CN102309970A - Hydro-treating catalyst and preparation method thereof - Google Patents

Abstract

The invention discloses a hydro-treating catalyst and a preparation method thereof. The catalyst comprises hydrogenation metal component, macroporous alumina and amorphous silicon aluminum; the specific surface area of the catalyst is 150 to 450m<2>/g, the pore volume is 0.3 to 0.7cm<3>/g, and the average aperture is 10 to 20 nanometers; the hydrogenation metal component is at least one of W, Mo, Ni and Co; and based on oxides, the weight content of the hydrogenation metal component in the catalyst is 35 to 70 percent. The hydro-treating catalyst has high active metal content and high pore volume and specific surface area, and is suitable for the hydro-treating process of inferior reduced pressure distillate.

Description

A kind of hydrotreating catalyst and preparation method thereof

Technical field

The present invention relates to a kind of carrier of hydrogenating catalyst and preparation method thereof, hydrotreating catalyst of a kind of especially large pore volume that is used to handle heavy distillate, bigger serface, high activity metal content and preparation method thereof.

Background technology

Along with crude quality becomes heavy, variation year by year, environmental regulation is strict day by day, and market constantly increases the demand of cleaning oil product, makes the hydrogen addition technology of producing clean fuel obtain application more and more widely.Distillate hydrogenation is handled and be meant under the HTHP that the saturated catalytic reaction of hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation, HDM and hydrogenation of unsaturated hydrocarbons takes place for feedstock oil and hydrogen on catalyst surface.Because crude quality is variation year by year; And the refinery is for increasing economic efficiency; Crude oil decompression deep drawing technology is generally adopted in beginning; Make doing by original 520 ℃ of vacuum distillate bring up to more than 600 ℃, its density is increasing, boiling range is increasingly high, the molecular weight of contained hydrocarbon molecule is increasing, impurity content is also more and more, and especially sulfur-bearing, the baroque condensed-nuclei aromatics compounds content of nitrogen impurity increase greatly; The difficulty of deviating from of impurity increases greatly, causes more easily that in process the carbon deposit coking reduces catalyst activity.Therefore, hydrotreated feed oil and product are all had higher requirement to hydrotreatment technology and hydrotreating catalyst, especially the hydrotreatment of decompressed wax oil technology and supporting catalyst thereof.

In catalytic field, how to prepare and have high activity, fine selectivity and long-life effective catalyst are the problems that people pay close attention to and pay attention to always.For catalyst with carrier loaded active component, use the carrier of high-specific surface area, can prepare the loaded catalyst of high dispersive, thereby improve the reactivity worth of catalyst; Have bigger pore volume in the catalyst, then can improve its anti-coking or anti-carbon deposit performance, and then prolong the service life of catalyst, also help catalyst regeneration simultaneously.Improve the pore volume and the specific area of carrier,, improve catalyst performance, positive meaning is arranged giving full play to the active constituent catalyst activity.

Hydrotreating catalyst belongs to the supported solid porous catalyst, and its activated centre mainly concentrates on inner surface, and internal surface area accounts for more than 95% of total surface area usually.The orifice diameter of catalyst and reactant molecule magnitude relationship will have direct influence to the process that reaction takes place, and when the hydrocarbon molecule diameter of reactant during greater than the orifice diameter of catalyst, diffusion will become the control step of reaction.Along with hydrotreated feed oil becomes heavy, variation, the hydrocarbon molecule diameter increases gradually, and its structure is also complicated more; It is more and more obvious to use the hydrotreating catalyst of conventional pore structure to receive the influence of DIFFUSION CONTROLLED; The hydrocarbon molecule of larger molecular weight, especially condensed-nuclei aromatics are because volume is bigger; Can not enter into the catalyst duct inner with the duct in hydrogenation sites contact, influence the hydrodenitrogenationactivity activity of catalyst, the desulphurizing activated and saturated performance of aromatic hydrocarbons.How research improves the pore structure of hydrotreating catalyst, improves the pore volume and the orifice diameter of hydrotreating catalyst, and the effective ratio area that keeps higher hydrogenation activity to distribute simultaneously is a problem that has very much realistic meaning.

