CN110038584A - The method for preparing Hydrobon catalyst - Google Patents

Abstract

The invention discloses a kind of preparation methods of Hydrobon catalyst.The Hydrobon catalyst be first by containing Ni, W mixed solution A and sodium metaaluminate alkaline solution cocurrent react, aging is carried out to gained slurries, the mixed solution B containing W, Mo, Al component is added in the slurries after above-mentioned aging with ammonium hydroxide cocurrent again, aging is carried out again, then through first dry, molding, second it is dry after with the processing of the mixed aqueous solution of aluminium salt and organic acid, then it is washed, third is dry, roasting and etc. Hydrobon catalyst is made.The catalyst can be applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction, hydrodesulfurization and hydrodenitrogeneration reactivity with higher, especially handle the diesel raw material of high nitrogen high sulfur content.

Description

The method for preparing Hydrobon catalyst

Technical field

The present invention relates to a kind of method for preparing Hydrobon catalyst, especially a kind of body phase Hydrobon catalyst Preparation method.

Background technique

Currently, crude oil heaviness and in poor quality increasingly, the sustainable development of world economy and environmental regulation is increasingly tight in addition Lattice need to produce a large amount of light clean fuels.Exploitation and using super-low sulfur even without sulphur vapour, diesel oil be within the scope of the world today it is clear The trend of clean fuel development.Reaction temperature, hydrogen are such as improved by increasing reaction severity using traditional Hydrobon catalyst The deep desulfuration even ultra-deep desulfurization of diesel oil also may be implemented in partial pressure or reduction reaction velocity etc., but reaction temperature is upper It rises the variation that will lead to product colour and catalyst life shortens, and reducing air speed then means the reduction for the treatment of capacity.For existing For some hydrogenation plants, design pressure has been fixed, and the amplitude for improving hydrogen partial pressure is limited.Therefore, currently by using The catalyst of more high desulfurization activity is one of the important means of deep desulfuration.

Sulfur-containing compound in petroleum distillate containing various structures and different molecular weight, but in the ultra-deep desulfurization stage (sulfur content is lower than 50 μ g/g), the mainly sulfur-containing compound of the substituted base such as removing 4,6- dimethyl Dibenzothiophene class.By Make to produce steric hindrance between sulphur atom and the activated centre of catalyst in the adjacent methyl of sulphur atom, sulphur atom is not easy to connect The activated centre of proximal response, thus lead to reaction rate sharp fall.

Conventional load type hydrogenation catalyst is limited by carrier pore structure, and active metal load capacity is usually no more than 30wt%, the activated centre quantity that loaded catalyst can be provided is limited, although can to activated centre number amount and type distribution Adjustment is optimized, but since the limit bottleneck of activated centre quantity can not be broken through, the space for increasing substantially hydrogenation activity has Limit, is difficult meet the needs of refinery is to V diesel product of producing country.The hydrogenation catalyst of body phase method preparation is most of by active gold Belong to component to constitute, the limitation of tenor can be got rid of, can in any regulating catalyst each active component ratio, improve catalysis The Hydrogenation of agent can be in the item for not improving device reaction severity since bulk phase catalyst has excellent hydrogenation activity Under part, directly production meet National V emission standard without sulfur diesel product, the processing of device can be improved without transformation in original device Amount reduces the production cost of refinery, realizes energy efficiency.

Body phase hydrogenation catalyst is divided into sulphided state body phase hydrogenation catalyst and oxidation state body phase hydrogenation catalyst.Oxidation state body Phase catalyst preparation process is relatively easy, at low cost, industrial application, it mainly uses coprecipitation to prepare, with active gold Belong to based on component, it typically is group VIB metallic elements (Mo, W) and group VIII metal element (Ni), and active metal atom is mutual Staggeredly, reaction compartment is provided for reactant molecule, active metal is exposed to catalyst surface, provides reaction for reactant molecule and lives Property center.Loaded catalyst is formed by mixing compared with low activity one kind activated centre with higher active two class activated centre , and it is two class activated centres that bulk phase catalyst activated centre is substantially all, bulk phase catalyst mainly passes through increase catalyst On activated centre density to greatly improving its catalytic activity.Chianelli etc. proposes spoke edge-seamed edge model to explain The generation in unsupported catalyst activated centre, model is by MoS₂/WS₂The seamed edge active sites of crystal grain layer side edge are known as spoke edge position, mention For adding hydrogen center, by MoS₂/WS₂The seamed edge active sites of crystal grain internal layer are known as seamed edge position, provide hydrogenolysis center.Therefore, catalyst Add the distribution of hydrogen and hydrogenolysis activity and active sites closely related.

During the reaction, reactant molecule only reacts in its close catalyst surface, using existing total The catalyst surface active metal dispersion of precipitation method preparation is uneven, while different hydrogenation active metals disorder distributions cause activity There is no good coordinative role between metal, the metal of high-content is easy to happen metallic particles excess accumulation in bulk phase catalyst, Reduce active mutually generation in this way, so that active metal is can't be hydrogenation sites, influence the benefit of the active metal of catalyst With rate, and improve the use cost of catalyst.

CN1951561A discloses the method for preparing hydrogenation catalyst using co-precipitation, and catalyst uses active metal Ni, W Component and precipitating reagent co-precipitation generate Ni_xW_yO_zIt is molten aluminium salt can be added in above process in composite oxides precursor Liquid, can also to be directly added into aluminium hydroxide after plastic, then with MoO₃Mashing mixing, filtering, molding, activation are final catalysis Agent.During this method prepares bulk phase catalyst, molybdenum oxide and Ni_xW_yO_zComposite oxides are directly beaten mixing, lead to active gold Belong to excess accumulation, reduces the quantity of active phase, reduce the utilization rate of active metal.

CN201410062726.8 discloses a kind of preparation method of non-loading type high-activity hydrogenation catalyst.This method is The acid solution A for containing at least one group VIII metallic compound and at least one vib metals compound is first prepared, and Alkaline solution B containing at least one silicon source or silicon source, two kinds of solution is slowly mixed together into precipitation reactor, in temperature 20 Coprecipitation reaction is carried out between ~ 120 DEG C, pH value 7 ~ 12, obtains slurries, and slurries are subjected to aging, suction filtration, washing, drying, molding And calcination process, obtain catalyst.This method does not use conventional alkaline precipitating agent, but uses and contain a kind of silicon source or silicon source Alkaline solution B do precipitating reagent, although this method changes precipitating reagent, but the active metal without changing bulk phase catalyst disperses Property, active phase amount do not obviously increase, and the utilization rate of metal does not improve.

Ammonium hydrogen carbonate is added in body phase hydrogenation catalyst disclosed in CN102049265A during coprecipitated, Carbon dioxide is added in body phase hydrogenation catalyst disclosed in CN102451703A during coprecipitated, generates carbonate or bicarbonate Salt, the above method is that a certain amount of gas is released in roasting process using it, under the percussion of gas, increases catalysis The Kong Rong of agent, specific surface area.Although this method under the percussion of gas, makes part metals active sites sudden and violent while reaming It is exposed at the surface of catalyst, but catalyst pores easily collapse under gas effect, therefore, the effect to active metal dispersibility is improved It is limited.

CN201510212110.9 discloses a kind of body phase Hydrobon catalyst and preparation method thereof.This method is using just Addition prepares nickel aluminium mixed sediment, prepares tungsten, molybdenum and aluminium mixed sediment using parallel flow precipitation, then after the two is mixed it is old Change after filtering obtained metal mixture and steam treatment and urea is added under appropriate conditions, the material warp after hydro-thermal process Dry, molding, roasting obtain catalyst.Table phase active metallic content is high in the resulting bulk phase catalyst of this method, is easy excessive Accumulation, to influence the active pattern and dispersibility for mutually accumulating pile layer.

