CN110038622A

CN110038622A - A kind of hydrocracking catalyst and its preparation method

Info

Publication number: CN110038622A
Application number: CN201810037432.8A
Authority: CN
Inventors: 徐学军; 王海涛; 刘东香; 王继锋; 冯小萍
Original assignee: China Petroleum and Chemical Corp; Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Dalian Petrochemical Research Institute Co ltd; China Petroleum and Chemical Corp
Priority date: 2018-01-16
Filing date: 2018-01-16
Publication date: 2019-07-23
Anticipated expiration: 2038-01-16
Also published as: CN110038622B

Abstract

The invention discloses a kind of hydrocracking catalysts and preparation method thereof.The hydrocracking catalyst is bulk phase catalyst, including hydrogenation active metal component, adjuvant component and carrier component, hydrogenation active metal component WO₃And NiO, after vulcanizing, WS₂The average tap number of plies is 5.0 ~ 7.0 layers, WS₂Lamella average length is 4.0 ~ 6.0nm.The catalyst is first to react the mixed solution A containing Ni, W, adjuvant component with sodium metaaluminate alkaline solution cocurrent, aging is carried out to gained slurries, it is reacted in slurries after above-mentioned aging is added with ammonium hydroxide cocurrent in mixed solution B containing W, Si, Al, adjuvant component, aging is carried out after adding the suspension of molecular sieve, hydrocracking catalyst then is made through drying, molding etc..The hydrocracking catalyst is suitable for middle oil type hydrocracking catalyst, has good activity and selectivity.

Description

A kind of hydrocracking catalyst and its preparation method

Technical field

The present invention relates to the hydrocracking catalyst and its preparation method of a kind for the treatment of of heavy hydrocarbon class, especially a kind of body is added hydrogen Cracking catalyst and its preparation method.

Background technique

It is hydrocracked and carries out at elevated pressures, hydrocarbon molecules and hydrogen carry out cracking and adding hydrogen in catalyst surface Reaction generates the conversion process of lighter molecule, while the hydrogenation reaction of hydrodesulfurization, denitrogenation and unsaturated hydrocarbons also occurs.Hydro carbons exists Cracking reaction in hydrocracking process is carried out on the acid centre of catalyst, it then follows carbon ion reaction mechanism, add hydrogen, With the generation of hydro carbons isomerization reaction while cracking reaction.

Hydrocracking catalyst is made of hydrogenation component and acidic components, and the two adds by a certain percentage as needed Enter, makes that hydrogen and cracking performance is added to reach balance, effect is that hydrocarbon mixture is made sufficiently to add hydrogen, cracking and isomerization reaction.Cause This, the catalyst that distillate hydrocracking process needs, which should have stronger hydrogenation sites again, to be had in good acidity The heart.Hydrogenation activity is usually by the group VIB and the offer of group VIII metal in the periodic table of elements, and acid source is wrapped Include the carriers such as zeolite and inorganic oxide.

The lytic activity of hydrocracking catalyst derives from the acidity of carrier component.The acid centre of hydrocracking catalyst There is very strong suction-operated, i.e. acid centre of the nitrogenous compound to hydrocracking catalyst to the nitrogenous compound in charging With different degrees of murder by poisoning (shielding) effect.Therefore, high-activity hydrocracking catalyst generally all has the nitrogen content of charging Stringent limitation, by being hydrocracked sulphur, nitrogen, oxygen and metal impurities in pretreatment removing raw material, general control feed nitrogen contains Amount is in 10 μ g/g hereinafter, just can guarantee that the activity of hydrocracking catalyst is not fully exerted.Crude oil is increasingly heavy in world wide Matter and in poor quality, sulphur, nitrogen content are high in Hydrocracking Raw Oil, while under high-speed, pretreated by being hydrocracked Raw material is often not achieved requirement of the hydrocracking catalyst to nitrogen content in charging, or due in raw material impurity it is more, cause plus hydrogen Pretreatment catalyst activity stability reduces, and treated, and raw material nitrogen content cannot still be met the requirements, this just needs to improve plus hydrogen The nitrogen resistance of Cracking catalyst.Hydrocracking catalyst has good resistance to nitrogen, and the raw material that catalyst can be improved adapts to Property, extend the operation cycle of commercial plant.