The carrier of hydrogenating catalyst pore volume of conventional method preparation is generally at 0.7mL/g～1.3mL/g, and the aperture is generally at 5～12nm, and surface area is generally at 250m ²/ g～600m ²/ g, support a certain amount of metal after pore volume generally can descend about 50%.CN02133144.8 has provided a kind of siliceous alumina support and preparation method thereof; This carrier adds a kind of nanometer silicon-containing compound such as nano silicon of polymolecularity in aluminium hydroxide or aluminium oxide and deionized water or aqueous solution process, mix and pinch into plastic; Moulding then, drying, roasting prepare catalyst carrier; This carrier pore volume is 0.55～0.68mL/g, and average pore diameter is 6.5～9.5nm, and specific area is 270～320m ²/ g, bulk density is 0.58～0.68g/mL, and the pore volume that floods the hydrotreating catalyst (CN02144544.3) behind about 30% the Mo-Ni metal is 0.35～0.38mL/g, and concentrate in the aperture is 3～6nm, and specific area is 150～180m ²/ g, doing in processing is 533 ℃, nitrogen content is 1552ppm, when sulfur content is the decompressed wax oil (VGO) of 4900ppm, shows extraordinary hydrogenation activity.Yet, use the hydrogenation catalyst of above-mentioned patent preparation to handle when more the decompression deep drawing of heavy, poor quality gets VGO, the HDN of catalyst, HDS and HDA activity are obviously not high, and can not guarantee long-term operation the service life of catalyst.Therefore, develop more high activity metal content, more the large aperture, more the hydrotreating catalyst of large pore volume becomes and solves heavy decompressed wax oil hydrotreatment important channel.

Improve hydrotreating catalyst pore volume and method for specific area and mainly be through improving the pore structure of catalyst carrier, mainly means have three kinds, and one of which adds expanding agent in the catalyst carrier forming process, like sesbania powder and macromolecular organic compound etc.; Its two improvement method for preparing catalyst for example adopts oil ammonia column to drip ball forming and prepares catalyst carrier; Its three catalysis material of selecting to have macroporous structure is as carrier component, and is furnished with corresponding preparation method.

Though add expanding agent the raising of carrier pore volume there is certain effect, in the preparation process of carrier, adds boehmite powder and alumina powder simultaneously like CN98121083.X and CN99113303.X; Mix mixed pinching such as back and compound expanding agent, become plastic, extruded moulding on banded extruder; Directly large pore volume, wide-aperture carrier of hydrogenating catalyst have been prepared in high-temperature roasting then, and its pore volume is 0.80～1.30mL/g, can several apertures be 15～20nm; The aperture accounts for more than 70% of total pore volume at the pore volume between 10～20nm, but because the expanding agent that adds in the catalyst carrier forming process, makes the large percentage in mechanical hole in the carrier hole structure; Not only actual catalytic reaction effect is helped little; Also certain influence can be arranged to the mechanical strength of catalyst, and its specific area is less, is merely 100～200m ²/ g, behind the carried metal, surface area can be littler.Therefore, certain catalytic effect is being arranged aspect the HDM of heavy distillate, and seeming that activity is not high aspect the desulfurization of heavy distillate, the denitrogenation by the macroporous catalyst of this preparing carriers.In addition, the pore volume majority that adopts expanding agent to improve is " ink bottle " formula, and the catalytic reaction utilization rate is low.

Can prepare the carrier of high pore volume and specific area though adopt the oil ammonia column forming method; But the mechanical strength of prepared carrier and scuff resistance do not reach the instructions for use of hydrocracking unit; As having provided a kind of preparing carriers method that combines above-mentioned two kinds of methods in the document " the reaming research of active aluminum oxide carrier " (2002 11 phase Yang Yuwang of petrochemical industry etc.); Add the organic matter expanding agent in the preparing carriers process; And adopted the preparation method of oil ammonia column moulding, though the pore volume of carrier up to 1.4mL/g, crushing strength is merely 10N/cm～20N/cm.Usually the crushing strength of fixed bed hydrogenation processing catalyst generally requires greater than more than the 100N/cm, can not satisfy the commercial plant instructions for use that fixed bed hydrogenation is handled catalyst.Simultaneously, the carrier of preparing is when infusion process supported active metal, and specific area and pore volume have obvious reduction again, and the pore volume of final catalyst and specific area improve limited.