Existing coprecipitation method is prepared in bulk phase catalyst technology, and different coprecipitation modes, Gelation Conditions can be living to catalyst Property metal fit system, interaction relationship has very big between the distributions of hydrogenation active metals and different hydrogenation active metals Influence, also result in vulcanization after bulk phase catalyst in MoS₂/WS₂Pattern occur it is apparent different.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provides a kind of methods for preparing Hydrobon catalyst.Party's legal system Standby catalyst is a kind of body phase Hydrobon catalyst, and effective active is mutually more, and mutual facilitation is stronger, is had Higher hydrodesulfurization and hydrodenitrogeneration reactivity worth are suitable for applying in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction, special It is not the diesel raw material for handling high nitrogen high sulfur content.

Under distillate ultra-deep hydrodesulfuration reaction environment, nitrogen-containing organic compound present in distillate is de- to hydrogen is added Reaction of Salmon-Saxl generates apparent inhibiting effect, and hydrodesulfurization activity is reduced as the nitrogen content in raw material increases, this is because evaporating Competitive Adsorption, the adsorption energy of nitrogenous compound occur on catalyst activity position for the nitrogenous compound and sulfur-containing compound divided in oil Power is stronger, occupies the active sites on catalyst, and sulfur-containing compound is made to be difficult to approach, it is suppressed that hydrodesulfurization reaction, so When the high heavy diesel of processing nitrogen content produces super-low sulfur product, the hydrodenitrogenationactivity activity that catalyst needs to have excellent, catalysis The hydrodenitrogenationactivity activity of agent improves, and after nitrogen content reduces, the nitrogenous compound that competitive Adsorption occurs with sulfur-containing compound is reduced, and contains Sulphur compound is easier, is also more adsorbed on catalyst activity position, promotes hydrodesulfurization reaction.Therefore, catalysis is improved The hydrodenitrogenationactivity activity of agent has extremely important effect to the ultra-deep hydrodesulfuration activity for improving bulk phase catalyst.

The preparation method of Hydrobon catalyst provided by the invention, comprising:

(1), the mixed solution A containing Ni, W component is prepared, the mixed solution B containing W, Mo, Al component is prepared；

(2), mixed solution A and sodium metaaluminate alkaline solution cocurrent are added in reactor tank and carry out plastic reaction, generate it is nickeliferous, Resulting slurries I are carried out aging by the sediment slurries I of aluminium, tungsten；

(3), mixed solution B and ammonium hydroxide cocurrent are added in the slurries I after aging and carry out plastic reaction, generate nickeliferous, molybdenum, tungsten, The sediment slurries II of aluminium, then carry out aging；

(4), step (3) resulting material is dry through first, molding, dry through second again, then mixed with aluminium salt and organic acid Heshui solution processing, then it is washed, third is dry, roasting, obtain Hydrobon catalyst.

The mixed solution A of step (1) is acid solution, wherein weight concentration of the Ni in terms of NiO is 5~100g/L, preferably For 10~80g/L, W is with WO₃The weight concentration of meter is 2~60g/L, preferably 10~50g/L.Mixed solution B is acid solution, Wherein, W is with WO₃The weight concentration of meter is 2~70g/L, and preferably 4~60g/L, Mo is with MoO₃5~80g/L of weight concentration of meter, Preferably 10~60g/L, Al are with Al₂O₃The weight concentration of meter is 2~60g/L, preferably 5~40g/L.Preparing mixed solution A When, the nickel source generally used can be one or more of nickel sulfate, nickel nitrate, nickel chloride；The tungsten source generally used is inclined Ammonium tungstate.When preparing mixed solution B, for ammonium metatungstate, molybdenum source is ammonium molybdate in the tungsten source generally used, and silicon source can be nitric acid One or more of aluminium, aluminum sulfate, aluminium chloride and aluminium acetate etc..

Step (2) accounts for Hydrobon catalyst obtained by step (4) as the weight that mixed solution A introduces W in terms of oxide The weight of middle W in terms of oxide 40%~80%, preferably 51%~75%.Step (3) introduces the weight of W by mixed solution B Account for 20%~60% of the weight of W in Hydrobon catalyst obtained by step (4) in terms of oxide in terms of oxide, preferably 25% ~49%, the weight of Al is introduced with Al by mixed solution B₂O₃Meter accounts for the weight of Al in Hydrobon catalyst obtained by step (4) With Al₂O₃The 15%~60% of meter, preferably 25%~49%.

The concentration of sodium metaaluminate alkaline solution described in step (2) is with Al₂O₃It is calculated as 5 ~ 80g/L, preferably 10 ~ 60g/L. In step (2), the reaction temperature of plastic is 20~90 DEG C, and preferably 30~70 DEG C, pH value control is 6.0 ~ 10.0, preferably 7.0 ~ 9.0, gelation time is 0.2 ~ 2.0 hour, preferably 0.3 ~ 1.5 hour.

The weight concentration of ammonium hydroxide described in step (3) is 5%~15%.

The reaction condition for carrying out plastic reaction is added in the slurries I after aging in step (3) mixed solution B and ammonium hydroxide cocurrent Are as follows: reaction temperature is 20~90 DEG C, and preferably 30~80 DEG C, pH value control is 6.0 ~ 11.0, preferably 6.5 ~ 9.0, when plastic Between be 0.5 ~ 4.0 hour, preferably 1.0 ~ 3.0 hours.

Aging condition described in step (2) is as follows: aging temperature is 40~90 DEG C, preferably 50~80 DEG C, when aging PH value control is 6.0 ~ 8.0, preferably 6.5 ~ 7.5, and ageing time is 0.1 ~ 1.0 hour, preferably 0.2 ~ 0.8 hour.Aging Carry out under stiring, preferred stirring condition is as follows: speed of agitator is 100~300 revs/min, preferably 150~250 revs/min.

Aging condition described in step (3) is as follows: aging temperature is 40~90 DEG C, preferably 50~80 DEG C, when aging PH value control is 7.5 ~ 11.0, preferably 7.5 ~ 9.5, and ageing time is 1.5 ~ 6.0 hours, preferably 2.0 ~ 5.0 hours.Aging Carry out under stiring, preferred stirring condition is as follows: speed of agitator is 300~500 revs/min, preferably 300~450 revs/min. The pH value of the pH value of step (3) the described aging aging more described than step (2) is at least high by 0.5, preferably at least high by 1.0.

First drying, molding described in step (4) can be carried out using conventional method in that art.First in step (4) Drying condition is as follows: it is 1 ~ 48 hour dry at 40 ~ 250 DEG C, preferably 50 ~ 180 DEG C drying 4 ~ 36 hours.It, can in forming process One of conventional shaping assistant, such as peptizing agent, extrusion aid etc. or a variety of to be added as needed.The peptizing agent is One or more of in hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid etc., the extrusion aid refers to the substance for being conducive to extrusion forming, One or more of such as sesbania powder, carbon black, graphite powder, citric acid, the 1wt% of the total material butt of the dosage Zhan of extrusion aid~ 10wt%.The second drying condition in step (4) are as follows:, preferably 50 ~ 180 DEG C dryings 4 ~ 36 1 ~ 48 hour dry at 40 ~ 250 DEG C Hour.

