CN106179388A - A kind of preparation method of hydrotreating catalyst - Google Patents

Abstract

The invention discloses the preparation method of a kind of hydrotreating catalyst.This catalyst is bulk phase catalyst, wherein contains Ni_xW_yO_zAnd MoO₃And alumina component, its preparation method is that W, Ni, Al component reacts plastic with precipitant, prepare tungsten, nickel, aluminum precipitation thing serosity, aging after, carry out hydrothermal treatment consists with water vapour and add carbamide, then with MoO₃After making beating mix homogeneously, then in the solution containing organic compound after immersion, prepare hydrotreating catalyst through steps such as molding.This catalyst is particularly suitable to be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

Description

A kind of preparation method of hydrotreating catalyst

Technical field

The present invention relates to the preparation method of a kind of hydrotreating catalyst, the preparation method of the most highly active body phase hydrotreating catalyst.

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.

Although active metallic content is high in body phase hydrogenation catalyst, but limited by aspects such as mechanical strength, active metal easily gatherings, need to add a certain amount of adhesive component, generally meeting the requirement of mechanical strength, the addition of binding agent is the most at more than 30wt%, the most not only reduce the consumption of active metal, in making again amount of activated metal entrance body mutually so that it is hydrogenation sites can not be become, there is the problem that active metal utilization rate is low.Therefore, for body phase hydrogenation catalyst, active metal utilization rate to be improved is it is necessary to improve catalyst surface active bit density, thus improves the activity of catalyst.

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-precipitation_xW_yO_zComposite 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, and 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 make catalyst surface active, reduces the activity of catalyst.

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, needs to add the carbamide that heat extraction is unnecessary, be subsequently adding binding agent and be shaped after reaction, and such the method yet suffers from the addition of binding agent and makes the low density problem of catalyst surface active position.

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 improve the distribution of hydrogenation active metals, more active metal is made to be distributed in channel surfaces and form hydrogenation sites, improving 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.

Summary of the invention

For the deficiencies in the prior art, the invention provides the preparation method of a kind of hydrotreating catalyst.Catalyst table prepared by the method middle tungsten and nickel active site density mutually is big, can be with molybdenum no-float, hydrogenation active metals utilization rate is high, catalyst pore structure is reasonable simultaneously, active metal disperses evenly, mechanical strength is high, particularly suitable application in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

The preparation method of hydrotreating catalyst of the present invention, including:

(1), preparation containing the mixed solution A of W, Ni, Al component, be added dropwise to precipitant and carry out plastic reaction, aging, generate tungstenic, nickel, aluminum precipitation thing serosity；

(2), the mix slurry of step (1) gained being filtered, the material water vapour obtained after filtration carries out hydrothermal treatment consists, wherein adds carbamide during hydrothermal treatment consists；

(3) mixtures of materials of step (2) gained and MoO₃Making beating mix homogeneously, filters, washs；

(4), step (3) gained material soak in the solution containing organic compound, drying, molding, then drying and roasting obtain final hydrotreating catalyst.

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..

The hydrotreating catalyst of the present invention, wherein W, Ni exist with composite oxides form: Ni_xW_yO_z, z=x+3y, Mo are with oxide form existence: MoO₃, composite oxides Ni_xW_yO_zThe ratio of middle x and y is 1:10 ~ 10:1, preferably 1:5 ~ 5:1, composite oxides Ni_xW_yO_zWith oxide M oO₃Weight ratio be 1:12 ~ 12:1, preferably 1:6 ~ 6:1.

The hydrotreating catalyst of the present invention, on the basis of the weight of hydrotreating catalyst, composite oxides Ni_xW_yO_zWith oxide M oO₃Gross weight content be 40% ~ 95%, preferably 45% ~ 85%, alumina content is 1% ~ 50%, preferably 5% ~ 35%.