The catalysis material that selection has macroporous structure is a kind of effective method for preparing the macroporous structure carrier of hydrogenating catalyst as carrier component; US6; The hydrogenation catalyst pore volume that 797,153 employing large pore materials are prepared is 0.5mL/g～1.4mL/g, and specific area is 600m ²/ g～1000m ²/ g; Be used in the heavy distillate hydrodesulfurization, the denitrogenation aspect has demonstrated advantages of high activity; But this method has adopted the active carbon with macroporous structure, requires to use special preparation technology and start-up method, has limited its further use on current fixed bed hydrogenation treating apparatus.

Summary of the invention

In order to overcome existing hydrotreating catalyst and preparation method's deficiency; The present invention provides high hydrotreating catalyst of a kind of active metallic content height, catalyst pore volume and specific area and preparation method thereof, is suitable for the hydrotreatment process of vacuum distillate more inferior.

Hydrotreating catalyst of the present invention comprises hydrogenation metal component, macroporous aluminium oxide and amorphous aluminum silicide, and specific surface area of catalyst is 150m ²/ g～450m ²/ g is preferably 220m ²/ g～400m ²/ g; Pore volume is 0.3cm ³/ g～0.7cm ³/ g is preferably 0.4cm ³/ g～0.6cm ³/ g; Average pore size 10～20nm, preferred 12～20nm.The hydrogenation metal component is at least a among W, Mo, Ni and the Co, is 35%～70% in the weight content of oxide hydrogenation metal component in catalyst, is preferably 40%～60%.The weight content of amorphous aluminum silicide in catalyst is 10%～60%, and the weight content of macroporous aluminium oxide in catalyst is 5%～50%.

In the hydrotreating catalyst of the present invention, macroporous aluminium oxide can be selected the suitable macroporous aluminium oxide product in this area, and preferred pore volume is 1.4mL/g～1.8mL/g, and specific area is 500m ²/ g～550m ²The macroporous aluminium oxide of/g.

In the hydrotreating catalyst of the present invention, the amorphous aluminum silicide specific area is 400-650m ²/ g is preferably 400～550m ²/ g; Pore volume is 1.0～2.0cm ³/ g is preferably 1.2～1.6cm ³/ g, the silica weight content is 20%～80%, is preferably 30%～65%.Average pore diameter is in 10～20nm scope; Preferably at 10～15nm; Meleic acid amount (160 ℃ of infrared absorption spectrographic determinations of pyridine) is between 0.3～0.8mmol/g; Acid centre evenly distributes, and amorphous aluminum silicide adopts silica, aluminium oxide to precipitate simultaneously, uses organic-silicon-modified method preparation then.

In the hydrotreating catalyst of the present invention, can also contain an amount of binding agent and auxiliary agent, auxiliary agent is generally one or more in phosphorus, boron, fluorine, titanium, the zirconium etc.

Preparation method of hydrotreatment catalyst of the present invention is following: powdery macroporous aluminium oxide precursor and powdery amorphous aluminum silicide precursor are mixed; The pulverulent mixture material is immersed in the solution that contains hydrogenation active metals; Filter then, drying; Pass through moulding, activation again, prepare final catalyst.

Among the hydrotreating catalyst preparation method of the present invention, required auxiliary agent can add in the catalyst at arbitrary steps.Catalyst preparation process and condition can adopt method well known to those skilled in the art.

Among the hydrotreating catalyst preparation method of the present invention, described macroporous aluminium oxide precursor is the macroporous aluminium oxide dry glue powder, and the amorphous aluminum silicide precursor is the amorphous aluminum silicide dry glue powder.The dried glue of macroporous aluminium oxide can adopt existing method preparation, and is of CN200510047483.1.