It in step (4), is handled with the mixed aqueous solution of aluminium salt and organic acid, wherein the mixing of aluminium salt and the organic acid In aqueous solution, aluminium salt is (with Al³⁺Meter) it rubs with the sum of active metal nickel, tungsten and molybdenum in Hydrobon catalyst in terms of oxide You are than being 0.2 ~ 6.0, preferably 0.3 ~ 5.0.Active metal nickel, tungsten in organic acid and Hydrobon catalyst in terms of oxide Molar ratio with the sum of molybdenum is 0.1 ~ 5.0, preferably 0.3 ~ 4.0.The mixed aqueous solution of aluminium salt and organic acid and step (4) are through the The volume ratio of material is 1:1~6:1, preferably 1:1~4:1 after two dryings.Wherein aluminium salt can be aluminium chloride, aluminum nitrate, sulphur One of sour aluminium is a variety of；Organic acid can selected from carbon number be C2 ~ C8 carboxylic acid, be further selected from malic acid, citric acid, Isocitric acid, tartaric acid, oxalic acid, succinic acid, salicylic acid, lactic acid, beta-hydroxy-butanoic acid, maleic acid, nitrilotriacetic acid, amion acetic acid, One of glutamic acid, glutaric acid, adipic acid, benzoic acid, malonic acid are a variety of, preferably malic acid, citric acid, tartaric acid, One of oxalic acid, succinic acid, salicylic acid, maleic acid, amion acetic acid are a variety of.The treatment conditions: temperature 30~100 DEG C, preferably 40~70 DEG C, the time is 1~16 hour, preferably 2~12 hours.

For step (4) after handling through the mixed aqueous solution of aluminium salt and organic acid, used third is dry, washs and roasts This field normal condition can be used by burning, and washing is usually used deionized water or containing decomposable salt (such as ammonium acetate, chlorination Ammonium, ammonium nitrate etc.) solution washing, it is washed till neutrality.Third drying condition in step (4) is as follows: at 40 ~ 250 DEG C dry 1 ~ 48 Hour, preferably drying condition is as follows: 4 ~ 36 hours dry at 50 ~ 180 DEG C, roasting condition is as follows: roasting 1 ~ 24 at 350 ~ 650 DEG C Hour, preferably roasting condition is as follows: roasting 2 ~ 12 hours at 400 ~ 600 DEG C.In Hydrobon catalyst of the present invention, adjuvant component It is preferred that Ti and/or Zr.In Hydrobon catalyst preparation process of the present invention, preferably it is added during preparing mixed solution A Compound containing adjuvant component, i.e. titanium source and/or zirconium source.Titanium source can be used one of Titanium Nitrate, titanium sulfate, titanium chloride etc. or A variety of, one of zirconium nitrate, zirconium chloride, zirconium oxychloride etc. or a variety of can be used in zirconium source.

In the preparation method of Hydrobon catalyst of the present invention, the shape of catalyst can according to need for sheet, it is spherical, Cylindrical bars and irregular strip (clover, bunge bedstraw herb), preferably cylindrical bars and irregular strip (clover, bunge bedstraw herb).Catalyst it is straight Diameter can be the slice of 0.8 ~ 2.0mm and the thick item of > 2.5mm.

The resulting Hydrobon catalyst of step (4) of the present invention is the body phase Hydrobon catalyst of oxidation state, is being used Before conventional method can be used vulcanized.The vulcanization is to convert corresponding sulphur for the oxide of active metal W, Ni and Mo Compound.The vulcanization process can be vulcanized using wet process, can also be used dry pre-sulfiding.The vulcanization process used in the present invention For wet process vulcanization, it can be organic sulfur-containing species, or inorganic sulfur-bearing that vulcanizing agent, which is sulphur-containing substance used in vulcanization, One of substance, such as sulphur, carbon disulfide, dimethyl disulfide etc. are a variety of, sulfurized oil be hydro carbons and/or distillate, Middle hydro carbons is one of hexamethylene, pentamethylene, cycloheptane etc. or a variety of, and distillate is kerosene, normal line diesel oil, normal two wires bavin One of oil etc. are a variety of.The dosage of vulcanizing agent is to be not less than the sulphidity of each active metal in Hydrobon catalyst 80%, it can be according to being actually adjusted, the dosage of vulcanizing agent can be each complete sulphur of active metal in Hydrobon catalyst The theory of change needs the 80% ~ 200% of sulfur content, preferably 100% ~ 150%.Presulfurization condition are as follows: 230 ~ 370 DEG C of temperature, Hydrogen Vapor Pressure 0.3 ~ 6.0h of volume space velocity when 2.0 ~ 10MPa, liquid^-1, vulcanization time 3 ~ for 24 hours, preferably are as follows: 250 ~ 350 DEG C of temperature, Hydrogen Vapor Pressure 1.0 ~ 3.0h of volume space velocity when 3.0 ~ 8.0MPa, liquid^-1, 5 ~ 16h of vulcanization time.

Vulcanization of the present invention is to convert corresponding sulfide for the oxide of active metal component W, Ni and Mo, Up to sulphided state Hydrobon catalyst；The sulphidity of each active metal is not less than 80% in the catalyst.

The Hydrobon catalyst of the method for the present invention preparation, on the basis of the weight of Hydrobon catalyst, NiO, WO₃With MoO₃Total content be 40% ~ 95%, preferably 50% ~ 85%, alumina content be 5% ~ 60%, preferably 15% ~ 50%.

In the Hydrobon catalyst of the method for the present invention preparation, the molar ratio of W/Mo is 1:10 ~ 8:1, preferably 1:8 ~ 5: 1, Ni/(Mo+W) molar ratio is 1:12 ~ 12:1, preferably 1:8 ~ 8:1.

The Hydrobon catalyst of the method for the present invention preparation is body phase Hydrobon catalyst, and composition includes hydrogenation activity Metal component WO₃, NiO and MoO₃And aluminium oxide, after vulcanizing, MoS₂/WS₂The average tap number of plies be 6.0 ~ 9.0 layers, it is excellent 6.5 ~ 9.0 layers are selected as, MoS₂/WS₂Lamella average wafer lamella length be 4.0 ~ 6.5nm, preferably 4.5 ~ 6.0nm.

The pore-size distribution of the Hydrobon catalyst of the method for the present invention preparation is as follows: diameter is shared by the hole below 3nm Kong Rong accounts for the 5% ~ 30% of total pore volume, and diameter is that Kong Rong shared by the hole of 3 ~ 10nm accounts for the 50% ~ 80% of total pore volume, and diameter is 10 ~ 15nm Hole shared by Kong Rong account for the 7% ~ 25% of total pore volume, it is 5% ~ 20% that the Kong Rong that diameter is 15nm or more, which accounts for total pore volume,.

The Hydrobon catalyst of the method for the present invention preparation, after vulcanizing, MoS₂/WS₂It is as follows to accumulate number of plies distribution: accumulation The piece number of plies that the number of plies is 7.0 ~ 9.0 accounts for the total tablet number of plies 55% ~ 85%, preferably 61% ~ 80%；MoS₂/WS₂Lamella distribution of lengths is as follows: Lamella length is that the piece number of plies of 4.0 ~ 6.0nm accounts for the total tablet number of plies 55.0% ~ 85.0%, preferably 65.0% ~ 80.0%.

The Hydrobon catalyst of the method for the present invention preparation, after vulcanizing, MoS₂/WS₂It is specific as follows to accumulate number of plies distribution: The piece number of plies of the number of plies less than 4.0 layers accounts for the total tablet number of plies 1% ~ 8%, the piece number of plies that the number of plies is 4.0 to less than 7.0 account for the total tablet number of plies 3% ~ 20%, the piece number of plies that the number of plies is 7.0 ~ 9.0 accounts for the total tablet number of plies 55% ~ 85%, the piece number of plies of the number of plies greater than 9.0 layers account for the total tablet number of plies 5% ~ 20%。

The Hydrobon catalyst of the method for the present invention preparation, after vulcanizing, MoS₂/WS₂Lamella distribution of lengths is specific as follows: The piece number of plies of the length less than 2.0nm accounts for the total tablet number of plies 1.0% ~ 12.0%, and length is that the piece number of plies of 2.0 to less than 4.0nm accounts for total tablet The number of plies 5.0% ~ 25.0%, length are that the piece number of plies of 4.0 ~ 6.0nm accounts for the total tablet number of plies 55.0% ~ 85.0%, length be greater than 6.0 to The piece number of plies of 8.0nm accounts for the total tablet number of plies 3.0% ~ 15.0%, and the piece number of plies of the length greater than 8.0nm accounts for the total tablet number of plies 0.2% ~ 4.0%.