In general, following method can be used to prepare for hydrocracking catalyst, such as: infusion process, kneading method, beating method and altogether Ion-exchange etc. can be used for noble metal in precipitation method etc..Infusion process is first to prepare carrier, then supported active metals, kneading Method is first to prepare carrier component, is then formed with active metal kneading, and mainly to pass through active metal solution, silicon molten for coprecipitation method Liquid, aluminum solutions, acidic components carry out precipitating and are prepared.Compared with conventional load type hydrocracking catalyst, body is added hydrogen and splits Change in catalyst on active metal component not instead of dip loading to carrier, active metal, silicon and aluminium are generated by co-precipitation Oxide, amorphous silica-alumina can also provide certain acidic cleavage function in body phase hydrocracking catalyst, become body addition The important composition of hydrogen Cracking catalyst acidic components.Metal loading is unrestricted in body phase hydrocracking catalyst.Conventional negative Load type hydrocracking catalyst is limited by carrier pore structure, and active metal load capacity is usually no more than 30wt%, and support type is urged The activated centre quantity that agent can be provided is limited, and the limit bottleneck of activated centre quantity can not be broken through, and increases substantially and adds hydrogen Active space is limited, is difficult meet the needs of refinery's production oil product.

Body phase hydrogenation catalyst is usually group VIB metallic element (Mo, W) and group VIII metal element (Ni), activity gold It is interlaced to belong to atom, provides reaction compartment for reactant molecule, active metal is exposed to catalyst surface, mentions for reaction molecular For chain carrier.Loaded catalyst is mixed by the two class activated centres in lower active a kind of activated centre and greater activity It is combined into, and it is two class activated centres that bulk phase catalyst activated centre is substantially all, bulk phase catalyst mainly passes through increase The density in the activated centre on catalyst is to greatly improve its catalytic activity.Chianelli etc. proposes spoke edge-seamed edge model 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 provides and adds 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 plus hydrogen and hydrogenolysis activity and active sites distributions are 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.

Hydrocracking catalyst disclosed in US 3954671, hydrogenation conversion catalyst disclosed in US 4313817, The hydrocracking catalyst of nitrogen-resistant type fecund intermediate oil disclosed in CN1253988A, heavy hydrocarbon disclosed in CN1253989A Hydrocracking catalyst, high activity, medium oil type hydrocracking catalyst disclosed in CN101239324A.These catalyst are to adopt It is prepared with coprecipitation, the acidic mixed solution containing active metal is reacted with precipitating reagent, is prepared into containing active Metal, silicon, aluminium sediment, be added molecular sieve after, through drying, molding, roasting, finished catalyst is made.

CN201611156531.5 discloses a kind of preparation method of hydrocracking catalyst.This method be by silicon source, Silicon source and nickel salt or nickel salt and metal promoter M(such as Mo, Co, W) salt mixed aqueous solution and precipitating reagent progress co-precipitation, Precipitate slurry is obtained by aging, molding, roasting, obtains hydrocracking catalyst.

CN103055923A discloses a kind of preparation method of hydrocracking catalyst.This method is using containing hydrogenation activity Acid solution, sodium metaaluminate alkaline solution and the gas CO of metal₂Plastic in the reactor tank equipped with deionized water is added in cocurrent, so The suspension that Y type molecular sieve is added afterwards is uniformly mixed, and through filtering, drying, molding, then washed, dry, roasting is made plus hydrogen is split Change catalyst.

CN104588082A discloses a kind of body phase hydrocracking catalyst and preparation method thereof.This method is by using just Addition prepares nickel, aluminum precipitation object, and cocurrent process prepares tungsten, silicon and aluminum precipitation object, above two sediment is mixed, and Y type point is added Son sieve suspension, through filtering, molding, roasting and etc. be prepared into hydrocracking catalyst.

The above method cannot control well the distribution of hydrogenation active metals, to influence point of different hydrogenation active metals Cloth is unfavorable for forming effective active phase, is unfavorable for effective cooperation of hydrogenation metal and acidic components, final influence catalyst Performance.

Summary of the invention

Aiming at the deficiencies in the prior art, the present invention provides a kind of hydrocracking catalyst and its preparation methods.The party Method can improve the distribution of hydrogenation active metals in hydrocracking catalyst, promote the formation and uniformly of catalyst effective active phase Distribution, while it is uniformly distributed acidic components in catalyst, and improve the mating reaction between acidic components and active metal component, The final activity and selectivity for improving catalyst, especially suitable for middle oil type hydrocracking catalyst.

