaction and control 7.8, gelation time control, at 60 minutes, generates tungstenic, molybdenum, aluminum precipitation thing serosity II.By above two containing aging after sediment slurry mixing, ageing time 2 hours, aging temperature 75 DEG C, at the end of aging, pH value controls 7.6, then filter, filter cake carries out hydrothermal treatment consists under the water vapour containing carbamide, the condition of hydrothermal treatment consists is: the mol ratio of carbamide and active metal atom total amount is 7:1, temperature is 250 DEG C, pressure is 4.0MPa, the process time is 4 hours, filter cake is dried 8 hours at 100 DEG C, by material, roll after Ammonium hyposulfite. (Ammonium hyposulfite. addition is calculated as catalyst theory with element sulphur and needs the 120% of sulfur content) and laurylene (laurylene addition accounts for the 10% of weight of material) mixing, extruded moulding.It is dried 10 hours at 80 DEG C.Carry out heat treatment in the presence of hydrogen gas, 450 DEG C of constant temperature 6 hours, obtain catalyst A.Catalyst composition, pore size distribution and main character are shown in Table 1.
Embodiment 2
According to the method for embodiment 1, by the constituent content proportioning of the catalyst B in table 1, in dissolving tank 1, add nickel nitrate, aluminum nitrate, prepare working solution A, in dissolving tank 2, add aluminum nitrate, ammonium metatungstate and ammonium molybdate preparation working solution B.Being that 15wt% ammonia under agitation adds solution A by concentration, gelling temperature is maintained at 55 DEG C, at the end of pH value control 8.0, gelation time control, at 50 minutes, generates nickeliferous, aluminum precipitation thing serosity I.600mL water purification is added in retort, being 15wt% ammonia and solution B by concentration and flow in addition retort, gelling temperature is maintained at 45 DEG C, and flows pH value in plastic course of reaction and control 7.8, gelation time control, at 60 minutes, generates tungstenic, molybdenum, aluminum precipitation thing serosity II.By above two containing aging after sediment slurry mixing, ageing time 3 hours, aging temperature 72 DEG C, at the end of aging, pH value controls 8.0, then filter, filter cake carries out hydrothermal treatment consists under the water vapour containing carbamide, hydrothermal conditions: the mol ratio of carbamide and active metal atom total amount is 3:1, temperature is 230 DEG C, pressure is 3.5MPa, the process time is 5 hours, material after hydrothermal treatment consists is dried 10 hours at 80 DEG C, by material, Ammonium hyposulfite. (Ammonium hyposulfite. addition is calculated as catalyst theory with element sulphur and needs the 130% of sulfur content) and catalytic gasoline (presence of unsaturates is as 53.6v%) are (in terms of unsaturated hydrocarbons weight, catalytic gasoline addition accounts for the 12% of weight of material) mixing after roll, extruded moulding.It is dried 7 hours at 120 DEG C.Carry out heat treatment in the presence of hydrogen gas, 400 DEG C of constant temperature 5 hours, obtain catalyst B.Catalyst composition, pore size distribution and main character are shown in Table 1.
Embodiment 3
According to the method for embodiment 1, by the constituent content proportioning of the catalyst C in table 1, in dissolving tank 1, add Nickel dichloride., aluminum chloride, prepare working solution A, in dissolving tank 2, add aluminum chloride, ammonium metatungstate and ammonium molybdate preparation working solution B.Being that 8wt% ammonia under agitation adds solution A by concentration, gelling temperature is maintained at 45 DEG C, at the end of pH value control 7.6, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I.1000mL water purification is added in retort, being 8wt% ammonia and solution B by concentration and flow in addition retort, gelling temperature is maintained at 60 DEG C, and flows pH value in plastic course of reaction and control 8.0, gelation time control, at 60 minutes, generates tungstenic, molybdenum, aluminum precipitation thing serosity II.By above two containing aging after sediment slurry mixing, ageing time 2 hours, aging temperature 70 DEG C, at the end of aging, pH value controls 7.6, then filter, filter cake carries out hydrothermal treatment consists under the water vapour containing carbamide, hydrothermal conditions: the mol ratio of carbamide and active metal atom total amount is 6:1, temperature is 240 DEG C, pressure is 5.0MPa, the process time is 4 hours, material after hydrothermal treatment consists is dried 9 hours at 110 DEG C, by material, roll after Ammonium hyposulfite. (Ammonium hyposulfite. addition is calculated as catalyst theory with element sulphur and needs the 115% of sulfur content) and hexene (hexene addition accounts for the 10% of weight of material) mixing, extruded moulding.It is dried 7 hours at 120 DEG C.Carry out heat treatment in the presence of hydrogen gas, 350 DEG C of constant temperature 8 hours, obtain catalyst C.Catalyst composition, pore size distribution and main character are shown in Table 1.