Precipitant described in step (1) 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%.The described preparation saline mixed solution containing active metal Ni, W, Al component, wherein Ni weight concentration in terms of NiO is 5～80g/L, preferably 10～60g/L；W is with WO₃The weight concentration of meter is 10～100g/L, preferably 20～80g/L；Al is with Al₂O₃The weight concentration of meter is 5～100g/L, preferably 10～80g/L.Can be one or more in nickel sulfate, nickel nitrate, basic nickel carbonate, Nickel dichloride. containing nickel salt, tungsten salt can be one or more in sodium tungstate, ethyl ammonium metatungstate, ammonium metatungstate, and 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 ~ 10.0.Gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.After plastic, 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 (2) 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, nickel) atom total amount in catalyst.

Dry, molding and washing described in step (3) can use this area conventional method to carry out.Drying condition is as follows: being dried 1 ~ 48 hour at 50 ~ 250 DEG C, preferably 80 ~ 180 DEG C are dried 4 ~ 36 hours.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.Washing is usually and uses deionized water or wash containing decomposable asymmetric choice net salt (such as ammonium acetate, ammonium chloride, ammonium nitrate etc.) solution, is washed till neutrality.

Organic solvent described in step (4) is one or more in organic compounds containing nitrogen or nonionic surfactant.One or more in the preferred organic amine of described organic compounds containing nitrogen, such as: one or more in ethylenediamine, EDTA, tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, cetyl trimethylammonium bromide etc..Described nonionic surfactant is one or more in poly-second diether, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, aliphatic alcohol polyethenoxy ester, polyoxyethylene amine, polyoxyethylate amide, fatty glyceride.Described organic compound is 0.1 ~ 3.0 with the mol ratio of the active metal nickel in terms of oxide and tungsten, molybdenum sum, preferably 0.3 ~ 2.0.Liquid-solid volume ratio when soaking with solution of organic compound is 1.0 ~ 4.0, preferably 1.0 ~ 2.5, and soak time is 0.5～12.0 hour, preferably 2.0～10.0 hours.

Being dried described in step (4) can use this area normal condition with roasting, drying condition is as follows: be dried 1 ~ 48 hour at 50 ~ 250 DEG C, roasting condition was as follows: 350 ~ 650 DEG C of roastings 1 ~ 24 hour, preferably drying condition is as follows: being dried 4 ~ 36 hours at 80 ~ 180 DEG C, roasting condition was as follows: 400 ~ 600 DEG C of roastings 2 ~ 12 hours.

In hydrotreating 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 the catalyst is 0 ~ 20%, preferably 1% ~ 15%.In hydrotreating catalyst preparation process of the present invention, preferably during preparation mixed solution A, add the compound containing adjuvant component, i.e. titanium source and/or zirconium source.Titanium source can use one or more in Titanium Nitrate, titanium sulfate, titanium chloride etc., zirconium source can use one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride etc..

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.

Hydrotreating catalyst prepared by the inventive method is body phase hydrotreating catalyst, and its composition includes hydrogenation active metals component W, Ni and Mo, aluminium oxide；Wherein W, Ni exist with composite oxides form: Ni_xW_yO_z, z=x+3y, Mo are with oxide form existence: MoO₃, wherein table phase active metal component WO₃Weight content and body phase active metal component WO₃The ratio of weight content be 2.0:1 ~ 7.0:1, preferably 2.5:1 ~ 5.0:1, the weight content of table phase active metal component NiO is 1.2:1 ~ 4.5:1 with the ratio of the weight content of body phase active metal component NiO, is preferably: 1.8 ~ 3.0:1, table mutually in MoO₃Weight content and body mutually in MoO₃The ratio of weight content be 0.95:1 ~: 1..2:1, be preferably: 1.0:1 ~ 1.1:1.