The property of the Hydrobon catalyst of the method for the present invention preparation is as follows: specific surface area is 180 ~ 500m²/ g, Kong Rongwei 0.20~0.80mL/g。

It can according to need in the Hydrobon catalyst of the method for the present invention preparation containing adjuvant component, adjuvant component is titanium And/or zirconium, weight content of the adjuvant component in Hydrobon catalyst is 20% hereinafter, preferably 15% or less based on the element.

In the Hydrobon catalyst of the method for the present invention preparation, MoS₂/WS₂The number of plies for accumulating pile is high, and length is small, especially collects In in the number of plies be 6.0 ~ 9.0 layers, lamella length is 4.0 ~ 6.5nm, and the effective active of generation is mutually more, mutual promotion work With stronger, activity is higher, while pore size distribution is suitable for, and high mechanical strength has higher hydrodesulfurization and hydrodenitrogeneration reactivity worth, It is suitable for being applied in diesel oil distillate ultra-deep hydrodesulfuration, denitrification reaction, especially handles the diesel raw material of high nitrogen-containing.

The method that the present invention prepares Hydrobon catalyst, previous precipitation are part W and Ni in sodium metaaluminate alkaline solution As silicon source and precipitating reagent, the particle containing W, Ni, Al sediment for the first time after preliminary aging is larger and arranged regular, to rear heavy Long-pending hydrogenation active metals have certain anchoring effect, and the active metal precipitated afterwards is to use ammonium hydroxide as precipitating reagent, The more uniform mitigation of the process precipitated after making in this way, deposits different hydrogenation active metals in an orderly manner in the catalyst, control gold Belong to the probability to contact with each other between the speed and active metal that oxide particle increases, WO₃And MoO₃The granular size of product is suitable Preferably and its distribution is made to obtain good control, MoS in bulk phase catalyst after increase vulcanization₂/WS₂The accumulation number of plies, reduce lamella it is long Degree, optimizes the pattern of active phase, and the effective active of generation is mutually more, and mutual facilitation is stronger, and activity is higher.Together When, this method also makes catalyst form more suitable pore structure, and reasonable pore distribution improves specific surface area and the hole of catalyst Hold.

The method that the present invention prepares Hydrobon catalyst, by the mixing of dried material aluminium salt and organic acid after molding Aqueous solution processing, is more advantageous to the sulfurate activity phase MoS that catalyst can be inhibited excessive₂/WS₂The generation of pile layer, further decreases Vulcanize rear catalyst activity phase lamella length, is conducive to improve catalyst hydrogenation activity.

It is with higher in the particularly suitable ultra-deep hydrodesulfuration and denitrification reaction as light fraction oil of the catalyst Hydrodesulfurization and hydrodenitrogenationactivity activity are especially to have higher plus hydrogen in the heavy diesel of working process high nitrogen high sulfur content Denitrogenation and desulphurizing activated.Sulfur content in the heavier diesel fraction is 1000~20000 μ g/g, wherein thiophene and derivatives The content of middle sulphur accounts for 60wt%~85wt% of raw material total sulfur content, and nitrogen content is 200~2000 μ g/g, wherein carbazole and its derivative The content of nitrogen accounts for 60wt%~80wt% of raw material total nitrogen content in object.

Specific embodiment

In the present invention, specific surface area and Kong Rong use low temperature liquid nitrogen determination of adsorption method, and mechanical strength is measured using side pressure method. MoS in the present invention, in bulk phase catalyst₂/WS₂The accumulation number of plies, lamella length be by transmissioning electric mirror determining, wherein right In W-Ni-Mo catalyst after vulcanizing, that be capable of forming stack layer is active phase MoS₂And WS₂, the present invention in MoS₂/WS₂Shape Formula indicates active phase.Hydrobon catalyst of the invention refers to after vulcanizing by unvulcanised state Hydrobon catalyst sulphur Sulphided state Hydrobon catalyst is turned to, that is, refers to sulphided state Hydrobon catalyst.

In the present invention, wt% is mass fraction, and v% is volume fraction.In the present invention, sulphidity uses X Ray Photoelectron energy Spectrometer (XPS) is measured, and the percentage that the content of sulphided state active metal accounts for the active metal total content is activity gold The sulphidity of category.

Embodiment 1

Nickel chloride, ammonium metatungstate are added to the dissolving tank 1 that deionized water is housed respectively, are configured to mixed solution A, mixed solution A Weight concentration of the middle Ni in terms of NiO is 28g/L, and W is with WO₃The weight concentration of meter is 27g/L.Respectively by ammonium metatungstate, ammonium molybdate, The dissolving tank 2 that deionized water is housed is added in aluminium chloride, is configured to mixed solution B, W is in mixed solution B with WO₃The weight of meter is dense Degree is 30g/L, and Mo is with MoO₃Meter weight concentration is 36g/L, and Al is with Al₂O₃The weight concentration of meter is 26g/L.By deionized water plus Enter in reactor tank, is with Al by weight concentration₂O₃Reactor tank is added in the sodium aluminate solution and mixed solution A cocurrent for being calculated as 30g/L In, gelling temperature is maintained at 62 DEG C, and 7.8, gelation time control is raw at 50 minutes for pH value control in cocurrent plastic reaction process At nickeliferous, tungsten, aluminum precipitation object slurries I.Sediment slurries I aging under stiring will be obtained, mixing speed is 205 revs/min, aging 75 DEG C of temperature, aging pH value is controlled 7.3, aging 0.8 hour.After aging, by mixed solution B, weight concentration 10wt% Ammonium hydroxide cocurrent is added in slurries I, and gelling temperature is maintained at 58 DEG C, and pH value control is at 7.8, plastic in cocurrent plastic reaction process Between control at 2.0 hours, obtain nickel, tungsten, molybdenum, aluminum precipitation object slurries II and stir the aging under agitation of sediment slurries II Mixing speed is 410 revs/min, and 75 DEG C of aging temperature, pH value is controlled 8.5, ageing time 3.0 hours, by the slurries mistake after aging Filter, filter cake is 8 hours dry at 120 DEG C, rolls, extruded moulding.Material after molding is 12 hours dry at 90 DEG C.In deionized water In, 108 grams of anhydrous aluminum chlorides are added, 139 grams of citric acids are configured to aluminium salt and organic acid processing aqueous solution, it will be dry after molding Material is put into processing solution, and it is 2:1 that liquid, which consolidates volume ratio, processing 10 hours under the conditions of temperature is 45 DEG C, after filtering, at room temperature It is washed with deionized 5 times.Then wet bar is 10 hours dry at 80 DEG C, and 500 DEG C roast 4 hours, obtains catalyst A.Catalyst Composition, pore size distribution and main character are shown in Table 1.