Embodiment 4
According to the method for embodiment 1, by the constituent content proportioning of the catalyst D in table 1, in dissolving tank 1, add Nickel dichloride., aluminum chloride, prepare working solution A, in dissolving tank 2, add aluminum nitrate, ammonium metatungstate and ammonium molybdate preparation working solution B.Being that 12wt% ammonia under agitation adds solution A by concentration, gelling temperature is maintained at 40 DEG C, at the end of pH value control 7.8, gelation time control, at 60 minutes, generates nickeliferous, aluminum precipitation thing serosity I.800mL water purification is added in retort, being 12wt% ammonia and solution B by concentration and flow in addition retort, gelling temperature is maintained at 55 DEG C, and flows pH value in plastic course of reaction and control 8.0, gelation time control, at 60 minutes, generates tungstenic, molybdenum, aluminum precipitation thing serosity II.By above two containing aging after sediment slurry mixing, ageing time 3 hours, aging temperature 70 DEG C, at the end of aging, pH value controls 8.2, then filter, filter cake carries out hydrothermal treatment consists under the water vapour containing carbamide, hydrothermal conditions: the mol ratio of carbamide and active metal atom total amount is 4:1, temperature is 250 DEG C, pressure is 3.0MPa, the process time is 6 hours, material after hydrothermal treatment consists is dried 6 hours at 80 DEG C, by material, Ammonium hyposulfite. (Ammonium hyposulfite. addition is calculated as catalyst theory with element sulphur and needs the 150% of sulfur content) and coker gasoline (presence of unsaturates is as 42.3v%) (calculate with the weight of unsaturated hydrocarbons, coker gasoline addition accounts for the 15% of weight of material) mixing after roll, extruded moulding.It is dried 10 hours at 100 DEG C.Carry out heat treatment in the presence of hydrogen gas, 500 DEG C of constant temperature 7 hours, obtain catalyst D.Catalyst composition, pore size distribution and main character are shown in Table 1.
Comparative example 1
Method for preparing catalyst as disclosed in CN102049265A, prepares the reference agent E identical with the catalyst composition of embodiment 1.In dissolving tank, add aluminum chloride, Nickel dichloride., ammonium metatungstate preparating acid sex work solution A, take 100g ammonium hydrogen carbonate and be made into the solution that molar concentration is 2.0mol/l.Adding 500mL water in retort, temperature rises to 60 DEG C.Stirring in the case of, by solution A, ammonium bicarbonate aqueous solution and concentration be 10%(weight) ammonia and flow addition retort in plastic, gelling temperature 60 DEG C, gelation time 1.0 hours, the pH value of plastic slurry is 7.8.After cemented into bundles aging 2 hours.Then filter, the filter cake obtained and molybdenum trioxide, making beating stirs, filter, filter cake is dried 8 hours at 100 DEG C, roll after material, Ammonium hyposulfite. (Ammonium hyposulfite. addition is calculated as catalyst theory with element sulphur and needs the 120% of sulfur content) and laurylene (laurylene addition accounts for the 10% of weight of material) are mixed, extruded moulding.It is dried 10 hours at 80 DEG C.Carry out heat treatment in the presence of hydrogen gas, 450 DEG C of constant temperature 6 hours, obtain final catalyst E, composition, pore size distribution and main character are shown in Table 1.
Comparative example 2
By embodiment 1 catalyst composition and preparation method, it is added without carbamide during hydrothermal treatment consists, prepares reference agent F.Composition, pore size distribution and main character are shown in Table 1.