In the present invention, table phase active metal component WO₃Weight content be table mutually in WO₃Weight content, body phase active metal component WO₃Weight content be WO in catalyst₃Weight content；The weight content of table phase active metal component NiO is the weight content of table middle NiO mutually, and the weight content of body phase active metal component NiO is the weight content of NiO in catalyst；Table phase active metal component MoO₃Weight content be table mutually in MoO₃Weight content, body phase active metal component MoO₃Weight content be MoO in catalyst₃Weight content.

The character of hydrotreating catalyst prepared by the inventive method is as follows: specific surface area is 180 ~ 450m²null/g，Pore volume is 0.20 ~ 0.80ml/g，Pore-size distribution is as follows: the pore volume shared by the hole of a diameter of below 4nm accounts for the 1% ~ 20% of total pore volume，Pore volume shared by the hole of a diameter of 4 ~ 8nm accounts for the 55% ~ 80% of total pore volume，Pore volume shared by the hole of a diameter of 8 ~ 15nm accounts for the 2% ~ 20% of total pore volume，The pore volume of a diameter of more than 15nm account for total pore volume for 0.1% ~ 5.0%，Preferably pore-size distribution is as follows: the pore volume shared by the hole of a diameter of below 4nm accounts for the 5% ~ 17% of total pore volume，Pore volume shared by the hole of a diameter of 4 ~ 8nm account for total pore volume for 61% ~ 75%，Pore volume shared by the hole of a diameter of 8 ~ 15nm accounts for the 4% ~ 17% of total pore volume，The pore volume of a diameter of more than 15nm account for total pore volume for 0.5% ~ 5.0%.

Hydrotreating catalyst of the present invention is the body phase hydrotreating catalyst of oxidation state, and conventional method can be used before use to carry out presulfurization.

In hydrotreating catalyst of the present invention, active metal tungsten and nickel surface active site density are 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.

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, 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, and promote the active metal MoO with follow-up addition₃Contact probability, improve its cooperation degree.In preparation process, the addition of organic compound makes the molybdenum oxide even particle size of roasting, and is uniformly distributed in the catalyst, increases MoO further₃Contact probability with W, Ni active metal.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 hydrotreating 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 hydrotreating 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.In the present invention, wt% is mass fraction, and v% is volume fraction.

Embodiment 1

Respectively Nickel dichloride., ammonium metatungstate and liquor alumini chloridi being dissolved in water purification, be configured to containing acidic components mixed solution, in mixed solution, the weight concentration of NiO is 20g/L, WO₃Weight concentration be 40g/L, Al₂O₃Weight concentration be 27g/L.The temperature of acidic components mixed solution being risen to 60 DEG C, in the case of stirring, is that 10wt% ammonia is added dropwise to acid solution and reacts by concentration, 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, filter cake is carried out containing hydrothermal treatment consists under urea water steam, hydrothermal conditions: the mol ratio of carbamide and active metal tungsten and nickle atom total amount is 5:1, temperature is 220 DEG C, pressure is 5.0MPa, the process time is 3 hours, after material making beating after hydrothermal treatment consists stirs, add molybdenum trioxide, filter, wash 2 times with water, filter cake is dipped in tetraethylammonium bromide solution, tetraethylammonium bromide and reactive metal oxides (nickel and tungsten, molybdenum) mol ratio is 0.6, liquid-solid volume ratio is 1.2, after soaking 5 hours, filter cake is dried 6 hours at 90 DEG C, then extruded moulding, preformed catalyst is dried 5 hours at 100 DEG C, 500 DEG C of roastings 4 hours, obtain final catalyst A, composition, pore size distribution and main character are shown in Table 1.

