CN106179377A - A kind of preparation method of Hydrobon catalyst compositions - Google Patents

Abstract

The invention discloses the preparation method of a kind of Hydrobon catalyst compositions.This carbon monoxide-olefin polymeric is body phase Hydrobon catalyst compositions, its composition includes hydrogenation active metals component W, Ni and Mo, aluminium oxide, its preparation method carries out the method for ammonia still process precipitation and prepares nickel aluminum mixed sediment in the presence of being utilized in organic compound, parallel flow precipitation is used to prepare tungsten, molybdenum and aluminum mixed sediment, by aging after both mixing, hydrothermal treatment consists adds carbamide simultaneously, then makes carbon monoxide-olefin polymeric through steps such as molding.The particularly suitable application in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction of carbon monoxide-olefin polymeric prepared by the method, has higher hydrodesulfurization and hydrodenitrogeneration reactivity worth.

Description

A kind of preparation method of Hydrobon catalyst compositions

Technical field

The present invention relates to the preparation method of a kind of Hydrobon catalyst compositions, the preparation method of the most highly active body phase hydrotreatment catalyst composition.

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 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-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, 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 the preparation method of a kind of Hydrobon catalyst compositions.Carbon monoxide-olefin polymeric prepared by the method, table phase active site density is big, hydrogenation active metals utilization rate is high, improve the distribution of hydrogenation active metals in carbon monoxide-olefin polymeric, improving mating reaction between hydrogenation active metals, carbon monoxide-olefin polymeric pore structure is reasonable simultaneously, and active metal disperses evenly, mechanical strength is high, particularly suitable application in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction.

The preparation method of Hydrobon catalyst compositions of the present invention, including:

(1), preparation is containing Ni, Al component salt and organic compound mixed solution A, ammonia adds in solution A makes the pH value of reaction system reach more than 10, under agitation solution A heating is carried out ammonia still process and produce precipitation, to slurry pH value less than 10, generate nickeliferous, aluminum precipitation thing serosity I；

(2), preparing the component saline solution B Han W, Mo, Al, ammonia also flows generation containing tungstenic, molybdenum, aluminum precipitation thing serosity II with material B；

(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 drying, molding, washing, then drying, roasting obtain final Hydrobon catalyst compositions.

The Hydrobon catalyst compositions of the present invention, on the basis of the weight of Hydrobon catalyst compositions, NiO, WO₃And MoO₃Gross weight content be 40% ~ 95%, preferably 50% ~ 85%, alumina content is 5% ~ 60%, preferably 15% ~ 50%.In the Hydrobon catalyst compositions 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.

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), organic compound is the macromolecular compound being dissolved in water, one or more in Polyethylene Glycol, polyvinyl alcohol etc., wherein the molecular weight of Polyethylene Glycol is 200 ~ 10000, being preferably 1000 ~ 8000, the molecular weight of polyvinyl alcohol is 5000 ~ 25000, preferably 12000 ~ 20000.The consumption of described organic compound accounts for and generates nickeliferous, the 5wt% ~ 70wt%, preferably 10wt% ~ 60wt% of aluminum precipitation thing (in terms of nickel oxide and aluminium oxide) weight in step (1).

When in step (1), ammonia adds solution A, it is 30～70 DEG C that system temperature controls, it is preferably 40～60 DEG C, adds and control the pH value of reaction system after ammonia more than 10, preferably 10～13, ammonia still process makes the pH value of reaction system less than 10, being preferably 7.5～9.5, ammonia still process temperature is 80～150 DEG C, preferably 80～120 DEG C, time of ammonia distillation controls at 0.2 ~ 4.0 hour, preferably 0.5 ~ 3.0 hour.In step (1), the weight concentration of ammonia used is 15%～28%.

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 (2), the weight concentration of ammonia used is 5%～15%.

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 carbon monoxide-olefin polymeric.

Dry, molding and washing described in step (4) 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.

Be dried and the roasting that are used after step (4) molding can use this area normal condition, 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 the preparation process of Hydrobon catalyst compositions of the present invention, can add required catalyst promoter according to a conventional method, adjuvant component is one or more in silicon, phosphorus, titanium, zirconium, boron etc., preferably titanium and/or zirconium.The consumption of auxiliary agent accounts for the 0% ~ 20% of Hydrobon catalyst composition weight, and preferably 1% ~ 15%.In Hydrobon catalyst compositions 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.