Comparative example 3
By embodiment 1 catalyst composition and preparation method, it is added without carbamide during hydrothermal treatment consists, but adds NH3, temperature is 250 DEG C, and pressure is 4.0MPa, and the process time is 4 hours, and the mol ratio of ammonia and active metal atom total amount is 7:1, prepares reference agent G.Composition, pore size distribution and main character are shown in Table 1.
Comparative example 4
By embodiment 1 catalyst composition and preparation method, it is added without carbamide during hydrothermal treatment consists, but adds CO2, temperature is 250 DEG C, and pressure is 4.0MPa, and the process time is 4 hours, CO2It is 7:1 with the mol ratio of active metal atom total amount, prepares reference agent H.Composition, pore size distribution and main character are shown in Table 1.
Comparative example 5
The reference agent I that method for preparing catalyst preparation as disclosed in CN101255356A is identical with the catalyst composition of embodiment 1.By catalytic component content proportioning in embodiment 1, by MoO3, wolframic acid, basic nickel carbonate, carbamide (quality of carbamide with active metal mass ratio 2.5) join in there-necked flask, and add a small amount of water and make it be uniformly dispersed, it is placed in oil bath and stirs 4 hours in 130 DEG C, while hot reactant is poured in pallet and cool down, with pulverizer, the product of cooling is pulverized, it is placed in 150 DEG C of baking ovens drying, makes unnecessary carbamide decompose.The dilute nitric acid solution weighing the boehmite addition 10wt% accounting for pressed powder 30wt% makes Alumina gel, pressed powder is added in Alumina gel, with become pasty state, through kneading, extrusion, make the catalyst bar of diameter 1.6mm, after being dried 8h under infrared lamp, roll after material, Ammonium hyposulfite. (Ammonium hyposulfite. addition is calculated as catalyst theory with element sulphur and needs the 120% of sulfur content) and laurylene (laurylene addition accounts for the 10% of weight of material) are mixed, extruded moulding.It is dried 10 hours at 80 DEG C.Carry out heat treatment in the presence of hydrogen gas, 450 DEG C of constant temperature 6 hours, prepare reference agent I.Catalyst composition, pore size distribution and main character are shown in Table 1.
Comparative example 6
The reference agent J that method for preparing catalyst preparation as disclosed in CN102451703A is identical with the catalyst composition of embodiment 1.By the catalytic component content proportioning in embodiment 1, in dissolving tank 1, add Nickel dichloride., ammonium metatungstate and zirconium oxychloride preparating acid sex work solution A, in dissolving tank 2, then add sodium metaaluminate alkalescence working solution B.Adding 350mL water in retort, temperature rises to 40 DEG C.In the case of stirring, by solution A, solution B and CO2And flow plastic in addition retort, CO2Concentration is 45v%, gelling temperature 60 DEG C, gelation time 1 hour, and the pH value of plastic serosity is 7.8.CO is added during plastic2The total amount of gas and the Al in alkalescence working solution B2O3Mol ratio is 4.0.After plastic aging 2 hours.Then filter, filter cake adds 500ml water purification and molybdenum trioxide, making beating stirs, filter, filter cake is dried 8 hours at 100 DEG C, roll after material, Ammonium hyposulfite. (Ammonium hyposulfite. addition is calculated as catalyst theory with element sulphur and needs the 120% of sulfur content) and laurylene (laurylene addition accounts for the 10% of weight of material) are mixed, extruded moulding.It is dried 10 hours at 80 DEG C.Carry out heat treatment in the presence of hydrogen gas, 450 DEG C of constant temperature 6 hours, obtain final catalyst J, composition, pore size distribution and main character are shown in Table 1.
Comparative example 7
Method as disclosed in CN1951561A, detailed process is as follows:
Forming by the catalyst of embodiment 1, Nickel dichloride. and ammonium metatungstate are prepared and be dissolved in water purification, be configured to mixed solution, wherein the weight concentration of NiO is 19g/L, WO3Weight concentration be 39g/L.Be 10%(weight by concentration) ammonia under agitation adds and carries out plastic in mixed solution, gelling temperature is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control, at 60 minutes, generates nickeliferous, tungsten precipitate serosity.Then carry out aging, ageing time 2 hours, aging temperature 75 DEG C, at the end of aging, pH value controls 7.6, after filtration, after adding water purification, aluminium hydroxide and molybdenum trioxide mix homogeneously in filter cake, it is dried 8 hours at 100 DEG C, roll after material, Ammonium hyposulfite. (Ammonium hyposulfite. addition is calculated as catalyst theory with element sulphur and needs the 120% of sulfur content) and laurylene (laurylene addition accounts for the 10% of weight of material) are mixed, extruded moulding.It is dried 10 hours at 80 DEG C.Carry out heat treatment in the presence of hydrogen gas, 450 DEG C of constant temperature 6 hours, obtain final catalyst K, composition, pore size distribution and main character are shown in Table 1.