Inventor it has been investigated that, in hydrocracking catalyst given activity mutually acidity of catalyst center will can be poisoned It is more, quickly plus hydrogen to act on big nitrogen-containing organic compound, plays the protective effect to acidity of catalyst center, improves The nitrogen resistance of hydrocracking catalyst can also improve the property of hydrocracked product.

The hydrocracking catalyst that one aspect of the present invention provides is body phase hydrocracking catalyst, and composition includes plus hydrogen is living Property metal component, adjuvant component and carrier component, the hydrogenation active metal component be WO₃And NiO, after vulcanizing, WS₂It is average Accumulate the number of plies be 5.0 ~ 7.0 layers, preferably 5.5 ~ 6.5 layers, WS₂Lamella average length be 4.0 ~ 6.0nm, preferably 4.5 ~ 5.5nm。

The hydrocracking catalyst that one aspect of the present invention provides is oxidation state hydrocracking catalyst.

The hydrocracking catalyst that another aspect of the present invention provides is the body phase hydrocracking catalyst of sulphided state, including adds Hydrogen activity metal component, adjuvant component and carrier component, hydrogenation active metal component are W and Ni, WS₂The average tap number of plies is 5.0 ~ 7.0 layers, preferably 5.5 ~ 6.5 layers, WS₂Lamella average length is 4.0 ~ 6.0nm, preferably 4.5 ~ 5.5nm.

The sulphided state hydrocracking catalyst that another aspect of the present invention provides can be by oxidation state hydrocracking catalyst through sulphur It is obtained after change.

In hydrocracking catalyst of the invention, the adjuvant component is one or both of phosphorus, boron.

Hydrocracking catalyst of the invention, on the basis of the weight of the hydrocracking catalyst of oxidation state, adjuvant component Content in terms of oxide is 2wt%~25wt%, preferably 3wt%~20wt%.

Hydrocracking catalyst of the present invention, on the basis of the weight of the hydrocracking catalyst of oxidation state, W is in terms of oxide Content be 10wt%~50wt%, the content of preferably 15wt%~45wt%, Ni in terms of oxide is 3wt%~45wt%, preferably For 5wt%~35wt%.

In hydrocracking catalyst of the present invention, W/Ni molar ratio is 0.05~1.2, preferably 0.1~1.0.

Hydrocracking catalyst of the present invention, the carrier component include molecular sieve and amorphous oxide, the molecule Sieve can be Y type molecular sieve, it is preferable to use following Y type molecular sieve, property are as follows: specific surface area is 750~900m²/ g, it is brilliant For born of the same parents' parameter in 2.423nm~2.545nm, relative crystallinity is 95%~110%, SiO₂/Al₂O₃Molar ratio is 7~60；It is amorphous Oxide is aluminium oxide and silica.

Hydrocracking catalyst of the present invention, on the basis of the weight of the hydrocracking catalyst of oxidation state, molecular sieve contains Amount is 3wt%~30wt%, preferably 5wt%~25wt%；The content of amorphous oxide is 10wt% ~ 67wt%, preferably 20wt% ~63wt%。

In hydrocracking catalyst of the present invention, the content of silica is 3wt%~45wt% in amorphous oxide, preferably 5wt%~40wt%.

Vulcanization of the present invention, be convert the oxide of active metal component W, Ni to corresponding sulfide to get To sulphided state hydrocracking catalyst, the sulphidity of each active metal is not less than 80% in the catalyst.

The pore-size distribution of hydrocracking catalyst of the present invention is as follows: diameter is the total hole Kong Rong Zhan shared by the hole below 4nm 5% ~ 20% held, diameter are that Kong Rong shared by the hole of 4 ~ 10nm accounts for the 55% ~ 80% of total pore volume, and diameter is shared by the hole of 10 ~ 15nm Kong Rong accounts for the 7% ~ 20% of total pore volume, and it is 7% ~ 15% that the Kong Rong that diameter is 15nm or more, which accounts for total pore volume, and preferred pore-size distribution is such as Under: diameter is that Kong Rong shared by the hole below 4nm accounts for the 8% ~ 18% of total pore volume, and diameter is the total hole Kong Rong Zhan shared by the hole of 4 ~ 10nm Appearance is 60% ~ 75%, and diameter is that Kong Rong shared by the hole of 10 ~ 15nm accounts for the 8% ~ 15% of total pore volume, and diameter is the hole of 15nm or more It is 8% ~ 13% that appearance, which accounts for total pore volume,.