Embodiment 2

Aluminum chloride, Nickel dichloride., ammonium metatungstate and zirconium oxychloride preparating acid sex work solution is added in dissolving tank.The temperature of acidic components mixed solution is risen to 50 DEG C.In the case of stirring, being that 15wt% ammonia is added dropwise to acid solution and reacts by concentration, gelling temperature 50 DEG C, gelation time 1.5 hours, the pH value of plastic slurry is 8.0.After cemented into bundles aging 2 hours.Then filter, filter cake is carried out containing hydrothermal treatment consists under urea water steam, hydrothermal conditions: the mol ratio of carbamide and active metal tungsten and nickle atom total amount is 4:1, temperature is 250 DEG C, pressure is 4.0MPa, the process time is 5 hours, after material making beating after hydrothermal treatment consists stirs, add molybdenum trioxide, filter, wash 3 times with water, filter cake is dipped in poly-second two ethereal solution, poly-second diether and reactive metal oxides (nickel and tungsten, molybdenum) mol ratio is 0.8, liquid-solid volume ratio is 1.1, after soaking 4 hours, it is dried 10 hours at 90 DEG C, then extruded moulding, wet bar is dried 5 hours at 100 DEG C, 450 DEG C of roastings 6 hours, obtain final catalyst B, 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 catalyst C in table 1, in dissolving tank, add Nickel dichloride., phosphoric acid, aluminum chloride, ammonium metatungstate preparating acid sex work solution.The temperature of acidic components mixed solution being risen to 45 DEG C, in the case of stirring, is that 12wt% ammonia is added dropwise to acid solution and reacts by concentration, gelling temperature 45 DEG C, gelation time 1.2 hours, the pH value of plastic slurry is 7.6.After cemented into bundles aging 2 hours.Then filter, filter cake is carried out containing hydrothermal treatment consists under urea water steam, hydrothermal conditions: the mol ratio of carbamide and active metal tungsten and nickle atom total amount is 3:1, temperature is 200 DEG C, pressure is 6.0MPa, the process time is 2 hours, after material making beating after hydrothermal treatment consists stirs, add molybdenum trioxide, filter, wash 1 time with water, filter cake is dipped in alkylphenol polyoxyethylene solution, alkylphenol polyoxyethylene and reactive metal oxides (nickel and tungsten, molybdenum) mol ratio is 1.0, liquid-solid volume ratio is 1.3, after soaking 3 hours, it is dried 8 hours at 130 DEG C, then extruded moulding, it is dried 5 hours at 100 DEG C, 600 DEG C of roastings 3 hours, obtain final catalyst C, composition, pore size distribution and main character are shown in Table 1.

Embodiment 4

Method according to embodiment 1, by the constituent content proportioning of catalyst D in table 1, Nickel dichloride., aluminum chloride, ammonium metatungstate, titanium chloride solution preparating acid sex work solution is added in dissolving tank, the temperature of acidic components mixed solution is risen to 55 DEG C, in the case of stirring, it is that 8wt% ammonia is added dropwise to acid solution and reacts by concentration, gelling temperature 55 DEG C, gelation time 1.0 hours, the pH value of plastic slurry is 8.8.After cemented into bundles aging 2 hours.Then filter, filter cake is carried out containing hydrothermal treatment consists under urea water steam, hydrothermal conditions: the mol ratio of carbamide and active metal tungsten and nickle atom total amount is 6:1, temperature is 300 DEG C, pressure is 6.0MPa, the process time is 4 hours, after material making beating after hydrothermal treatment consists stirs, add molybdenum trioxide, filter, washing, filter cake is dipped in cetyl trimethylammonium bromide solution, cetyl trimethylammonium bromide and reactive metal oxides (nickel and tungsten, molybdenum) mol ratio is 1.2, liquid-solid volume ratio is 1.1, after soaking 6 hours, it is dried 10 hours at 80 DEG C, then extruded moulding, wet bar is dried 6 hours at 100 DEG C, 550 DEG C of roastings 4 hours, obtain final catalyst D, 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 10wt% 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 filtering, the filter cake obtained and molybdenum trioxide, making beating stirs, and filters, filter cake is dried 6 hours at 90 DEG C, then extruded moulding, washs 3 times with water purification, and wet bar is dried 5 hours at 100 DEG C, 500 DEG C of roastings 4 hours, obtaining 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, treatment temperature 220 DEG C, pressure 5MPa, 3 hours time, the mol ratio of ammonia and active metal atom total amount is 5:1, 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, treatment temperature 220 DEG C, pressure 5MPa, 3 hours time, CO₂It is 5:1 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 the mass ratio of active metal substance be 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 10% accounting for pressed powder 30% weight 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 5h under infrared lamp, put in baking oven and be dried 10 hours at 110 DEG C, 400 DEG C of roasting 5h in Muffle furnace, prepare reference agent I.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, and filters, and filter cake is dried 6 hours at 90 DEG C, then extruded moulding, washing 3 times with water purification, wet bar was dried 5 hours at 100 DEG C, 500 DEG C of roastings 4 hours, obtaining 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, aging at the end of pH value control 7.6, after filtration, after adding water purification, aluminium hydroxide and molybdenum trioxide mix homogeneously in filter cake, extruded moulding, wash with water purification under room temperature.Then it is dried 5 hours at 100 DEG C, 500 DEG C of roastings 4 hours, obtains catalyst K.Catalyst 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 3, 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 4.Use sulfur compound in gas chromatography-atomic emission detector device (GC-AED) detection hydrotreating oil, the results are shown in Table 5.