Embodiment 2

According to the method for embodiment 1, by the catalyst B in table 1 constituent content match, into dissolving tank 1 be added nickel chloride, partially Ammonium tungstate, zirconyl chloride solution prepare mixed solution A, and into dissolving tank 2, addition ammonium metatungstate, ammonium molybdate, aluminum nitrate are prepared mixed Close solution B.Deionized water is added in reactor tank, is with Al by weight concentration₂O₃It is calculated as the sodium aluminate solution of 40g/L and mixes Solution A cocurrent is closed to be added in reactor tank, gelling temperature is maintained at 45 DEG C, in cocurrent plastic reaction process pH value control 7.6, at The glue time controlled at 1.2 hours, generated nickeliferous, tungsten, aluminium, zirconium sediment slurries I.It is old under stiring will to obtain sediment slurries I Change, mixing speed is 170 revs/min, and 74 DEG C of aging temperature, aging pH value is controlled 7.2, aging 0.7 hour.After aging, It is that 15wt% ammonium hydroxide and mixed solution B cocurrent are added in slurries I by weight concentration, gelling temperature is maintained at 55 DEG C, and cocurrent plastic is anti- 7.8, gelation time control obtained nickel, tungsten, molybdenum, aluminium, zirconium precipitating at 2.0 hours after reaction for pH value control during answering Object slurries II, by the aging under agitation of sediment slurries II, mixing speed is 380 revs/min, ageing time 4.2 hours, always Change 75 DEG C of temperature, aging pH value is controlled 8.5.By the slurries filtering after aging, filter cake is 12 hours dry at 100 DEG C, then squeezes Item molding.Material after molding is 16 hours dry at 80 DEG C.In deionized water, 200 grams of aluminum sulfate, 132 grams of tartaric acid are added It is configured to aluminium salt and organic acid treating solution, the material dried after molding is put into processing solution, it is 2.5:1 that liquid, which consolidates volume ratio, It handling 8 hours under the conditions of temperature is 50 DEG C, after filtering, is washed with deionized 4 times, wet bar is 14 hours dry at 90 DEG C, 550 DEG C roast 6 hours, obtain final catalyst B, and composition, pore size distribution and main character are shown in Table 1.

Embodiment 3

According to the method for embodiment 1, by the catalyst C in table 1 constituent content match, into dissolving tank 1 be added nickel nitrate, partially Ammonium tungstate solution prepares mixed solution A, and ammonium metatungstate, ammonium molybdate, aluminium chloride are added into dissolving tank 2 and prepares mixed solution B. Deionized water is added in reactor tank, is with Al by weight concentration₂O₃The sodium aluminate solution and mixed solution A for being calculated as 36g/L are simultaneously Stream is added in reactor tank, and gelling temperature is maintained at 50 DEG C, and pH value control is 7.9 in cocurrent plastic reaction process, gelation time control System generated nickeliferous, tungsten, aluminum precipitation object slurries I at 1.0 hours.It will obtain sediment slurries I aging under stiring, mixing speed It is 220 revs/min, 72 DEG C of aging temperature, aging pH value is controlled 6.9, aging 0.6 hour.After aging, it is by weight concentration 8wt% ammonium hydroxide and mixed solution B cocurrent are added in slurries I, and gelling temperature is maintained at 50 DEG C, pH value in cocurrent plastic reaction process 8.0, gelation time control obtained nickel, tungsten, molybdenum, aluminum precipitation object slurries II after reaction, and will precipitate at 2.3 hours for control The aging under agitation of object slurries II, mixing speed be 430 revs/min, ageing time 4.1 hours, 78 DEG C of aging temperature, aging PH value is controlled 8.3.By the slurries filtering after aging, filter cake is 12 hours dry at 80 DEG C, then extruded moulding, object after molding Material is 8 hours dry at 100 DEG C.In deionized water, 356 grams of ANN aluminium nitrate nonahydrates are added, 152 grams of salicylic acids are configured to aluminium salt and The material dried after molding is put into processing solution by organic acid treating solution, and it is 1.5:1 that liquid, which consolidates volume ratio, is 48 DEG C in temperature Under the conditions of handle 8 hours, after filtering, be washed with deionized 5 times, wet bar is 15 hours dry at 90 DEG C, small in 560 DEG C of roastings 4 When, final catalyst C is obtained, composition, pore size distribution and main character are shown in Table 1.

Embodiment 4

According to the method for embodiment 1, by the catalyst D in table 1 constituent content match, into dissolving tank 1 be added nickel chloride, partially Ammonium tungstate solution prepares mixed solution A, and ammonium metatungstate, ammonium molybdate, aluminium chloride are added into dissolving tank 2 and prepares mixed solution B. Deionized water is added in reactor tank, is with Al by weight concentration₂O₃It is calculated as 29g/L sodium aluminate solution and mixed solution A cocurrent It is added in reactor tank, gelling temperature is maintained at 55 DEG C, and pH value control is 8.0 in cocurrent plastic reaction process, gelation time control At 55 minutes, nickeliferous, tungsten, aluminum precipitation object slurries I are generated.Obtained sediment slurries I is stirred into lower aging, mixing speed is 230 revs/min, 77 DEG C of aging temperature, aging pH value is controlled 6.8, aging 0.6 hour.After aging, it is by weight concentration 12wt% ammonia spirit and mixed solution B cocurrent are added in slurries I, and gelling temperature is maintained at 50 DEG C, in cocurrent plastic reaction process PH value is controlled 8.2, and gelation time control obtained nickel, tungsten, molybdenum, aluminum precipitation object slurries II at 2.4 hours after reaction, will Sediment slurries II stir lower aging, and mixing speed is 420 revs/min, and ageing time 4.4 hours, 76 DEG C of aging temperature, aging pH Value control is 8.3.By the slurries filtering after aging, filter cake is 14 hours dry at 110 DEG C, then extruded moulding, object after molding Material is 10 hours dry at 100 DEG C.In deionized water, 132 grams of anhydrous aluminum chlorides are added, 118 grams of malic acid are configured to aluminium salt and The material dried after molding is put into processing solution by organic acid treating solution, and it is 2.2:1 that liquid, which consolidates volume ratio, is 55 DEG C in temperature Under the conditions of handle 9 hours, after filtering, be washed with deionized 5 times, wet bar is 12 hours dry at 90 DEG C, small in 480 DEG C of roastings 7 When, final catalyst D is obtained, composition, pore size distribution and main character are shown in Table 1.

Comparative example 1

By method disclosed in CN1951561A, preparation and the catalyst of embodiment 1 form identical reference agent E, and detailed process is such as Under:

It is formed by the catalyst of embodiment 1, nickel chloride and ammonium metatungstate preparation is dissolved in deionized water, are configured to mixed solution, Wherein weight concentration of the Ni in terms of NiO is 28g/L, and W is with WO₃The weight concentration of meter is 46g/L, and Al is with Al₂O₃The weight of meter is dense Degree is 38g/L.500mL deionized water is added in reactor tank, is that reaction is added in 10wt% ammonium hydroxide and mixed solution cocurrent by concentration Plastic is carried out in tank, gelling temperature is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control is raw at 3.0 hours At nickeliferous, tungsten sediment slurries.Then aging is carried out, ageing time 3.8 hours, 75 DEG C of aging temperature, pH value controlled when aging After 7.8, filtering, deionized water, aluminium hydroxide and molybdenum trioxide are added in filter cake, is beaten, after mixing, filters, filter Cake is 8 hours dry at 120 DEG C, rolls, extruded moulding.It is washed with deionized at room temperature 5 times.Then wet bar is at 80 DEG C dry 10 Hour, 500 DEG C roast 4 hours, obtain catalyst E.Catalyst composition, pore size distribution and main character are shown in Table 1.

Comparative example 2

It is formed by the catalyst of embodiment 1, the preparation of aluminium chloride, nickel chloride, ammonium molybdate and ammonium metatungstate is dissolved in deionized water, is matched Mixed solution is made, wherein weight concentration of the Ni in terms of NiO is 28g/L, and W is with WO₃The weight concentration of meter is 46g/L, and Mo is with MoO₃ The weight concentration of meter is 27g/L, and Al is with Al₂O₃The weight concentration of meter is 38g/L.It is 10wt% ammonium hydroxide and mixed solution by concentration Cocurrent is added in reactor tank and carries out plastic, and gelling temperature is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control At 3.0 hours, tungstenic, nickel, molybdenum, aluminum precipitation object slurries are generated.Then aging is carried out, ageing time 3.8 hours, aging temperature 75 DEG C, after 8.0, filtering, filter cake is 8 hours dry at 120 DEG C for pH value control when aging, rolls, extruded moulding.Spend at room temperature from Sub- water washing 5 times.Then wet bar is 10 hours dry at 80 DEG C, and 500 DEG C roast 4 hours, obtains catalyst F.Catalyst composition, hole Distribution and main character are shown in Table 1.