Among the hydrotreating catalyst preparation method of the present invention, described amorphous aluminum silicide dry glue powder adopts following method preparation:

(1) acid aluminium salt solution is (like AlCl ₃, Al (NO ₃) ₃, Al ₂(SO ₄) ₃In the solution one or more) be neutralized into the glue reaction with the alkaline sodium silicate of preparation in proportion and the mixed solution of sodium aluminate, reaction temperature is controlled at 20～80 ℃, and the pH value is in 4.0～9.5 scopes.

(2) after becoming glue, add the organosilicon source; The silicon source can comprise one or more in organic silicone oil or the estersil class etc.; Organosilyl addition is pressed 5%～40% of the required total silicon amount of final products, is preferably 10%～30%, and adjustment pH value and temperature are carried out aging temperature and be controlled at 60～80 ℃; The pH value is in 6.0～10.0 scopes, and ageing time is 60～300min.

(3) (2) gained colloidal sol is filtered, washs.

(4) (3) gained filter cake is carried out drying, pulverizing, make the amorphous aluminum silicide dry glue powder.

Among the hydrotreating catalyst preparation method of the present invention, hydrogenation active metals is generally group vib and VIII family metallic salt, like the salt of metals such as W, Mo, Ni, Co one or more, can add the required various auxiliary agents of catalyst in the dipping solution as required.Dipping process generally can adopt excessive impregnation method, and the dipping solution amount is more than the saturated pick up of carrier material, and general solid-liquid volume ratio is 1: 5～1: 20, is beneficial to abundant dipping.The concentration of slaines such as W, Mo, Ni, Co is confirmed according to catalyst activity metal requirement in the dipping solution, is generally 10～150g/100mL like metal salt concentrations in the dipping solution by oxide.Filtration behind the dipping and dry this area commonsense method and the condition of adopting.In the shaping of catalyst process, can add in peptization acid, adhesive component, expanding agent, the extrusion aid etc. one or more as required, so that moulding smoothly.First dry roasting process is adopted in activation after the moulding, obtains final catalyst prod, and roasting is generally 300～600 ℃ of following roastings 1～10 hour, and drying adopts this area usual terms.

Hydrotreating catalyst of the present invention is through the raw material of preparation large pore volume, bigger serface; And the suitable preparation method of employing; Can guarantee that catalyst is when having higher hydrogenation tenor alive; Have bigger pore volume and specific area, be suitable for the more hydrotreatment process of heavy vacuum distillate more inferior.

Catalyst of the present invention not only has the pore structure of super large; Quite high crushing strength and scuff resistance have also been guaranteed simultaneously; And can be according to actual needs; In wide region, regulate the acid strength of carrier, can satisfy the instructions for use that hydrotreating catalyst supports hydrogenation metal and commercial plant, so the present invention has very high practicality.

The process for preparing hydrotreating catalyst of the present invention adopts carrier material powder dipping method, compares with carrier impregnation after the moulding of routine, and the powder dipping can absorb more maceration extract, pick up than moulding after the carrier pick up improve several times.Therefore maceration extract does not need higher metal concentration just can prepare the higher final catalyst prod of active metallic content.Owing to do not need the dipping solution of high concentration, the solution preparation is simple, and stable in properties is fit to commercial scale and uses.Rarer slaine maceration extract can reduce the viscosity of solution, reduces solution surface tension, can weaken the influence of capillary resistance phenomenon in the dipping process like this.Can guarantee that not only metal component has higher content in the catalyst, can also further improve the decentralization of metal at carrier surface.

Catalyst carrier material is through after the hydrothermal treatment consists, and pore passage structure is more stable, at follow-up dipping, roll, still can keep pore passage structure preferably in the moulding, calcination process process, has bigger pore volume and specific area.Support acidity after the hydrothermal treatment consists weakens greatly, and residue is acid to be main with weak acid, helps improving the hydrogenation performance of catalyst.In addition, behind the carrier material dipping reactive metal solution of hydrothermal treatment consists, be easy to and excessive residue dipping solution isolated by filtration.