Can be seen that from table 1-2, catalyst of the present invention is not in the case of active metal amount changes, catalyst surface metal relative atomic 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 5, 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
					NiO, wt%	19	18	16	24
WO3, wt%	38	36	34	30
					MoO3, wt%	16	20	14	16
Al2O3, wt%	Surplus	Surplus	Surplus	Surplus
					Other/wt%	Nothing	ZrO2/2.0	P2O5/2.0	TiO2/3.0
Specific surface area, m2/g	238	228	218	224
					Pore volume, mL/g	0.331	0.315	0.302	0.319
Mechanical strength, N/mm	23.0	22.2	22.9	23.4
					Pore size distribution, %
＜ 4nm	12.14	11.25	12.12	12.91
					4nm~8nm	70.01	69.41	71.16	71.89
8nm~15nm	15.18	15.54	13.45	12.49
					＞ 15nm	2.67	3.8	3.27	2.71

Continued 1

Catalyst is numbered	E	F	G	H	I	J	K
								NiO, wt%	19	19	19	19	19	19	19
WO3, wt%	38	38	38	38	38	38	38
								MoO3, wt%	16	16	16	16	16	16	16
Al2O3, wt%	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus
								Other/wt%	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing	Nothing
Specific surface area, m2/g	212	201	203	199	232	218	198
								Pore volume, mL/g	0.315	0.293	0.301	0.292	0.340	0.242	0.212
Mechanical strength, N/mm	20.3	19.5	19.7	20.5	11.5	20.5	18.5
								Pore size distribution, %
＜ 4nm	19.23	17.44	16.22	15.48	14.25	17.25	54.45
								4nm~8nm	32.45	32.51	33.14	33.56	28.42	35.28	21.14
8nm~15nm	38.17	35.39	33.74	35.94	38.81	33.85	18.32
								＞ 15nm	10.15	14.66	16.9	16.13	16.25	13.62	6.09

The weight content of table 2 catalyst table phase reactive metal oxides and the ratio of the weight content of body phase reactive metal oxides

Catalyst is numbered	A	B	C	D	E
						Table phase IW/ body phase IW	4.39	3.84	4.13	3.85	0.95
Table phase INi/ body phase INi	3.35	2.81	3.14	2.90	0.91
						Table phase IMo/ body phase IMo	1.01	1.01	0.99	1.00	1.01

Continued 2

Catalyst is numbered	F	G	H	I	J	K
							Table phase IW/ body phase IW	1.12	1.04	1.12	0.99	1.42	1.04
Table phase INi/ body phase INi	1.11	1.08	1.18	0.94	1.38	0.99
							Table phase IMo/ body phase IMo	0.99	1.01	1.02	1.01	1.00	-