Comparative example 3

According to method for preparing catalyst disclosed in CN201510212110.9, prepare identical with the catalyst of embodiment 1 composition Reference agent G.Aluminium chloride, nickel chloride solution are added into dissolving tank 1, prepares working solution A, Ni is in terms of NiO in mixed solution A Weight concentration is 28g/L, and Al is with Al₂O₃The weight concentration of meter is 19g/L.Into dissolving tank 2 be added aluminium chloride, ammonium metatungstate and Ammonium molybdate prepares working solution B, and W is in mixed solution B with WO₃The weight concentration of meter is 30g/L, and Mo is with MoO₃Counting weight concentration is 36g/L, Al are with Al₂O₃The weight concentration of meter is 26g/L.It is that solution A, plastic temperature is added in 10wt% ammonium hydroxide under stiring by concentration Degree is maintained at 60 DEG C, at the end of pH value control 7.8, gelation time control generated nickeliferous, aluminum precipitation object slurries I at 50 minutes. 500mL deionized water is added in reactor tank, is that 10wt% ammonium hydroxide and solution B cocurrent are added in reactor tank by concentration, gelling temperature Be maintained at 60 DEG C, in cocurrent plastic reaction process pH value control 7.8, gelation time control at 2.0 hours, generate tungstenic, molybdenum, Aluminum precipitation object slurries II.By it is above two containing sediment slurry mix after aging, ageing time 3.8 hours, 75 DEG C of aging temperature, always At the end of change then pH value control is filtered, filter cake carries out hydro-thermal process, hydro-thermal process under the water vapour containing urea 7.8 Condition: the molar ratio of urea and active metal atom total amount is 3:1, and temperature is 230 DEG C, pressure 3.5MPa, and the processing time is 4 Hour, the material after hydro-thermal process is 8 hours dry at 120 DEG C, rolls, extruded moulding.It is washed with deionized at room temperature 5 times. Then wet bar is 10 hours dry at 80 DEG C, and 500 DEG C roast 4 hours, obtains catalyst G.Catalyst composition, pore size distribution and main property Matter is shown in Table 1.

Comparative example 4

By method for preparing catalyst disclosed in CN102049265A, preparation and the catalyst of embodiment 1 form identical reference agent H.Aluminium chloride, nickel chloride, ammonium metatungstate preparating acid sex work solution A are added into dissolving tank, takes 100g ammonium hydrogen carbonate to be made into and rubs The solution that your concentration is 2.0mol/L.500mL water is added into reactor tank, temperature rises to 60 DEG C.It in the case of stirring, will be molten Liquid A, ammonium bicarbonate aqueous solution and concentration be 10wt% ammonium hydroxide cocurrent be added reactor tank in plastic, 60 DEG C of gelling temperature, gelation time 3.0 hours, the pH value of plastic slurry was 7.8.Aging 3.8 hours after cemented into bundles, pH value is 8.0 at the end of aging.So After filter, molybdenum trioxide is added in obtained filter cake, and mashing stirs evenly, and filters, and filter cake is 8 hours dry at 120 DEG C, rolls, and squeezes Item molding.It is washed with deionized at room temperature 5 times.Then wet bar is 10 hours dry at 80 DEG C, and 500 DEG C roast 4 hours, is urged Agent H.Catalyst composition, pore size distribution and main character are shown in Table 1.

Embodiment 5

The present embodiment is WS in sulphided state catalyst₂/MoS₂The measurement of lamella average length and the average tap pile number of plies.To made The TEM photo of standby bulk phase catalyst is statisticallyd analyze, and statistics area is about 20000nm², the WS of statistics₂/MoS₂Lamella Sum is more than 400.According to calculation formula (1) and (2) to bulk phase catalyst WS₂/MoS₂Lamella average length and average tap pile The number of plies carries out statistics calculating, is as a result listed in table 3.

(1)

(2)

In formula (1), (2),L _A For WS₂/MoS₂Lamella average length,L _i For WS₂/MoS₂Lamella length, nm；n _i It is for lengthL _i 's WS₂/MoS₂Piece number of layers,N _A For WS₂/MoS₂The average tap number of plies；N _i For WS₂/MoS₂The number of plies is accumulated,m _i It is for the accumulation number of pliesN _i WS₂/MoS₂Piece number of layers.

Using catalyst A, B, C, D of the present invention and comparative example catalyst E, F, G, H, sulphur is carried out on adding hydrogen microreactor Change, the admission space of catalyst is 10mL, vulcanizing agent CS₂, sulfurized oil is hexamethylene, CS₂Dosage be theory need sulfur content 110%.Presulfurization condition are as follows: 320 DEG C of temperature, Hydrogen Vapor Pressure 6.0MPa, air speed 2.0h^-1, time 10h.

Embodiment 6

The present embodiment is catalyst activity evaluation experimental of the present invention, and is compared with comparative example catalyst.It is urged using the present invention Agent A, B, C, D and comparative example catalyst E, F, G, H, on 200mL small hydrogenation device carry out comparative evaluation's test, in order into One step evaluates the ability of catalyst Deitrogenatin, therefore has selected the huge port catalytic diesel oil that nitrogen content is high, difficulty of processing is big former for test Material, raw material main character are shown in Table 4.Catalyst activity evaluates process conditions: hydrogen partial pressure 6.4MPa, and reaction temperature is 360 DEG C, liquid When volume space velocity be 2.0h^-1, hydrogen to oil volume ratio 500:1, evaluation result is shown in Table 5.It is examined using gas chromatography-flame photometric detector Sulfur compound and nitride type in device (GC-AED) detection hydrofined oil are surveyed, the results are shown in Table 6 and table 7.

As seen from Table 2, compared with comparative example catalyst, feelings that catalyst of the present invention does not change substantially in active metal amount Under condition, MoS₂/WS₂The average tap number of plies increase, average platelet length reduces, and hydrogenation sites number increased significantly.From Table 3 can be seen that catalyst of the present invention after vulcanizing, MoS₂/WS₂The accumulation number of plies be concentrated mainly on 6.0 ~ 9.0 layers, lamella is long Degree is concentrated mainly on 4.0 ~ 6.5nm.From table 4, it can be seen that catalyst activity evaluation is high using feedstock oil nitrogen content, this will also increase The difficulty of the ultra-deep hydrodesulfuration of big feedstock oil.Find out from the evaluation result of table 5- table 7, catalyst of the present invention has excellent Hydrodenitrogenationactivity activity shows high hydrogenation activity in 1,8-DMCB of removing and Isosorbide-5-Nitrae, 8-TMCB macromolecular nitride, favorably In the hydrodesulfurization activity for improving catalyst.Catalyst of the present invention is for working process light fraction oil, in particular for processing When the poor-quality diesel-oil by cut fraction that nitrogen content is high, difficulty of processing is big, there is excellent ultra-deep hydrodesulfuration and nitrogen removal performance, and improve The Cetane number of diesel oil.