Hydrobon catalyst compositions prepared by the inventive method is body phase Hydrobon catalyst compositions, and its composition includes hydrogenation active metals component W, Ni and Mo, aluminium oxide；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, it is 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 phase active metal component MoO₃Weight content and body phase active metal component MoO₃The ratio of weight content be 1.8:1 ~ 6:1, preferably 2.0:1 ~ 4.5:1.

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 carbon monoxide-olefin polymeric₃Weight 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 carbon monoxide-olefin polymeric；Table phase active metal component MoO₃Weight content be table mutually in MoO₃Weight content, body phase active metal component MoO₃Weight content be MoO in carbon monoxide-olefin polymeric₃Weight content.

The character of Hydrobon catalyst compositions 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%.

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

Hydrobon catalyst compositions prepared by the inventive method, surface activity bit density is big, active metal disperses evenly, cooperation between active metal is good, active metal utilization rate is high, and carbon monoxide-olefin polymeric 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.

The inventive method uses the method then carrying out ammonia still process in the metal salt solution that ammonia is added to acidity, available crystal grain is relatively large and evengranular nickel, aluminum precipitation thing, the introducing of organic compound simultaneously, prevent nickel in ammonia still process course of reaction, the gathering of aluminum precipitation thing, be more beneficial for active metal nickel be present in carbon monoxide-olefin polymeric table mutually in；Cocurrent process is used to prepare 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, table middle tungsten, molybdenum, nickel active metal mutually can better contact with, 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 compositions.

In the preparation method of inventive catalyst composition, 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 carbon monoxide-olefin polymeric can also be made more to concentrate, more uniformly, be conducive to improving the mechanical strength of carbon monoxide-olefin polymeric.The Hydrobon catalyst compositions 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 compositions 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.Carbon monoxide-olefin polymeric table phase active metallic content uses x-ray photoelectron spectroscopy (XPS) to measure, carbon monoxide-olefin polymeric body phase active metallic content uses inductively coupled plasma atomic emission spectrum (ICP-AES) to measure, transmissioning electric mirror determining carbon monoxide-olefin polymeric surface WS₂/MoS₂Density i.e. WS₂And MoS₂Density.In the present invention, wt% is mass fraction, and v% is volume fraction.

Embodiment 1

Nickel dichloride. and liquor alumini chloridi are dissolved in water purification respectively, and it is the Polyethylene Glycol of 6000 that addition accounts for nickel and the aluminum molecular weight of weight 25wt% in terms of nickel oxide and aluminium oxide in solution, is configured to mixed solution A, and in mixed solution A, the weight concentration of NiO is 19g/L, Al₂O₃Weight concentration be 13g/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 39g/L, MoO₃Weight concentration is 16g/L, Al₂O₃Weight concentration be 13g/L.In retort 1, solution temperature is raised to 40 DEG C, in solution A add concentration be 25wt% ammonia until formed dark blue solution, solution ph is 10.5, continue solution is warming up to 100 DEG C, ammonia still process 2 hours, pH value is 7.8, obtains nickeliferous, the precipitate serosity I of aluminum.1000mL water purification is added in retort 2, being 10 wt % ammonia and solution B by concentration and flow in addition retort 2, 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 filtering, filter cake carries out hydrothermal treatment consists under the water vapour containing carbamide, and 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, and the process time is 4 hours, and filter cake is dried 8 hours at 100 DEG C, roll, extruded moulding.Wash with water purification under room temperature.Then it is dried 10 hours at 80 DEG C, 530 DEG C of roastings 4 hours, obtains carbon monoxide-olefin polymeric A.Carbon monoxide-olefin polymeric composition, pore size distribution and main character are shown in Table 1.

Embodiment 2

Method according to embodiment 1, constituent content proportioning by the carbon monoxide-olefin polymeric B in table 1, nickel nitrate, aluminum nitrate, zirconyl chloride solution is added in dissolving tank 1, it is the polyvinyl alcohol of 18000 that addition accounts for nickel and the aluminum molecular weight of weight 15wt% in terms of nickel oxide and aluminium oxide in solution, is configured to solution A after stirring.Aluminum nitrate, ammonium metatungstate and ammonium molybdate preparation working solution B is added in dissolving tank 2.In retort 1, solution temperature is raised to 50 DEG C, in solution A add concentration be 20wt% ammonia until formed dark blue solution, solution ph is 12.0, continue solution is warming up to 120 DEG C, ammonia still process 1.5 hours, pH value is 8.2, obtains nickeliferous, the precipitate serosity I of aluminum.1000mL water purification is added in retort 2, being 8 wt % ammonia and solution B by concentration and flow in addition retort 2, gelling temperature is maintained at 55 DEG C, and flows pH value in plastic course of reaction and control 7.6, 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 4 hours, material after hydrothermal treatment consists is dried 12 hours at 70 DEG C, then extruded moulding, wash 3 times with water purification, wet bar is dried 10 hours at 100 DEG C, 480 DEG C of roastings 5 hours, obtain final carbon monoxide-olefin polymeric B, composition, pore size distribution and main character are shown in Table 1.