Embodiment 5
The present embodiment is catalyst activity evaluation experimental of the present invention, and contrasts with comparative example catalyst.Using A, B, C, D catalyst of the present invention and comparative example E, F, G, H, I, J, K catalyst, carry out comparative evaluation's test on 200mL small hydrogenation device, test raw material is Zhenghai mixed diesel (catalytic diesel oil accounts for the 40% of miscella weight).Raw material main character is shown in Table 4, and catalyst activity evaluates process conditions: hydrogen dividing potential drop is 6.4MPa, and reaction temperature is 360 DEG C, and during liquid, volume space velocity is 2.0h-1, hydrogen to oil volume ratio is 500:1, and evaluation result is shown in Table 5.Use sulfur compound in gas chromatography-atomic emission detector device (GC-AED) detection hydrofined oil, the results are shown in Table 6.
Can be seen that from table 1, table 2 and table 3, catalyst of the present invention is not in the case of active metal amount changes, catalyst surface active metal atom concentration increases, hydrogenation sites density increases, pore size distribution$ is more concentrated, find out that catalyst has the hydrodenitrogenationactivity activity of excellence from evaluation result table 6, in removing 4, during 6-DMDBT class macromole sulfide, demonstrate high hydrogenation activity.Catalyst is used for processed distillate, during in particular for processing nitrogen content high heavier diesel fraction, has the ultra-deep hydrodesulfuration activity of excellence.
Table 1 catalyst composition and character
| Catalyst is numbered | A | B | C | D |
| NiS, wt% | 20 | 18 | 16 | 22 |
| WS2, wt% | 36 | 38 | 32 | 34 |
| MoS2, wt% | 17 | 18 | 14 | 16 |
| Al2O3, wt% | Surplus | Surplus | Surplus | Surplus |
| Specific surface area *, m2/g | 233 | 224 | 218 | 225 |
| Pore volume *, mL/g | 0.339 | 0.306 | 0.321 | 0.327 |
| Mechanical strength, N/mm | 21.1 | 21.8 | 20.1 | 20.4 |
| Pore size distribution *, % | ||||
| ＜ 4nm | 11.45 | 12.13 | 13.57 | 13.21 |
| 4nm~8nm | 70.62 | 69.54 | 70.44 | 71.46 |
| 8nm~15nm | 15.21 | 14.94 | 12.31 | 12.12 |
| ＞ 15nm | 2.72 | 3.39 | 3.68 | 3.21 |
Continued 1
| Catalyst is numbered | E | F | G | H | I | J | K |
| NiS, wt% | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| WS2, wt% | 36 | 36 | 36 | 36 | 36 | 36 | 36 |
| MoS2, wt% | 17 | 17 | 17 | 17 | 17 | 17 | 17 |
| Al2O3, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Other/wt% | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing | Nothing |
| Specific surface area *, m2/g | 199 | 201 | 209 | 205 | 212 | 208 | 204 |
| Pore volume *, mL/g | 0.294 | 0.289 | 0.293 | 0.304 | 0.325 | 0.277 | 0.218 |
| Mechanical strength, N/mm | 17.8 | 18.1 | 19.4 | 19.2 | 9.8 | 19.4 | 17.9 |
| Pore size distribution *, % | |||||||
| ＜ 4nm | 57.23 | 17.88 | 15.85 | 15.12 | 14.42 | 18.21 | 52.98 |
| 4nm~8nm | 22.85 | 32.65 | 37.61 | 33.34 | 28.12 | 35.11 | 22.57 |
| 8nm~15nm | 14.84 | 34.12 | 31.03 | 35.97 | 39.81 | 34.24 | 19.11 |
| ＞ 15nm | 5.08 | 15.35 | 15.51 | 15.57 | 17.65 | 12.44 | 5.34 |
* note: in table 1 specific surface area of catalyst, pore volume and pore size distribution be by sulfide type catalyst in Muffle furnace, it is passed through air, room temperature is warming up to 230 DEG C ~ 260 DEG C constant temperature for 3 hours 4 hours, continues within 3 hours, to be warming up to 400 DEG C ~ 420 DEG C constant temperature 4 hours, is converted into the result that oxidized catalyst records