Hydrocracking catalyst of the invention, after vulcanizing, WS₂It is as follows to accumulate number of plies distribution: the average tap number of plies is 5.0 ~ 7.0 layers, preferably 5.5 ~ 6.5 layers, the piece number of plies that the accumulation number of plies is 5.0 ~ 7.0 account for the total tablet number of plies 55% ~ 85%, preferably 60% ~ 80%；WS₂Lamella distribution of lengths is as follows: lamella average length is 4.0 ~ 6.0nm, and preferably 4.5 ~ 5.5nm, lamella length is 4.0 The piece number of plies of ~ 6.0nm accounts for the total tablet number of plies 60.0% ~ 85.0%, preferably 65.0% ~ 80.0%.

Hydrocracking catalyst of the invention, after vulcanizing, WS₂It is specific as follows to accumulate number of plies distribution: the number of plies is less than 3.0 The piece number of plies accounts for the total tablet number of plies 1% ~ 8%, and the piece number of plies that the number of plies is 3.0 to less than 5.0 accounts for the total tablet number of plies 3% ~ 15%, and the number of plies is 5.0 ~ The 7.0 piece number of plies accounts for the total tablet number of plies 55% ~ 85%, and the piece number of plies of the number of plies greater than 7.0 accounts for the total tablet number of plies 8% ~ 25%；Preferred stack layer Number distribution is as follows: the piece number of plies of the number of plies less than 3.0 accounts for the total tablet number of plies 1% ~ 5%, and the piece number of plies Zhan that the number of plies is 3.0 to less than 5.0 is total The piece number of plies 5% ~ 15%, the piece number of plies that the number of plies is 5.0 ~ 7.0 account for the total tablet number of plies 60% ~ 80%, and the piece number of plies of the number of plies greater than 7.0 accounts for total tablet The number of plies 10% ~ 20%.

Hydrocracking catalyst of the invention, after vulcanizing, WS₂Lamella distribution of lengths is specific as follows: length is less than 4.0nm The piece number of plies account for the total tablet number of plies 5.0% ~ 25.0%, length is that the piece number of plies of 4.0 ~ 6.0nm accounts for the total tablet number of plies 60.0% ~ 85.0%, long Degree accounts for the total tablet number of plies 1.0% ~ 15.0% for the piece number of plies greater than 6.0 to 8.0nm, and length is greater than the total lamella of piece number of plies Zhan of 8.0nm Number 0.5% ~ 4.0%；Preferred lamella distribution of lengths is as follows: the piece number of plies of the length less than 4.0nm accounts for the total tablet number of plies 8.0% ~ 20.0%, The piece number of plies that length is 4.0 ~ 6.0nm accounts for the total tablet number of plies 65.0% ~ 80.0%, and length is that the piece number of plies Zhan greater than 6.0 to 8.0nm is total The piece number of plies 3.0% ~ 10.0%, the piece number of plies of the length greater than 8.0nm account for the total tablet number of plies 0.7% ~ 3.0%.

The property of hydrocracking catalyst of the present invention is as follows: specific surface area is 250~650m²/ g, Kong Rongwei 0.20~ 0.90mL/g。

The present invention provides a kind of preparation methods of hydrocracking catalyst, comprising:

(1), prepare the mixed solution A containing Ni, W, adjuvant component, prepare containing W, Si, Al, adjuvant component mixed solution B；

(2), the mixed solution A is added progress plastic in reactor tank with sodium metaaluminate alkaline solution cocurrent and reacts, and generation contains Resulting slurries I are carried out aging by nickel, tungsten, aluminum precipitation object slurries I；

(3), it is anti-that progress plastic in the slurries I after step (2) resulting aging is added in the mixed solution B and ammonium hydroxide cocurrent It answers, generates nickeliferous, tungsten, silicon, aluminum precipitation object slurries II, the suspension of molecular sieve is added into slurries II, then in stirring condition Lower carry out aging；

(4), it after aging, by step (3) resulting material through drying, then formed, washed, through drying, roasting, obtain adding hydrogen Cracking catalyst.