Embodiment 3

Method according to embodiment 1, constituent content proportioning by the carbon monoxide-olefin polymeric C in table 1, Nickel dichloride., aluminum chloride, phosphoric acid solution is added in dissolving tank 1, it is the polyvinyl alcohol of 14000 that addition accounts for nickel and the aluminum molecular weight of weight 40wt% in terms of nickel oxide and aluminium oxide in solution, it is configured to solution A after stirring, in dissolving tank 2, adds aluminum chloride, ammonium metatungstate and ammonium molybdate preparation working solution B.In retort 1, solution temperature is raised to 55 DEG C, in solution A add concentration be 18wt% ammonia until formed dark blue solution, solution ph is 12.5, continue solution is warming up to 110 DEG C, ammonia still process 2.5 hours, pH value is 8.0, obtains nickeliferous, the precipitate serosity I of aluminum.1000mL water purification is added in retort, being 12 wt % ammonia and solution B by concentration and flow in addition retort, gelling temperature is maintained at 50 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 220 DEG C, pressure is 5.0MPa, the process time is 4 hours, material after hydrothermal treatment consists is dried 8 hours at 120 DEG C, then extruded moulding, wash 1 time with water, wet bar is dried 6 hours at 110 DEG C, 600 DEG C of roastings 4 hours, obtain final carbon monoxide-olefin polymeric C, composition, pore size distribution and main character are shown in Table 1.

Embodiment 4

Method according to embodiment 1, constituent content proportioning by the carbon monoxide-olefin polymeric D in table 1, Nickel dichloride., aluminum chloride, titanium chloride solution is added in dissolving tank 1, it is the Polyethylene Glycol of 4000 that addition accounts for nickel and the aluminum molecular weight of weight 30wt% in terms of nickel oxide and aluminium oxide in solution, it is configured to solution A after stirring, in dissolving tank 2, adds aluminum nitrate, ammonium metatungstate and ammonium molybdate preparation working solution B.In anti-retort 1, solution temperature is raised to 45 DEG C, and adding concentration in solution A is 20wt%'s until forming dark blue solution, and solution ph is 11.0, continues solution is warming up to 105 DEG C, and ammonia still process 2 hours, pH value is 7.8, obtains nickeliferous, the precipitate serosity I of aluminum.1000mL water purification is added in retort 2, being 10wt% ammonia and solution B by concentration and flow in addition retort 2, 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 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, then extruded moulding, wash 4 times with water purification, wet bar is dried 8 hours at 100 DEG C, 550 DEG C of roastings 5 hours, obtain final carbon monoxide-olefin polymeric D, composition, pore size distribution and main character are shown in Table 1.

Comparative example 1

Carbon monoxide-olefin polymeric preparation method as disclosed in CN102049265A, prepares the reference agent E identical with the carbon monoxide-olefin polymeric 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, and filter cake is dried 8 hours at 100 DEG C, rolls, extruded moulding.Wash with water purification under room temperature.Then being dried 10 hours at 80 DEG C, 530 DEG C of roastings 4 hours, obtain final carbon monoxide-olefin polymeric E, composition, pore size distribution and main character are shown in Table 1.

Comparative example 2

By embodiment 1 carbon monoxide-olefin polymeric 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 carbon monoxide-olefin polymeric 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 carbon monoxide-olefin polymeric 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 carbon monoxide-olefin polymeric preparation method preparation as disclosed in CN101255356A is identical with the carbon monoxide-olefin polymeric composition of embodiment 1.By catalyst composition 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 carbon monoxide-olefin polymeric 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.Carbon monoxide-olefin polymeric composition, pore size distribution and main character are shown in Table 1.