The weight content of table 2 catalyst table phase active metal sulphides and the ratio of the weight content of body phase active metal sulphides
| Catalyst is numbered | A | B | C | D | E |
| Table phase IW/ body phase IW | 5.49 | 3.65 | 4.99 | 7.86 | 0.99 |
| Table phase INi/ body phase INi | 3.92 | 2.49 | 3.69 | 3.54 | 1.03 |
| Table phase IMo/ body phase IMo | 4.34 | 3.81 | 4.18 | 3.99 | - |
Continued 2
| Catalyst is numbered | F | G | H | I | J | K |
| Table phase IW/ body phase IW | 1.17 | 1.16 | 1.22 | 0.94 | 1.48 | 1.11 |
| Table phase INi/ body phase INi | 1.15 | 1.18 | 1.10 | 0.99 | 1.32 | 1.08 |
| Table phase IMo/ body phase IMo | 0.94 | 1.05 | 1.09 | - | - | - |
Table 3 transmissioning electric mirror determining catalyst surface MoS2/WS2Density
| Catalyst is numbered | A | B | C | D | E | F | G | H | I | J | K |
| MoS2/WS2Density, grain/100nm | 95 | 91 | 89 | 87 | 52 | 55 | 58 | 54 | 49 | 66 | 54 |
Table 4 raw oil main character
| Project | Analysis result |
| Density (20 DEG C), g/cm3 | 0.8814 |
| Boiling range scope, DEG C | 178-375 |
| S, g/g | 13300 |
| N, g/g | 728 |
| Cetane number | 41.5 |
Table 5 catalyst activity evaluation result
| Catalyst is numbered | A | B | C | D | E |
| Generate oil density (20 DEG C), g/cm3 | 0.8395 | 0.8402 | 0.8406 | 0.8417 | 0.8534 |
| Boiling range scope, DEG C | 169-366 | 171-367 | 170-366 | 171-367 | 176-375 |
| S, g/g | 6.8 | 7.9 | 8.1 | 9.4 | 200.8 |
| N, g/g | 1.0 | 1.0 | 1.0 | 1.0 | 19.8 |
| Cetane number | 51.1 | 51.6 | 51.4 | 51.2 | 46.5 |
Continued 5
| Catalyst is numbered | F | G | H | I | J | K |
| Generate oil density (20 DEG C), g/cm3 | 0.8488 | 0.8501 | 0.8503 | 0.8542 | 0.8491 | 0.8502 |
| Boiling range scope, DEG C | 185-373 | 179-372 | 167-374 | 168-375 | 169-372 | 171-373 |
| S, g/g | 173.2 | 16.4.9 | 179.2 | 224.3 | 186.1 | 216.4 |
| N, g/g | 16.3 | 17.2 | 18.3 | 21.8 | 19.3 | 22.7 |
| Cetane number | 49.1 | 50.1 | 48.8 | 47.1 | 47.6 | 15.9 |
The content of different sulfide in table 6 hydrofined oil
| Catalyst is numbered | A | B | C | D | E |
| Nitrogen content in hydrofined oil, g/g | 1.0 | 1.0 | 1.0 | 1.0 | 19.8 |
| Sulfur content in hydrofined oil, g/g | 6.8 | 7.9 | 8.1 | 9.4 | 200.8 |
| C1-DBT, g/g | 0 | 0 | 0 | 0 | 28.3 |
| 4-BMDBT, g/g | 1.2 | 1.9 | 1.5 | 1.7 | 39.2 |
| 6-BMDBT, g/g | 0.7 | 1.2 | 1.8 | 2.1 | 35.6 |
| 4,6-BMDBT, g/g | 4.9 | 4.8 | 4.8 | 5.6 | 97.7 |
Continued 6
| Catalyst is numbered | F | G | H | I | J | K |
| Nitrogen content in hydrofined oil, g/g | 16.3 | 17.2 | 18.3 | 21.8 | 19.3 | 22.7 |
| Sulfur content in hydrofined oil, g/g | 173.2 | 164.9 | 179.2 | 224.3 | 186.1 | 216.4 |
| C1-DBT, g/g | 20.7 | 23.4 | 27.8 | 35.1 | 30.3 | 39.1 |
| 4-BMDBT, g/g | 31.5 | 35.9 | 33.9 | 49.9 | 38.1 | 40.3 |
| 6-BMDBT, g/g | 38.4 | 30.6 | 31.3 | 46.7 | 34.6 | 35.8 |
| 4,6-BMDBT, g/g | 82.6 | 75.0 | 86.2 | 92.6 | 83.1 | 101.2 |
Claims (18)