The catalyst composition and property of 1 embodiment of table and comparative example preparation

Catalyst number	A	B	C	D	E	F	G	H
									NiO, wt%	19	22	20	16	19	19	19	19
WO3, wt%	35	28	32	33	35	35	35	35
									MoO3, wt%	18	18	15	20	18	18	18	18
Al2O3, wt%	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus
									Other/wt%	-	ZrO2/3.0	-	-	-	-	-	-
Specific surface area, m2/g	212	205	208	209	175	179	219	225
									Kong Rong, mL/g	0.320	0.313	0.312	0.314	0.271	0.273	0.325	0.334
Mechanical strength, N/mm	19.9	20.2	19.6	20.5	16.7	17.2	15.8	14.7
									Pore size distribution, %
< 3nm	8.45	8.84	8.62	8.58	65.16	63.81	11.51	20.18
									3nm~10nm	70.05	69.26	69.89	69.56	20.27	21.69	61.52	40.56
10nm~15nm	11.18	11.47	11.35	11.50	8.03	9.12	23.47	30.24
									> 15nm	10.32	10.43	10.14	10.36	6.54	5.38	3.50	9.02

MoS in 2 bulk phase catalyst of table₂/WS₂The average tap number of plies and average platelet length

Catalyst number	Average stacking number NA	Average length LA, nm
			A	8.49	4.80
B	8.32	4.83
			C	8.36	4.82
D	8.37	4.84
			E	4.88	7.92
F	5.03	8.01
			G	5.97	7. 85
H	5.93	7. 62

MoS in 3 bulk phase catalyst of table₂/WS₂The accumulation number of plies and lamella length distribution

Catalyst number	A	B	C	D	E	F	G	H
									The distribution of the piece number of plies, %
4.0 layers of <	3.13	3.43	3.36	3.54	30.22	32.56	24.98	20.56
									4.0 to less than 7.0 layers	9.35	9.24	9.51	9.67	66.22	64.98	71.26	74.26
7.0 ~ 9.0 layers	75.47	75.36	75.22	75.28	3.56	2.46	3.76	5.18
									9.0 layers of >	12.05	11.97	11.91	11.51	-	-	-	-
Distribution of lengths, %
									< 2.0nm	5.35	5.21	5.18	5.24	1.19	1.23	1.09	1.54
2.0 to less than 4.0nm	14.09	14.04	14.15	14.16	4.58	5.26	4.98	4.74
									4.0~6.0nm	75.39	75.21	74.99	74.966	8.27	8.56	8.69	8.19
Greater than 6.0 to 8.0nm	4.31	4.64	4.72	4.69	65.17	64.21	65.59	66.58
									> 8.0nm	0.86	0.90	0.96	0.95	20.79	20.74	19.65	18.95

4 feedstock oil main character of table

Project	Analyze result
		Density (20 DEG C), g/cm3	0.9025
Boiling range range, DEG C	162-375
		S, μ g/g	5026
N, μ g/g	1024

5 catalyst activity evaluation result of table

Catalyst number	A	B	C	D
					It generates oil density (20 DEG C), g/cm3	0.8695	0.8700	0.8698	0.8697
Boiling range range, DEG C	169-371	170-371	171-370	171-371
					S, μ g/g	6.5	7.2	7.0	6.8
N, μ g/g	6.9	7.1	7.0	7.2

5 catalyst activity evaluation result of continued

Catalyst number	E	F	G	H
					It generates oil density (20 DEG C), g/cm3	0.8856	0.8883	0.8804	0.8812
Boiling range range, DEG C	173-374	172-374	176-373	175-373
					S, μ g/g	265.6	260.2	217.5	228.6
N, μ g/g	78.2	74.8	60.9	62.1

The content of different sulfide in 6 hydrofined oil of table

Catalyst number	A	B	C	D	E
						Sulfur content in hydrofined oil, μ g/g	6.5	7.2	7.0	6.8	265.6
C1- DBT, μ g/g	0	0	0	0	48.3
						4- BMDBT, μ g/g	1.3	1.5	1.5	1.4	69.2
6-BMDBT, μ g/g	1.8	1.9	1.8	1.9	65.6
						4,6- BMDBT, μ g/g	3.4	3.8	3.7	3.5	82.5

Continued 6

Catalyst number	F	G	H
				Sulfur content in hydrofined oil, μ g/g	260.2	217.5	228.6
C1- DBT, μ g/g	40.7	33.4	37.8
				4- BMDBT, μ g/g	61.5	54.9	56.5
6-BMDBT, μ g/g	68.4	56.3	60.3
				4,6- BMDBT, μ g/g	89.6	72.9	74.0

The content of different nitride in 7 hydrofined oil of table

Catalyst number	A	B	C	D	E
						Nitrogen content in hydrofined oil, μ g/g	6.9	7.1	7.0	7.2	78.2
1- MCB, μ g/g	1.3	1.3	1.3	1.3	28.3
						1,8-BMCB, μ g/g	1.8	1.9	1.9	1.9	34.9
Isosorbide-5-Nitrae, 8- TMCB, μ g/g	3.8	3.9	3.8	4.0	15.0

Continued 7

Catalyst number	F	G	H
				Nitrogen content in hydrofined oil, μ g/g	74.8	60.9	62.1
1-MCB, μ g/g	24.2	18.1	17.8
				1,8-BMCB, μ g/g	35.3	28.3	29.5
Isosorbide-5-Nitrae, 8-TMCB, μ g/g	15.3	14.5	14.8

Note: the main difficult de- nitrogenous compound of hydrodenitrogeneration is the carbazole (CB) that molecule is larger, has steric hindrance, 1- methyl carbazole (1-MCB), 1,8- Dimethylcarbazole (1,8-BMCB), Isosorbide-5-Nitrae, 8- trimethyl carbazole (Isosorbide-5-Nitrae, 8-TMCB) etc..

Claims (19)

1. a kind of preparation method of Hydrobon catalyst, it is characterised in that: the following steps are included:

(1), the mixed solution A containing Ni, W component is prepared, the mixed solution B containing W, Mo, Al component is prepared；

(2), mixed solution A and sodium metaaluminate alkaline solution cocurrent are added in reactor tank and carry out plastic reaction, generate it is nickeliferous, Resulting slurries I are carried out aging by the sediment slurries I of aluminium, tungsten；

(3), mixed solution B and ammonium hydroxide cocurrent are added in the slurries I after aging and carry out plastic reaction, generate nickeliferous, molybdenum, tungsten, The sediment slurries II of aluminium, then carry out aging；

(4), step (3) resulting material is dry through first, molding, dry through second again, then mixed with aluminium salt and organic acid Heshui solution processing, then it is washed, third is dry, roasting, obtain Hydrobon catalyst.

2. according to the method for claim 1, it is characterised in that: the mixed solution A of step (1) is acid solution, wherein Ni Weight concentration in terms of NiO is 5~100g/L, and preferably 10~80g/L, W is with WO₃The weight concentration of meter is 2~60g/L, excellent It is selected as 10~50g/L；Mixed solution B is acid solution, wherein W is with WO₃The weight concentration of meter be 2~70g/L, preferably 4~ 60g/L, Mo are with MoO₃5~80g/L of weight concentration of meter, preferably 10~60g/L, Al is with Al₂O₃The weight concentration of meter be 2~ 60g/L, preferably 5~40g/L.

3. according to the method for claim 1, it is characterised in that: step (2) introduces the weight of W by mixed solution A with oxygen Compound meter accounts for 40%~80% of the weight of W in Hydrobon catalyst obtained by step (4) in terms of oxide, preferably 51%~ 75%；Step (3) accounts for W in Hydrobon catalyst obtained by step (4) as the mixed solution B weight for being introduced into W in terms of oxide Weight in terms of oxide 20%~60%, preferably 25%~49%, by mixed solution B introduce Al weight with Al₂O₃Meter accounts for step Suddenly obtained by (4) in Hydrobon catalyst the weight of Al with Al₂O₃The 15%~60% of meter, preferably 25%~49%.