Comparative example 6

The reference agent J that carbon monoxide-olefin polymeric preparation method preparation as disclosed in CN102451703A is identical with the carbon monoxide-olefin polymeric composition of embodiment 1.By the catalyst composition 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 filtering, filter cake adds 500mL water purification and molybdenum trioxide, and making beating stirs, and filters, and filter cake is dried 8 hours at 100 DEG C, rolls, extruded moulding.Wash with water purification under room temperature.Then being dried 10 hours at 80 DEG C, 530 DEG C of roastings 4 hours, obtain final carbon monoxide-olefin polymeric 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 10 hours at 80 DEG C, 530 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 inventive catalyst composition active appraisal experiment, and contrasts with comparative example carbon monoxide-olefin polymeric.Use A, B, C, D carbon monoxide-olefin polymeric of the present invention and comparative example E, F, G, H, I, J, K carbon monoxide-olefin polymeric; carrying 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, carbon monoxide-olefin polymeric activity rating 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, inventive catalyst composition is not in the case of active metal amount changes, carbon monoxide-olefin polymeric surface-active metal atomic concentration increases, hydrogenation sites density increases, pore size distribution$ is more concentrated, find out that carbon monoxide-olefin polymeric has the hydrodenitrogenationactivity activity of excellence from evaluation result table 6, in removing 4, during 6-DMDBT class macromole sulfide, demonstrate high hydrogenation activity.Carbon monoxide-olefin polymeric 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 carbon monoxide-olefin polymeric composition and character

Carbon monoxide-olefin polymeric is numbered	A	B	C	D
					NiO, wt%	19	18	22	14
WO3, wt%	38	34	32	30
					MoO3, wt%	16	22	18	20
Al2O3, wt%	Surplus	Surplus	Surplus	Surplus
					Other/wt%	Nothing	ZrO2/2.0	P2O5/2.0	TiO2/3.0
Specific surface area, m2/g	235	229	226	238
					Pore volume, mL/g	0.335	0.318	0.324	0.335
Mechanical strength, N/mm	22.9	22.6	22.4	23.2
					Pore size distribution, %
＜ 4nm	12.03	11.99	13.45	13.41
					4nm~8nm	71.09	69.05	70.62	71.73
8nm~15nm	14.29	14.98	13.33	12.36
					＞ 15nm	2.59	3.98	2.60	2.50

Continued 1

Carbon monoxide-olefin polymeric 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	202	204	211	232	218	198
								Pore volume, mL/g	0.315	0.303	0.314	0.301	0.340	0.242	0.212
Mechanical strength, N/mm	20.1	18.6	19.7	19.3	11.5	20.5	18.5
								Pore size distribution, %
＜ 4nm	19.23	17.42	15.12	15.05	14.25	17.25	54.45
								4nm~8nm	32.45	32.63	37.42	33.84	28.42	35.28	21.14
8nm~15nm	38.17	35.32	32.10	35.63	38.81	33.85	18.32
								＞ 15nm	10.15	14.63	15.36	15.48	19.52	13.62	6.09

The weight content of table 2 carbon monoxide-olefin polymeric table phase reactive metal oxides and the ratio of the weight content of body phase reactive metal oxides

Carbon monoxide-olefin polymeric is numbered	A	B	C	D	E
						Table phase IW/ body phase IW	4.51	3.24	4.18	3.99	0.95
Table phase INi/ body phase INi	2.85	2.01	2.72	2.45	0.91
						Table phase IMo/ body phase IMo	4.12	3.15	4.07	3.98	-

Continued 2

Carbon monoxide-olefin polymeric is numbered	F	G	H	I	J	K
							Table phase IW/ body phase IW	1.04	1.08	1.24	0.99	1.42	1.04
Table phase INi/ body phase INi	1.09	1.17	1.19	0.95	1.38	0.99
							Table phase IMo/ body phase IMo	1.01	1.11	1.05	-	-	-

Table 3 transmissioning electric mirror determining carbon monoxide-olefin polymeric surface MoS₂/WS₂Density

Carbon monoxide-olefin polymeric is numbered	A	B	C	D	E	F	G	H	I	J	K
												MoS2/WS2Density, grain/100nm	94	92	89	87	51	54	56	55	50	66	51

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 carbon monoxide-olefin polymeric Activity evaluation

Carbon monoxide-olefin polymeric is numbered	A	B	C	D	E
						Generate oil density (20 DEG C), g/cm3	0.8399	0.8401	0.8402	0.8404	0.8534
Boiling range scope, DEG C	1170-366	171-367	171-366	171-366	176-376
						S, g/g	7.7	8.3	7.1	9.2	189.8
N, g/g	1.0	1.0	1.0	1.0	19.4
						Cetane number	51.5	51.6	51.7	51.4	45.6

Continued 5

Carbon monoxide-olefin polymeric is numbered	F	G	H	I	J	K
							Generate oil density (20 DEG C), g/cm3	0.8499	0.8501	0.8503	0.8546	0.8498	0.8516
Boiling range scope, DEG C	175-372	174-371	169-373	168-376	169-373	169-374
							S, g/g	170.5	168.5	199.2	215.2	169.8	204.8
N, g/g	17.7	16.8	20.1	21.2	16.4	19.7
							Cetane number	49.2	49.6	48.3	46.1	45.6	45.9