1. a sulfurized hydrogenation catalyst for refining, this catalyst is body phase Hydrobon catalyst, and its composition includes the sulfide of hydrogenation active metals component W, Ni, Mo, aluminium oxide；Wherein the sulfide of table phase active metal component W is with WS2The sulfide of the weight content of meter and body middle active metal component W mutually is with WS2The ratio of the weight content of meter is 2.0:1 ~ 7.0:1, the ratio of the weight content that the sulfide of the weight content that the sulfide of table phase active metal component Ni is counted with NiS and body phase active metal component Ni is counted with NiS as 1.5:1 ~ 5.0:1, the sulfide of table phase active metal component Mo is with MoS2The weight content of meter and the sulfide of body phase active metal component Mo are with MoS2The ratio of the weight content of meter is 1.8:1 ~ 6:1.
2. according to the catalyst described in claim 1, it is characterised in that: in described catalyst, the sulfide of table phase active metal component W is with WS2The sulfide of the weight content of meter and body middle active metal component W mutually is with WS2The ratio of the weight content of meter is 3.0:1 ~ 6.0:1, the ratio of the sulfide of the sulfide of table phase active metal component Ni weight content in terms of NiS and body phase active metal component Ni weight content in terms of NiS is 1.8 ~ 4.5:1, and the sulfide of table phase active metal component Mo is with MoS2The weight content of meter and the sulfide of body phase active metal component Mo are with MoS2The ratio of the weight content of meter is 2.5:1 ~ 4.5:1.
3. according to the catalyst described in claim 1, it is characterised in that: on the basis of the weight of Hydrobon catalyst, the sulfide of Ni, W and Mo is with NiS, WS2、MoS2Meter gross weight content is 40% ~ 95%, preferably 50% ~ 85%, and alumina content is 5% ~ 60%, preferably 15% ~ 50%.
4. according to the catalyst described in claim 1, it is characterized in that: in described Hydrobon catalyst, the mol ratio of Ni/W is 1:8 ~ 8:1, and (Ni+W)/Mo mol ratio is 1:10 ~ 10:1, being preferably as follows: the mol ratio of Ni/W is 1:4 ~ 4:1, (Ni+W)/Mo mol ratio is 1:5 ~ 5:1.
5. according to the catalyst described in claim 1, it is characterized in that: containing adjuvant component in described Hydrobon catalyst, adjuvant component is one or more in silicon, phosphorus, titanium, zirconium, boron, and in terms of element, adjuvant component weight content in Hydrobon catalyst is 1% ~ 15%.
6. the preparation method of the arbitrary described catalyst of Claims 1 to 4, including:
(1), prepare the component saline mixed solution A Han Ni and Al, precipitant is added dropwise to solution A and carries out plastic reaction, generate nickeliferous, aluminum precipitation thing serosity I；
(2), prepare the component saline mixed solution B Han W, Mo and Al, solution B and precipitant carried out and flows plastic reaction, generating tungstenic, molybdenum, aluminum precipitation thing serosity II；
(3), by the serosity I of step (1) gained and the serosity II mix homogeneously of step (2) gained, the most aging, after aging end, filter, the material water vapour obtained carries out hydrothermal treatment consists, wherein adds carbamide during hydrothermal treatment consists；
(4), step (3) gained material add Ammonium hyposulfite. and adjuvant kneading, molding after drying, be dried, carry out heat treatment the most in the presence of an inert gas, obtain sulfurized hydrogenation catalyst for refining.