In the preparation method of hydrocracking catalyst of the present invention, as needed, by hydrocracking catalyst described in step (4) Agent is vulcanized, and sulphided state hydrocracking catalyst is made.

In the mixed solution A of step (1), weight concentration of the Ni in terms of NiO is 5~100g/L, preferably 10~80g/ L, W are with WO₃The weight concentration of meter be 2~60g/L, preferably 10~50g/L, weight concentration of the auxiliary agent in terms of oxide be 1~ 30g/L, preferably 5~25g/L.In mixed solution B, W is with WO₃The weight concentration of meter be 2~50g/L, preferably 4~40g/L, Si is with SiO₂Weight concentration is 10~100g/L, and preferably 20~80g/L, Al is with Al₂O₃The weight concentration of meter is 2~60g/L, Preferably 2~50g/L, weight concentration of the auxiliary agent in terms of oxide are 1~30g/L, preferably 3~25g/L.Preparing, mixing is molten When liquid A, the nickel source generally used can be one or more of nickel sulfate, nickel nitrate, nickel chloride, the tungsten source generally used for Ammonium metatungstate.When preparing mixed solution B, ammonium metatungstate is in the tungsten source generally used；Silicon source can be silica solution, sodium metasilicate, water One of glass is a variety of；Silicon source can be one or more of aluminum nitrate, aluminum sulfate, aluminium chloride, aluminium acetate etc..Matching Mixed solution A processed and when mixed solution B, is added one or more of the compound containing boron and phosphate builder component, mixes molten The auxiliary agent that liquid A and mixed solution B is added can be identical or different, and wherein boron source is boric acid, and phosphorus source is phosphoric acid, ammonium hydrogen phosphate and phosphorus One of acid dihydride ammonium is a variety of.

Step (2) is introduced into the W in catalyst as mixed solution A and is accounted in catalyst obtained by step (4) in terms of oxide always W is with the 40%~80% of oxide weight calculation amount, preferably 51%~75%；The adjuvant component being introduced by mixed solution A in catalyst Auxiliary agent is accounted in catalyst in terms of oxide with the 20%~80% of oxide weight calculation amount, preferably 35%~65%.Step (3) passes through mixed It closes solution B and is introduced into the W in catalyst accounts for the weight of W in catalyst obtained by step (4) 20%~60%, preferably 25%~49%； The adjuvant component being introduced into catalyst by mixed solution B accounts in catalyst auxiliary agent in terms of oxide with oxide weight calculation amount 20%~80%, preferably 35%~65%.

The Al in catalyst is introduced into as sodium metaaluminate in step (2) to account in terms of oxide in catalyst obtained by step (4) Al is with 10wt%~75wt% of oxide weight calculation amount, preferably 20wt%~70wt%.

Si, the Al being introduced into catalyst in step (3) as mixed solution B are accounted in terms of oxide and are catalyzed obtained by step (4) Si, Al are in agent with 20wt%~75wt% of oxide weight calculation amount, preferably 25wt%~65wt%, and wherein Si is accounted for mixed in terms of silica Close 5wt% ~ 80wt%, preferably 20wt% ~ 75wt% that solution B is introduced into the total weight of Si, Al in catalyst in terms of oxide.

The concentration of sodium metaaluminate alkaline solution described in step (2) is with Al₂O₃It is calculated as 15 ~ 100g/L, preferably 20 ~ 80g/ 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 plastic reaction condition reacted in the slurries I that step (3) mixed solution B and ammonium hydroxide cocurrent are added after aging 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.

Drying, molding and washing described in step (4) can be carried out using conventional method in that art.Wherein, drying condition It is as follows: it is 1 ~ 48 hour dry at 50 ~ 250 DEG C, preferably 80 ~ 180 DEG C drying 4 ~ 36 hours.In forming process, it can be added without Conventional shaping assistant such as peptization acid, extrusion aid etc., straight forming.Washing is usually used deionized water or containing decomposable The washing of salt (such as ammonium acetate, ammonium chloride, ammonium nitrate) solution, is washed till neutrality.

After formation, used drying and roasting can use this field normal condition to step (4), and drying condition is such as Under: 1 ~ 48 hour dry at 50 ~ 250 DEG C, roasting condition is as follows: roasting 1 ~ 24 hour at 350 ~ 650 DEG C, preferably drying condition is such as Under: 4 ~ 36 hours dry at 80 ~ 180 DEG C, roasting condition is as follows: roasting 2 ~ 12 hours at 400 ~ 600 DEG C.