The content of different sulfide in table 6 hydrofined oil

Carbon monoxide-olefin polymeric is numbered	A	B	C	D	E
						Nitrogen content in hydrofined oil, g/g	1.0	1.0	1.0	1.0	19.4
Sulfur content in hydrofined oil, g/g	7.7	8.3	7.1	9.2	189.8
						C1-DBT, g/g	0	0	0	0	28.3
4-BMDBT, g/g	1.1	1.5	1.2	1.6	39.2
						6-BMDBT, g/g	0. 7	1.7	1.6	1.3	35.6
4,6-BMDBT, g/g	4.9	5.1	4.3	6.3	86.7

Continued 6

Carbon monoxide-olefin polymeric is numbered	F	G	H	I	J	K
							Nitrogen content in hydrofined oil, g/g	17.7	16.8	20.1	21.2	16.4	19.7
Sulfur content in hydrofined oil, g/g	170.5	168.5	199.2	215.2	169.8	204.8
							C1-DBT, g/g	21.5	22.3	29.7	35.1	30.3	35.4
4-BMDBT, g/g	32.4	35.7	35.8	39.9	38.1	40.8
							6-BMDBT, g/g	39.6	33.6	43.5	36.7	34.6	44.5
4,6-BMDBT, g/g	77.0	76.9	90.2	103.5	66.8	84.1

Claims (13)

1. the preparation method of a Hydrobon catalyst compositions, it is characterised in that:

(1), preparation is containing Ni, Al component salt and organic compound mixed solution A, ammonia adds in solution A makes the pH value of reaction system reach more than 10, under agitation solution A heating is carried out ammonia still process and produce precipitation, to slurry pH value less than 10, generate nickeliferous, aluminum precipitation thing serosity I；

(2), preparing the component saline solution B Han W, Mo, Al, ammonia also flows generation tungstenic, molybdenum, aluminum precipitation thing serosity II with material B；

(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 drying, molding, washing, then drying, roasting obtain Hydrobon catalyst compositions.

The most in accordance with the method for claim 1, it is characterised in that: on the basis of the weight of Hydrobon catalyst compositions, NiO, WO₃And MoO₃Gross weight content be 40% ~ 95%, preferably 50% ~ 85%, alumina content is 5% ~ 60%, preferably 15% ~ 50%.

3. according to the method described in claim 1 or 2, it is characterized in that: in described Hydrobon catalyst compositions, the mol ratio of Ni/W is 1:8 ~ 8:1, (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.

The most in accordance with the method for claim 1, it is characterised in that used by step (1), the weight concentration of ammonia is 15%～28%, used by step (2), the weight concentration of ammonia is 5%～15%.

The most in accordance with the method for claim 1, 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 1, it is characterized in that one or more in Polyethylene Glycol, polyvinyl alcohol of the organic compound used by step (1), wherein the molecular weight of Polyethylene Glycol is 200 ~ 10000, it is preferably 1000 ~ 8000, the molecular weight of polyvinyl alcohol is 5000 ~ 25000, preferably 12000 ~ 20000；The consumption of described organic compound accounts for and generates nickeliferous, aluminum precipitation thing 5wt% ~ 70wt% of weight, preferably 10wt% ~ 60wt% in terms of nickel oxide and aluminium oxide in step (1).

The most in accordance with the method for claim 1, it is characterized in that when in step (1), ammonia adds solution A, it is 30～70 DEG C that system temperature controls, the pH value controlling reaction system after adding ammonia is 10～13, ammonia still process makes the pH value of reaction system be 7.5～9.5, ammonia still process temperature is 80～150 DEG C, and time of ammonia distillation controlled at 0.2 ~ 4.0 hour.

The most in accordance with the method for claim 1, 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.

The most in accordance with the method for claim 1, 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.

The most in accordance with the method for claim 1, 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 carbon monoxide-olefin polymeric.

11. in accordance with the method for claim 1, 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 carbon monoxide-olefin polymeric.

12. in accordance with the method for claim 1, it is characterised in that: being dried after step (4) molding is as follows with roasting condition: be dried 1 ~ 48 hour at 50 ~ 250 DEG C, 350 ~ 650 DEG C of roastings 1 ~ 24 hour.

13. in accordance with the method for claim 1, it is characterized in that: in Hydrobon catalyst compositions 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.