Table 3 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 4 catalyst activity evaluation result

Catalyst is numbered	A	B	C	D	E
						Generate oil density (20 DEG C), g/cm3	0.8388	0.8403	0.8405	0.8401	0.8534
Boiling range scope, DEG C	168-368	170-367	169-368	170-369	176-376
						S, g/g	7.2	8.3	9.1	8.8	189.8
N, g/g	1.0	1.0	1.0	1.0	19.4
						Cetane number	51.8	52.1	51.6	51.9	45.6

Continued 4

Catalyst is numbered	F	G	H	I	J	K
							Generate oil density (20 DEG C), g/cm3	0.8497	0.8501	0.8515	0.8546	0.8498	0.8516
Boiling range scope, DEG C	178-372	178-373	172-373	168-376	169-373	169-374
							S, g/g	174.3	168.5	181.9	215.2	169.8	204.8
N, g/g	17.3	18.1	19.9	21.2	16.4	19.7
							Cetane number	49.4	50.7	45.8	46.1	45.6	45.9

The content of different sulfide in table 5 hydrotreating oil

Catalyst is numbered	A	B	C	D	E
						Nitrogen content in hydrotreating oil, g/g	1.0	1.0	1.0	1.0	19.4
Sulfur content in hydrotreating oil, g/g	7.2	8.3	9.1	8.8	189.8
						C1-DBT, g/g	0	0	0	0	28.3
4-BMDBT, g/g	1.0	1.6	1.4	1.4	39.2
						6-BMDBT, g/g	1.2	1.5	1.8	1.5	35.6
4,6-BMDBT, g/g	5.0	5.2	5.9	4.9	86.7

Continued 5

Catalyst is numbered	F	G	H	I	J	K
							Nitrogen content in hydrotreating oil, g/g	17.3	18.1	19.9	21.2	16.4	19.7
Sulfur content in hydrotreating oil, g/g	174.3	168.5	181.9	215.2	169.8	204.8
							C1-DBT, g/g	20.7	23.4	27.8	35.1	30.3	35.4
4-BMDBT, g/g	31.5	35.9	33.9	39.9	38.1	40.8
							6-BMDBT, g/g	38.4	30.6	31.3	36.7	34.6	44.5
4,6-BMDBT, g/g	83.9	78.6	88.9	103.5	66.8	84.1

Claims (14)

1. a preparation method for hydrotreating catalyst, including:

(1), preparation containing the mixed solution A of W, Ni, Al component, be added dropwise to precipitant and carry out plastic reaction, aging, generate tungstenic, nickel, aluminum precipitation thing serosity；

(2), the mix slurry of step (1) gained being filtered, the material water vapour obtained after filtration carries out hydrothermal treatment consists, wherein adds carbamide during hydrothermal treatment consists；

(3), the mixtures of materials of step (2) gained and MoO₃Making beating mix homogeneously, filters, washs；

(4), step (3) gained material soak in the solution containing organic compound, drying, molding, then drying and roasting obtain hydrotreating catalyst.

The most in accordance with the method for claim 1, it is characterised in that in described hydrotreating catalyst, W, Ni exist with composite oxides form: Ni_xW_yO_z, z=x+3y, Mo are with oxide form existence: MoO₃, composite oxides Ni_xW_yO_zThe ratio of middle x and y is 1:10 ~ 10:1, preferably 1:5 ~ 5:1, composite oxides Ni_xW_yO_zWith oxide M oO₃Weight ratio be 1:12 ~ 12:1, preferably 1:6 ~ 6:1.

3. according to the method described in claim 1 or 2, it is characterised in that: on the basis of the weight of hydrotreating catalyst, composite oxides Ni_xW_yO_zWith oxide M oO₃Gross weight content be 40% ~ 95%, preferably 45% ~ 85%, alumina content is 1% ~ 50%, preferably 5% ~ 35%.