In the method for the present invention, the shape of catalyst be can according to need as sheet, spherical, cylindrical bars and irregular strip (three leaves Grass, bunge bedstraw herb), preferably cylindrical bars, irregular strip (clover, bunge bedstraw herb), the diameter of catalyst can be the thin of 0.8 ~ 2.0mm Item is also possible to the thick item of 2.5mm or more.

In hydrocracking catalyst of the present invention, all in the prior art can be used for plus hydrogen is can be used in Y type molecular sieve used Y type molecular sieve in Cracking catalyst, such as: CN102441411A, CN1508228A, CN101450319A, CN Y type molecular sieve disclosed in 96119840.0.Y type molecular sieve in the present invention disclosed in preferred CN102441411A, with The molecular sieve that CN 96119840.0 is reported is raw material, is 650~800 DEG C in temperature, and pressure is normal pressure to 0.3MPa, and the time is It is deep sealumination modified that hydro-thermal process is carried out in 20~30 hours condition and ranges, when hydro-thermal process can be containing a small amount of in water vapour Ammonia, ammonia partial pressure are 50 ~ 3000Pa(absolute pressure), it is then 0.5~10.0mol/L in acid concentration, the time is 0.5~20.0 hour, Temperature is 30~80 DEG C, and the ratio of sour dosage and molecular sieve is that sour processing is carried out in the condition and range of 1:1~20:1, is used Inorganic acid is hydrochloric acid, sulfuric acid or nitric acid etc., obtains being suitable for the Y type molecular sieve that the present invention uses after hydro-thermal process and acid processing, Its property is as follows: specific surface area is 750~900m²/ g, cell parameter be 2.423nm~2.545nm, relative crystallinity 95%~ 110%, SiO₂/Al₂O₃Molar ratio is 7~60.

The resulting hydrocracking catalyst of step (4) of the present invention is the body phase hydrocracking catalyst of oxidation state, is being used Before can be used conventional method carry out presulfurization.The vulcanization is to convert corresponding sulphur for the oxide of active metal W and Ni 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 hydrocracking catalyst 80%, it can be according to being actually adjusted, the dosage of vulcanizing agent can be each complete sulphur of active metal in hydrocracking catalyst The theory of change needs the 80% ~ 200% of sulfur content, preferably 100% ~ 150%.Presulfurization condition are as follows: 230 ~ 400 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 ~ 370 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.

Hydrocracking catalyst of the present invention once passes through in hydrocracking process especially suitable for one-stage serial, is hydrocracked Operating condition is as follows: reaction temperature is 300~500 DEG C, more preferably 350~450 DEG C；Pressure be 6~20MPa, more preferably 13~ 17MPa；Volume space velocity is 0.5~3.0 h when liquid^-1, preferably 0.8~2.0 h^-1；Hydrogen to oil volume ratio is 400~2000:1, excellent It is selected as 800~1500:1.

The applicable heavy charge range of hydrocracking catalyst of the present invention is very wide, they include vacuum gas oil (VGO), coking watt One of various hydrocarbon ils such as this oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, catalytic cracking recycle oil or Hydro carbons that are a variety of, being usually 250~550 DEG C containing boiling point, nitrogen content can be in 300~2500 μ g/g, by being hydrocracked pretreatment After technique, nitrogen content is less than 150 μ g/g in the charging of hydrocracking catalyst of the present invention, i.e. hydrocracking catalyst conversion zone Nitrogen content is further 10 μ g/g or more less than 150 μ g/g in charging, even 50 μ g/g or more.

Hydrocracking catalyst of the present invention, after vulcanizing, WS₂The number of plies for accumulating pile is high, and length is small, is particularly concentrated on the number of plies It is 5.0 ~ 7.0 layers, length is 4.0 ~ 6.0nm, and the effective active of generation is mutually more, and mutual facilitation is stronger, favorably Acidic components are introduced in the hydrogenation activity for improving catalyst, and using the method for the present invention, make acidic site and hydrogenation active metals The alternate cooperation of activity is good, is especially suitable as middle oil type hydrocracking catalyst, has excellent hydrogenation cracking activity And middle distillates oil selectivity.