The present invention adopts the modified macroporous aluminium oxide of extraordinary silicon as carrier, and this patented product has the pore volume and the specific area of super large, can support more metal component, and can guarantee that metal component can be good on carrier, disperseing.The inventive method can adopt single macropore alumina supporter, can not only guarantee that catalyst has the higher tenor and the uniformity that better metal component distributes, and can also guarantee that catalyst has bigger pore volume and surface area.

The amorphous aluminum silicide that uses in the catalyst carrier of the present invention adopts sial coprecipitation mode preparation simultaneously; Becoming glued bundle back introducing organosilicon source as the modification expanding agent; So not only can obtain the amorphous aluminum silicide that sial is evenly distributed; Can also improve the silica alumina ratio of amorphous aluminum silicide, increase amorphous aluminum silicide pore volume and specific area, can prepare the amorphous aluminum silicide of the macropore that satisfies the catalyst performance needs, bigger serface, high silica alumina ratio.Because the even distribution of aluminium oxide and silica makes the acid centre of amorphous aluminum silicide also can evenly distribute.After introducing organosilicon in the preparation process of amorphous aluminum silicide; In dry and roasting process; Organic matter expands and volatilizees, and makes amorphous aluminum silicide obtain bigger pore volume and specific area, and can adjust pore volume and the specific area that organosilyl addition is adjusted product according to actual instructions for use.In the unbodied sial preparation process, do not use pollutants such as ammoniacal liquor, do not have the ammonia nitrogen discharging.The silicon source adopts cheap waterglass and a spot of organosilicon source to combine, and makes preparation cost be controlled effectively.Therefore this method has characteristics such as preparation technology is simple, cost is low, pollution-free, and suitable commercial scale is promoted the use of.Amorphous aluminum silicide can be through the ratio of adjustment alkaline solution mesosilicic acid sodium and sodium aluminate in the preparation process; And adjustment sodium metasilicate and organosilyl ratio; Come the silica alumina ratio of control amorphous aluminum silicide product flexibly; Can obtain the amorphous aluminum silicide of dioxide-containing silica at 20%～80% relative broad range, the content of silica has direct relation with acidity again in the amorphous aluminum silicide, therefore can further come its acidity of modulation; Come to different instructions for uses, preparation has different acid amorphous silicon aluminums.

In the preparation process of hydrotreating catalyst of the present invention, maceration extract can recycle.Therefore this method has characteristics such as preparation technology is simple, cost is low, pollution is little, and suitable commercial scale is promoted the use of.

The specific embodiment

A kind of concrete preparation process of amorphous aluminum silicide in the catalyst of the present invention is following:

(1) preparation of acid solution is with AlCl ₃Solution be prepared as example: general aluminium oxide and hydrochloric acid are reacted under 90～120 ℃, use the active carbon deferrization, make Fe/Al by weight ₂O ₃Value makes smart AlCl less than 0.005% ₃Solution dilutes again, and concentration is 10～60g Al ₂O ₃Working solution when/L can be used as into glue.

(2) preparation of alkaline solution makes NaAlO earlier ₂Solution adds sodium silicate solution under stirring condition, prepare transparent mixed solution, in the mixed solution with Al ₂O ₃Meter contains 5～80g Al ₂O ₃/ L is with SiO ₂Meter contains 5～120g SiO ₂/ L.

(3) become the glue process: acid solution is joined in the glue jar with certain flow velocity with alkaline solution simultaneously; And stir; Gelation time is controlled at 60～100min; Become the glue reaction temperature to be controlled at 20～80 ℃, preferably be controlled at 50～70 ℃, become the pH value of glue course of reaction to be controlled in 4.0～9.5 scopes.Become glue reaction back to add organic silicon solvent, then slurries are worn out, aging pH value is 6.0～10.0, and temperature is controlled at 60～80 ℃, and ageing time is 60～300min.

(4) filter, wash: the slurries that will wear out filter, and mother liquor is separated, and the cakes with deionized water that obtains is washed, and washing pulp time control system temperature is between 60～80 ℃, and wash time is 20～50min, and washing times is 3～5 times.