4. according to the method for claim 1, it is characterised in that: the concentration of sodium metaaluminate alkaline solution described in step (2) With Al₂O₃It is calculated as 5 ~ 80g/L, preferably 10 ~ 60g/L；In step (2), the reaction temperature of plastic is 20~90 DEG C, preferably 30 ~70 DEG C, pH value control is 6.0 ~ 10.0, preferably 7.0 ~ 9.0, and gelation time is 0.2 ~ 2.0 hour, and preferably 0.3 ~ 1.5 is small When.

5. according to the method for claim 1, it is characterised in that: aging condition described in step (2) is as follows: aging temperature It is 40~90 DEG C, preferably 50~80 DEG C, pH value control is 6.0 ~ 8.0, preferably 6.5 ~ 7.5 when aging, ageing time 0.1 ~ 1.0 hours, preferably 0.2 ~ 0.8 hour, aging carries out under stiring, and preferred stirring condition is as follows: speed of agitator 100 ~300 revs/min, preferably 150~250 revs/min.

6. according to method described in claim 1 or 5, it is characterised in that: the weight concentration of ammonium hydroxide described in step (3) be 5%~ 15%；The reaction condition of step (3) plastic reaction are as follows: reaction temperature is 20~90 DEG C, and preferably 30~80 DEG C, pH value, which controls, is 6.0 ~ 11.0, preferably 6.5 ~ 9.0, gelation time is 0.5 ~ 4.0 hour, preferably 1.0 ~ 3.0 hours.

7. according to method described in claim 1 or 5, it is characterised in that: aging condition described in step (3) is as follows: aging Temperature is 40~90 DEG C, and preferably 50~80 DEG C, pH value control is 7.5 ~ 11.0, preferably 7.5 ~ 9.5 when aging, ageing time It is 1.5 ~ 6.0 hours, preferably 2.0 ~ 5.0 hours, aging carries out under stiring, and preferred stirring condition is as follows: speed of agitator It is 300~500 revs/min, preferably 300~450 revs/min.

8. according to the method for claim 7, it is characterised in that: the pH value of step (3) described aging is more described than step (2) old The pH value of change is at least high by 0.5, preferably at least high by 1.0.

9. according to the method for claim 1, it is characterised in that: step (4) first drying condition is as follows: 40 ~ 250 DEG C dry 1 ~ 48 hour, preferably 50 ~ 180 DEG C drying 4 ~ 36 hours；The second drying condition in step (4) is as follows: 40 ~ 250 DEG C drying 1 ~ 48 hour, preferably 50 ~ 180 DEG C drying 4 ~ 36 hours；Step (4) the third drying condition is as follows: 40 ~ 250 DEG C drying 1 ~ 48 hour, preferably drying condition is as follows: 4 ~ 36 hours dry at 50 ~ 180 DEG C, roasting condition is as follows: 350 ~ 650 DEG C roast 1 ~ 24 hour, and preferably roasting condition is as follows: roasting 2 ~ 12 hours at 400 ~ 600 DEG C.

10. according to the method for claim 1, it is characterised in that: in step (4), the mixing with aluminium salt and organic acid is water-soluble Liquid processing, wherein aluminium salt is in the mixed aqueous solution of the aluminium salt and organic acid with Al³⁺With oxygen in meter and Hydrobon catalyst The molar ratio of the sum of active metal nickel, tungsten and the molybdenum of compound meter is 0.2 ~ 6.0, preferably 0.3 ~ 5.0；Organic acid and hydrofinishing The molar ratio of active metal nickel, tungsten and the sum of molybdenum in catalyst in terms of oxide is 0.1 ~ 5.0, preferably 0.3 ~ 4.0；Aluminium salt Volume ratio with material after mixed aqueous solution and step (4) second drying of organic acid is 1:1~6:1, preferably 1:1~4:1； The treatment conditions: 30~100 DEG C of temperature, preferably 40~70 DEG C, time are 1~16 hour, preferably 2~12 hours.

11. according to method described in claim 1 or 10, it is characterised in that: the aluminium salt is aluminium chloride, aluminum nitrate, sulfuric acid One of aluminium is a variety of；Organic acid is selected from the carboxylic acid that carbon number is C2 ~ C8, is further selected from malic acid, citric acid, different lemon Acid, tartaric acid, oxalic acid, succinic acid, salicylic acid, lactic acid, gamma-hydroxybutyric acid, maleic acid, nitrilotriacetic acid, amion acetic acid, paddy ammonia One of acid, glutaric acid, adipic acid, benzoic acid, malonic acid are a variety of, preferably malic acid, citric acid, tartaric acid, oxalic acid, One of succinic acid, salicylic acid, maleic acid, amion acetic acid are a variety of.

12. according to the method for claim 1, it is characterised in that: in the Hydrobon catalyst, be containing adjuvant component The compound containing adjuvant component, i.e. titanium source and/or zirconium source is added in Ti and/or Zr during preparing mixed solution A.

13. according to the method for claim 1, it is characterised in that: on the basis of the weight of Hydrobon catalyst, NiO, WO₃ And MoO₃Total content be 40% ~ 95%, preferably 50% ~ 85%, alumina content be 5% ~ 60%, preferably 15% ~ 50%.

14. according to method described in claim 1 or 13, it is characterised in that: in the Hydrobon catalyst, mole of W/Mo Than being 1:12 ~ 12:1, preferably 1:8 ~ 8:1 for 1:10 ~ 8:1, preferably 1:8 ~ 5:1, Ni/(Mo+W) molar ratio.

15. according to the method for claim 1, it is characterised in that Hydrobon catalyst described in step (4) is carried out sulphur Change, sulphided state Hydrobon catalyst is made.

16. according to the method for claim 15, it is characterised in that: the vulcanization is vulcanized using wet process, and vulcanizing agent is to have Machine sulphur-containing substance and/or inorganic sulphur-containing substance, are further selected from one of sulphur, carbon disulfide, dimethyl disulfide or a variety of； Sulfurized oil is hydro carbons and/or distillate, it is preferable that hydro carbons is one of hexamethylene, pentamethylene, cycloheptane or a variety of, fraction Oil is one of kerosene, normal line diesel oil, normal two wires diesel oil or a variety of；Presulfurization condition are as follows: 230 ~ 370 DEG C of temperature, hydrogen 0.3 ~ 6.0h of volume space velocity when 2.0 ~ 10MPa of pressure, liquid^-1, vulcanization time 3 ~ for 24 hours, preferably are as follows: 250 ~ 350 DEG C of temperature, hydrogen 1.0 ~ 3.0h of volume space velocity when 3.0 ~ 8.0MPa of pressure, liquid^-1, 5 ~ 16h of vulcanization time.

17. according to method described in claim 15 or 16, it is characterised in that: in sulphided state Hydrobon catalyst, each activity The sulphidity of metal is not less than 80%.

18. according to method described in claim 15,16 or 17, it is characterised in that: the Hydrobon catalyst is through vulcanizing Afterwards, MoS₂/WS₂The average tap number of plies be 6.0 ~ 9.0 layers, preferably 6.5 ~ 9.0 layers, MoS₂/WS₂Lamella average length is 4.0 ~ 6.5nm, preferably 4.5 ~ 6.0nm.

19. according to method described in claim 15,16 or 17, it is characterised in that the Hydrobon catalyst is through vulcanizing Afterwards, MoS₂/WS₂Accumulation number of plies distribution is as follows: the number of plies accounts for the total tablet number of plies 55% ~ 80% for 7.0 ~ 9.0 piece number of plies, preferably 61% ~ 80%；Lamella distribution of lengths is as follows: length is that the piece number of plies of 4.0 ~ 6.0nm accounts for the total tablet number of plies 55% ~ 85%, preferably 65% ~ 80%.