The method of the present invention will first be carried out containing Ni, the mixed solution A of part W and auxiliary agent and sodium metaaluminate alkaline solution cocurrent Coprecipitation reaction generates W, Ni, Al mix slurry and carries out preliminary aging for the first time, makes containing W, Ni, Al sediment in this way The larger and arranged regular of grain has certain anchoring effect to the hydrogenation active metals of rear deposition, then by remaining W and auxiliary agent with And the mixed solution B of Si, Al are added in the slurries of above-mentioned aging with ammonium hydroxide cocurrent and are reacted, and it is old then to carry out second of depth Change prepares tungsten, nickel and silicon, aluminium mixed serum, makes to make different hydrogenation active metals in the more uniform mitigation of rear deposition process in this way It deposits, contacts with each other between the speed and active metal of control metal oxide particle growth several in an orderly manner in the catalyst Rate, WO₃The granular size of product is suitable for and its distribution is made to obtain good control, WS in bulk phase catalyst after increase vulcanization₂'s It accumulates the number of plies, reduce lamella length, optimize the pattern of active phase, the effective active of generation is mutually more, mutual promotion Act on it is stronger, activity it is higher.

Using the preparation method of catalyst of the present invention, the intermediate formed between adjuvant component and hydrogenation active metals, favorably Mating reaction between improvement auxiliary agent and hydrogenation active metals, and the caking property of molding can also be improved, it is being added without molding In the case where auxiliary agent can straight forming, not only there is good mechanical strength in this way, and the distribution of pore structure is more reasonable, adds Hydrogen activity metal forms more high activity phases.The final activity and selectivity for improving catalyst, adds especially suitable for middle oil type Hydrogen Cracking catalyst.

Hydrocracking catalyst of the present invention work still with higher (less than 150 μ g/g) under high nitrogen-containing feed conditions Property and stability, it might even be possible to reach the middle oil type catalyst for being equivalent to and having been widely used at present (10 μ g/g of <) under low nitrogen Activity when operation, while to guarantee that catalyst operates still with good stability and middle distillates oil selectivity under conditions of high nitrogen And good product quality, catalyst still have good activity stability.

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. WS in the present invention, in bulk phase catalyst₂The accumulation number of plies, lamella length be by transmissioning electric mirror determining.Of the invention adds Hydrogen Cracking catalyst refers to that by unvulcanised state Sulfidation of Hydrocracking Catalysts be sulphided state hydrocracking catalyst after vulcanizing, Refer to sulphided state hydrocracking catalyst.In the present invention, wt% is mass fraction, and v% is volume fraction.

In the present invention, sulphidity is measured using X X-ray photoelectron spectroscopy X instrument (XPS), sulphided state active metal Content account for the active metal total content percentage be the active metal sulphidity.