(5) drying: the filter cake of (4) gained was carried out drying 1～20 hour under 100～150 ℃.

Hydrotreating catalyst of the present invention prepares in the process, and the preparation of active hydrogenation component solution can be by this area conventional method.With tungsten and nickel is example, the dipping solution preparation: get a certain amount of deionized water under stirring, add nickel nitrate and ammonium metatungstate crystal gradually, and static after treating all to dissolve, filter, obtain metal impregnation solution, wherein WO ₃Content 20.0～50.0gWO ₃/ 100mL, NiO content 2.0～15.0gNiO/100mL.The preparation of various metal impregnation solution belongs to this area mature technology.Solid-liquid volume ratio when dipping solution and carrier material dipping was generally 1: 5～1: 20, and dip time is generally 30～120min.Carry out suction filtration then, the filter cake butt is controlled at 15%～30%, and drying is 2～6 hours under 100～150 ℃ of conditions, and containing metal powder butt is 60%～90%, pulverizes granularity control 100～200 orders then.

Hydrogenation catalyst of the present invention most preferably adopts the mode moulding of extrusion, generally can adopt cylindrical, clover, bunge bedstraw herb or other abnormal shape, carries out drying then, and hydrotreating catalyst is prepared in roasting.Drying was generally descended dry 2～20 hours at 50～200 ℃, and roasting is generally 350～550 ℃ of roastings 1～10 hour.

Among the present invention, specific surface and pore volume adopt the low temperature liquid nitrogen physisorphtion, and the pyridine adsorption infra-red sepectrometry is adopted in meleic acid amount, B acid and L acid, and wherein the summation of B acid and L acid is the meleic acid amount, and trace element adopts plasma emission spectrometry.

Following embodiment is used to illustrate in greater detail the preparation method of carrier of the present invention, but scope of the present invention is not only limited to the scope of these embodiment, and the percentage composition that relates to is a weight percentage.

Instance 1

Adopt patent CN02144544.3 instance (1) and (2) method preparation contrast hydrotreating catalyst numbering CatA and CatB.

Instance 2 (contrast scheme)

(Tianjin is cut Noya Inc. and is produced, pore volume 0.80mL/g, specific area 295m to get the 580g macroporous aluminium oxide ²/ g, butt 72.1%), the little porous aluminum oxide of 386g (Germany produces the SB powder) preparation adhesive (butt 26.2%); Add 6g sesbania powder, rolled 30 minutes, add an amount of distilled water; Make mixture become can squeeze the paste shape, extrusion, banded extruder orifice plate diameter is a 1.5mm clover.Wet bar descended dry 4 hours at 120 ℃, carried out roasting then, 550 ℃ of temperature, 3 hours time, numbering HT-1S.Get HT-1S carrier (MoO in the molybdenum nickel solution ₃Content 40.7g/100mL, NiO content 6.5g/100mL) carry out the supersaturation dipping, the dipping rear catalyst is prepared the catalyst finished product and is numbered HT-1 480 ℃ of roastings 3 hours.

Instance 3 (contrast scheme)

Get the 880g macroporous aluminium oxide, add the rare nitric acid of 4g/100mL and be rolled into the paste shape, extrusion, banded extruder orifice plate diameter is a 1.5mm clover.Wet bar descended dry 4 hours at 120 ℃, carried out roasting then, 550 ℃ of temperature, 3 hours time, numbering HT-2S.Get HT-2S carrier (MoO in the molybdenum nickel solution ₃Content 38.8g/100mL, NiO content 5.6g/100mL) carry out the supersaturation dipping, the dipping rear catalyst floods active component one time by the same way again 480 ℃ of roastings 3 hours.Prepare the catalyst finished product and be numbered HT-2.