The most in accordance with the method for claim 1, it is characterized in that: the precipitant described in step (1) 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 1, it is characterised in that the described preparation saline mixed solution containing active metal Ni, W, Al component, wherein Ni weight concentration in terms of NiO is 5～80g/L, preferably 10～60g/L；W is with WO₃The weight concentration of meter is 10～100g/L, preferably 20～80g/L；Al is with Al₂O₃The weight concentration of meter is 5～100g/L, preferably 10～80g/L.

The most in accordance with the method for claim 1, 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, being preferably 7.0 ~ 10.0, gelation time is 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour, after plastic, aging temperature is 40～90 DEG C, being 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.

The most in accordance with the method for claim 1, it is characterized in that the hydrothermal conditions described in step (2) is as follows: carry out under airtight container, temperature is 200 ~ 300 DEG C, it is preferably 210 ~ 260 DEG C, pressure is 1.0 ~ 8.0 MPa, being preferably 3.0 ~ 6.0MPa, the process time is 0.5 ~ 10.0 hour, preferably 1.0 ~ 6.0 hours.

The most in accordance with the method for claim 1, it is characterised in that in step (2), during hydrothermal treatment consists, the addition of carbamide is 0.5:1 ~ 10.0:1, preferably 2.0:1 ~ 8.0:1 with active metal tungsten, the mol ratio of nickle atom total amount in catalyst.

The most in accordance with the method for claim 1, it is characterised in that the organic compound described in step (4) is one or more in organic compounds containing nitrogen or nonionic surfactant.

The most in accordance with the method for claim 9, it is characterised in that the organic compounds containing nitrogen described in step (4) is one or more in ethylenediamine, EDTA, tetraethylammonium bromide, tetraethyl ammonium hydroxide, 4-propyl bromide, cetyl trimethylammonium bromide；Described nonionic surfactant is one or more in poly-second diether, alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, aliphatic alcohol polyethenoxy ester, polyoxyethylene amine, polyoxyethylate amide, fatty glyceride.

11. in accordance with the method for claim 1, it is characterized in that step (4) described organic compound is 0.1 ~ 3.0 with the mol ratio of the active metal nickel in terms of oxide and tungsten, molybdenum sum, it is preferably 0.3 ~ 2.0, it is 1.0 ~ 4.0 by liquid-solid volume ratio during solution soaking containing organic compound, it is preferably 1.0 ~ 2.5, soak time is 0.5～12.0 hour, preferably 2.0～10.0 hours.

12. in accordance with the method for claim 1, it is characterized in that the drying condition described in step (4) is as follows: be dried 1 ~ 48 hour at 50 ~ 250 DEG C, roasting condition was as follows: 350 ~ 650 DEG C of roastings 1 ~ 24 hour, preferably drying condition is as follows: being dried 4 ~ 36 hours at 80 ~ 180 DEG C, roasting condition was as follows: 400 ~ 600 DEG C of roastings 2 ~ 12 hours.

13. in accordance with the method for claim 1, it is characterized in that: in hydrotreating catalyst preparation process, the compound containing adjuvant component is added in mixed solution A, i.e. titanium source and/or zirconium source, titanium source uses one or more in Titanium Nitrate, titanium sulfate, titanium chloride, and zirconium source uses one or more in zirconium nitrate, zirconium chloride, zirconium oxychloride.

14. in accordance with the method for claim 1, it is characterised in that in described hydrotreating catalyst, table phase active metal component WO₃Weight content and body phase active metal component WO₃The ratio of weight content be 2.0:1 ~ 7.0:1, preferably 2.5:1 ~ 5.0:1, the weight content of table phase active metal component NiO is 1.2:1 ~ 4.5:1 with the ratio of the weight content of body phase active metal component NiO, is preferably: 1.8 ~ 3.0:1, table mutually in MoO₃Weight content and body mutually in MoO₃The ratio of weight content be 0.95:1 ~: 1..2:1, be preferably: 1.0:1 ~ 1.1:1.