The most in accordance with the method for claim 6, it is characterized in that the precipitant described in step (1) or step (2) is one or more in sodium carbonate, sodium bicarbonate, ammonia, sodium hydroxide, potassium hydroxide, potassium carbonate, potassium bicarbonate, being preferably ammonia, weights of ammonia concentration is 5%～15%.
The most in accordance with the method for claim 6, it is characterised in that in step (1) mixed solution A, Ni weight concentration in terms of NiO is 5～80g/L, and Al is with Al2O3The weight concentration of meter is 2～60g/L；In step (2) mixed solution B, W is with WO3The weight concentration of meter is 10～100g/L, and Mo is with MoO3The weight concentration 5～80g/L of meter, Al is with Al2O3The weight concentration of meter is 2～60g/L.
The most in accordance with the method for claim 6, it is characterised in that: in step (1), reaction temperature is 20～90 DEG C, preferably 30～70 DEG C；During cemented into bundles, pH value controls is 6.0
~ 11.0, preferably 7.0 ~ 9.0；Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.
The most in accordance with the method for claim 6, it is characterised in that: in step (2), reaction temperature is 30～90 DEG C, preferably 40～80 DEG C, and when flowing plastic, pH value control is 6.0
~ 11.0, preferably 7.0 ~ 9.0, gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.
11. in accordance with the method for claim 6, it is characterised in that: in step (3), aging temperature is 40～90 DEG C, preferably 50～80 DEG C, time aging, pH value controls is 6.0 ~ 10.0, being preferably 6.5 ~ 9.0, ageing time is 0.5 ~ 6.0 hour, preferably 1.0 ~ 4.0 hours.
12. in accordance with the method for claim 6, it is characterised in that: the hydrothermal conditions described in step (3) is as follows: carry out under airtight container, and temperature is 200 ~ 300 DEG C, and pressure is 1.0 ~ 8.0 MPa, and the process time is 0.5 ~ 10.0 hour；During hydrothermal treatment consists, the addition of carbamide is 0.5:1 ~ 10.0:1 with active metal tungsten, molybdenum, the mol ratio of nickle atom total amount in catalyst.
13. in accordance with the method for claim 6, it is characterised in that: the hydrothermal conditions described in step (3) is as follows: carry out under airtight container, and temperature is 210 ~ 260 DEG C, and pressure is 3.0 ~ 6.0MPa, and the process time is 1.0 ~ 6.0 hours；During hydrothermal treatment consists, the addition of carbamide is 2.0:1 ~ 8.0:1 with active metal tungsten, molybdenum, the mol ratio of nickle atom total amount in catalyst.
14. in accordance with the method for claim 6, it is characterized in that: the addition of the Ammonium hyposulfite. described in step (4) is calculated as catalyst theory with element sulphur and needs the 100%～200% of sulfur content, described adjuvant is unsaturated hydro carbons, including one or more in alkene, alkadienes, alkynes.
15. in accordance with the method for claim 6, it is characterized in that: described adjuvant is the mixture containing unsaturated hydro carbons, including one or more in coker gasoline, coker gas oil, catalytically cracked gasoline, catalytic cracking diesel oil, the boiling point of adjuvant is 110～370 DEG C, and wherein the concentration of unsaturated hydro carbons is 30v%～60v%.
16. in accordance with the method for claim 6, it is characterised in that: the addition of the Ammonium hyposulfite. described in step (4) is calculated as catalyst theory with element sulphur and needs the 105%～160% of sulfur content.
17. in accordance with the method for claim 6, it is characterised in that: in step (4), the addition of adjuvant is calculated as the 3%～50% of step (3) gained material gained dried material weight after drying with unsaturated hydro carbons.
18. in accordance with the method for claim 6, it is characterized in that: the heat treatment described in step (4) is to carry out in the presence of noble gas, at least one gas of hydrogen, and treatment temperature is 200～600 DEG C, preferably 350～500 DEG C, the process time is 2～12 hours, preferably 4～10 hours.
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