Instance 4 (the present invention program)

Get super big hole modified aluminas dried glue 556g (pore volume 1.70mL/g, the specific area 520m of CN200510047483.1 preparation ²/ g, butt 75.1%), the dried glue of 100g amorphous aluminum silicide (pore volume 1.40mL/g, specific area 550m ²/ g, butt 74.3%, average pore diameter is 13.6nm), mix, add the solution impregnation that contains Mo, Ni salt (catalyst such as reactive metal addition form press table 1 catalyst form design and confirm), filter then, dry, pulverizing.Add the binding agent for preparing by the aperture aluminium oxide in right amount, add 6g sesbania powder, rolled 30 minutes, add an amount of distilled water, make mixture become can squeeze the paste shape, extrusion, banded extruder orifice plate diameter is a 1.5mm clover.Wet bar descended dry 4 hours at 120 ℃, carried out roasting then, and 550 ℃ of temperature, are prepared the catalyst finished product and are numbered HT-3 at 3 hours time.

It is following that amorphous aluminum silicide prepares process: 2000mL is contained Al ₂O ₃The AlCl of 5g/100mL ₃Solution with contain Al ₂O ₃5g/100mL and SiO ₂It is becoming during the glue reaction irritates of 65 ℃ of stirrings that the sodium aluminate of 15g/100mL and sodium metasilicate mixed solution and drip are added to temperature, and keeping the pH value is 8.0, and reaction contact time 40min. is with AlCl ₃Solution drips off and is as the criterion.Continue to stir 10min, dropping contains SiO ₂10g/100mL organic silicone oil (trade mark 5001) 350mL, the dropping time is 20min.Using 5% sodium hydroxide solution that slurry pH value is adjusted into 9.0 then wears out.Ageing time is 1.5 hours.Product is filtered, and using solid-to-liquid ratio then is 1: 20 deionized water washing, 70 ℃ of wash temperatures, washing times 3 times.To gained filter cake dry 3h under 120 ℃.

Instance 5 (the present invention program)

Press embodiment 4 described methods (the catalyst composition is pressed table 1 design and confirmed), amorphous aluminum silicide wherein (pore volume 1.32mL/g, specific area 485m ²/ g, butt 75.4%, average pore diameter is 12.7nm) and adopt following method preparation: 6000mL is contained Al ₂O ₃The AlCl of 5g/100mL ₃Solution with contain Al ₂O ₃5g/100mL and SiO ₂It is becoming during the glue reaction irritates of 65 ℃ of stirrings that the sodium aluminate of 15g/100mL and sodium metasilicate mixed solution and drip are added to temperature, and keeping the pH value is 8.0, and reaction contact time 40min. is with AlCl ₃Solution drips off and is as the criterion.Continue to stir 10min, drip ethyl orthosilicate 120mL, the dropping time is 20min.Using 5% sodium hydroxide solution that slurry pH value is adjusted into 9.0 then wears out.Ageing time is 1.5 hours.Product is filtered, and using solid-to-liquid ratio then is 1: 20 deionized water washing, 70 ℃ of wash temperatures, washing times 3 times.To gained filter cake dry 3h under 120 ℃.

Prepare the catalyst finished product and be numbered HT-4.

Instance 6 (the present invention program)

According to embodiment 5 described methods (the catalyst composition is pressed table 1 design and confirmed), prepare the catalyst finished product and be numbered HT-5.

Instance 7 (the present invention program)

According to embodiment 5 described methods (the catalyst composition is pressed table 1 design and confirmed), prepare the catalyst finished product and be numbered HT-6.

Instance 8 (the present invention program)

Press instance 4 methods, add auxiliary agents such as a certain amount of ammonium fluoride, phosphoric acid, zirconia (the catalyst composition is pressed table 1 design and confirmed) in the forming process respectively, prepare the catalyst finished product and be numbered HT-F, HT-P and HT-Zr respectively.

In the present embodiment, above each routine catalyst is carried out instrumental analysis and activity rating.Each routine catalyst physico-chemical property sees shown in the table 1 that it is benchmark that catalyst is formed with weight.

Table 1 catalyst physico-chemical property

Table 1 (continuing) catalyst physico-chemical property

Evaluating apparatus carries out on the 200mL small hydrogenation device, before the activity rating catalyst is carried out presulfurization.The raw materials used grease separation of evaluation of catalyst activity is done feedstock oil with a kind of height of the deep drawing of reducing pressure, and character and reaction process condition are seen table 2 and table 3, and catalyst denitrogenation relative activity comparing result is seen table 4.

Table 2. feedstock oil character

Table 3. evaluating catalyst process conditions

Table 4. catalyst denitrogenation relative activity comparing result

Claims (10)

1. a hydrotreating catalyst comprises hydrogenation metal component, macroporous aluminium oxide and amorphous aluminum silicide, it is characterized in that: specific surface area of catalyst is 150m ²/ g～450m ²/ g, pore volume are 0.3cm ³/ g～0.7cm ³/ g, average pore size 10～20nm, the hydrogenation metal component is at least a among W, Mo, Ni and the Co, is 35%～70% in the weight content of oxide hydrogenation metal component in catalyst.

2. according to the described catalyst of claim 1, it is characterized in that: the weight content of amorphous aluminum silicide in catalyst is 10%～60%, and the weight content of macroporous aluminium oxide in catalyst is 5%～50%.

3. according to claim 1 or 2 described catalyst, it is characterized in that: specific surface area of catalyst is 220m ²/ g～400m ²/ g, pore volume are 0.4cm ³/ g～0.6cm ³/ g, average pore size 12～20nm is 40%～60% in the weight content of oxide hydrogenation metal component in catalyst.

4. according to claim 1 or 2 described catalyst, it is characterized in that: the macroporous aluminium oxide pore volume is 1.4mL/g～1.8mL/g, and specific area is 500m ²/ g～550m ²/ g.

5. according to claim 1 or 2 described catalyst, it is characterized in that: the amorphous aluminum silicide specific area is 400-650m ²/ g, pore volume are 1.0～2.0cm ³/ g, silica weight content are 20%～80%, and average pore diameter is in 10～20nm scope.

6. according to claim 1 or 2 described catalyst, it is characterized in that: the amorphous aluminum silicide specific area is 400～550m ²/ g, pore volume are 1.2～1.6cm ³/ g, silica weight content are 30%～65%, and average pore diameter is in 10～15nm scope.

7. according to the described catalyst of claim 1, it is characterized in that: in the hydrotreating catalyst, also contain binding agent and auxiliary agent, auxiliary agent is one or more in phosphorus, boron, fluorine, titanium, the zirconium.

8. arbitrary Preparation of catalysts method of claim 1 to 7; Powdery macroporous aluminium oxide precursor and powdery amorphous aluminum silicide precursor are mixed, the pulverulent mixture material is immersed in the solution that contains hydrogenation active metals, then filtration, drying; Pass through moulding, activation again; Prepare final catalyst, described macroporous aluminium oxide precursor is the macroporous aluminium oxide dry glue powder, and the amorphous aluminum silicide precursor is the amorphous aluminum silicide dry glue powder.

9. according to the described method of claim 8, it is characterized in that described amorphous aluminum silicide dry glue powder adopts following method preparation:

(1) acid aluminium salt solution is neutralized into the glue reaction with the alkaline sodium silicate of preparation in proportion and the mixed solution of sodium aluminate, and reaction temperature is controlled at 20～80 ℃, and the pH value is in 4.0～9.5 scopes;

(2) after becoming glue, add the organosilicon source; The silicon source can comprise one or more in organic silicone oil or the estersil class; Organosilyl addition is pressed 5%～40% of the required total silicon amount of final products, and adjustment pH value and temperature wear out, and aging temperature is controlled at 60～80 ℃; The pH value is in 6.0～10.0 scopes, and ageing time is 60～300min;

(3) (2) gained colloidal sol is filtered, washs;

(4) (3) gained filter cake is carried out drying, pulverizing, make the amorphous aluminum silicide dry glue powder.

10. according to the described method of claim 9, it is characterized in that: in the mixed solution of alkaline sodium silicate and sodium aluminate, with Al ₂O ₃Meter contains 5～80g Al ₂O ₃/ L is with SiO ₂Meter contains 5～120g SiO ₂/ L.