Embodiment 1

Nickel chloride, ammonium metatungstate and ammonium dihydrogen phosphate are dissolved in deionized water respectively, are configured in mixed solution A mixed solution A Weight concentration of the Ni in terms of NiO is 42g/L, and W is with WO₃The weight concentration of meter is 30g/L, and auxiliary agent is with P₂O₅The weight concentration of meter is 12g/L.Ammonium metatungstate, aluminium chloride, ammonium dihydrogen phosphate are dissolved in deionized water respectively, dilute water glass solution is added, is configured to mix Solution B is closed, W is in mixed solution B with WO₃The weight concentration of meter is 24g/L, and Al is with Al₂O₃The weight concentration of meter is 28g/L, SiO₂Weight concentration be 40g/L, auxiliary agent is with P₂O₅The weight concentration of meter is 16g/L.Reactor tank is added in 500mL deionized water In, it is with Al by weight concentration₂O₃The sodium aluminate solution and solution A cocurrent for being calculated as 32g/L are added in reactor tank, gelling temperature Be maintained at 60 DEG C, in cocurrent plastic reaction process pH value control 7.6, gelation time control at 30 minutes, generate nickeliferous, tungsten, Aluminum precipitation object slurries I.Sediment slurries I aging will be obtained, 75 DEG C of aging temperature, aging pH value is controlled 7.0, and aging 0.5 is small When, aging carries out under stiring, and speed of agitator is 220 revs/min.After aging, solution B and 10wt% ammonium hydroxide cocurrent are added Gelling temperature is maintained at 60 DEG C in aging rear slurry I, and pH value control is 7.6 in cocurrent plastic reaction process, gelation time control At 2 hours, nickel, tungsten, silicon, aluminum precipitation object slurries II are obtained after reaction, and hydrothermal treatment is added to sediment slurries II and changes Property Y type molecular sieve suspension (by CN102441411A embodiment 3 prepare), the additional amount of Y type molecular sieve is total by catalyst is accounted for Weight 10wt% is added, and Y type molecular sieve property is shown in Table 6, carries out aging under agitation, and speed of agitator is 400 revs/min, aging 75 DEG C of temperature, pH value control filters the slurries after aging 8.0, ageing time 3 hours, and filter cake is small in 100 DEG C of dryings 12 When, it rolls, extruded moulding.It is washed with deionized at room temperature 6 times.Then wet bar is 10 hours dry at 80 DEG C, 530 DEG C of roastings 4 Hour, obtain catalyst A.Catalyst composition 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 nitrate, partially Ammonium tungstate, zirconium oxychloride, boric acid are dissolved in deionized water, prepare working solution A, and ammonium metatungstate, chlorination are added into dissolving tank 2 Aluminium, boric acid are dissolved in deionized water, and waterglass is added, and prepare working solution B, and 800mL deionized water is added in reactor tank, will Weight concentration is with Al₂O₃The sodium aluminate solution and solution A cocurrent for being calculated as 38g/L are added in reactor tank, and gelling temperature is maintained at 50 DEG C, 8.0, it is heavy to generate nickeliferous, tungsten, aluminium, zirconium at 52 minutes for gelation time control for pH value control in cocurrent plastic reaction process Starch slurries I.The sediment slurries I aging that will be obtained, 75 DEG C of aging temperature, the control of aging pH value 7.2, aging 0.8 hour, Aging carries out under stiring, and speed of agitator is 200 revs/min.After aging, slurry is added with for 8wt% ammonium hydroxide cocurrent in solution B In liquid I, gelling temperature is maintained at 55 DEG C, and 8.0, gelation time control is small 2.5 for pH value control in cocurrent plastic reaction process When, nickel, tungsten, zirconium, silicon, aluminum precipitation object slurries II are obtained after reaction, and it is modified that hydrothermal treatment is added to sediment slurries II Y type molecular sieve suspension (being prepared by CN102441411A embodiment 3), the additional amount of Y type molecular sieve is by accounting for overall catalyst weight It measures 12wt% to be added, Y type molecular sieve property is shown in Table 6, carries out aging under agitation, and speed of agitator is 380 revs/min, when aging Between 4.5 hours, 76 DEG C of aging temperature, aging pH value control 8.5.By the slurries filtering after aging, filter cake is at 110 DEG C dry 13 Hour, then extruded moulding, is washed with deionized 5 times, and wet bar is 12 hours dry at 80 DEG C, roasts 5 hours, obtains at 500 DEG C To final catalyst B, catalyst composition 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 chloride, partially Ammonium tungstate matches, ammonium dihydrogen phosphate, is dissolved in deionized water, prepares working solution A, and aluminium chloride, ammonium metatungstate are added into dissolving tank 2 Solution, boric acid are dissolved in deionized water, and waterglass is added, and prepare working solution B, and 700mL deionized water is added in reactor tank, It is with Al by weight concentration₂O₃The sodium aluminate solution and solution A cocurrent for being calculated as 29g/L are added in reactor tank, and gelling temperature is kept 8.2, it is heavy to generate nickeliferous, tungsten, aluminium at 70 minutes for gelation time control for pH value control in 48 DEG C, cocurrent plastic reaction process Starch slurries I.The sediment slurries I aging that will be obtained, 78 DEG C of aging temperature, the control of aging pH value 7.0, aging 0.6 hour, Aging carries out under stiring, and speed of agitator is 190 revs/min.After aging, solution B is added with concentration for 15wt% ammonium hydroxide cocurrent Enter in slurries I, gelling temperature is maintained at 50 DEG C, and 8.0, gelation time control exists for pH value control in cocurrent plastic reaction process 1.8 hours, nickel, tungsten, silicon, aluminum precipitation object slurries II are obtained after reaction, and hydrothermal treatment is added to sediment slurries II and changes Property Y type molecular sieve suspension (by CN102441411A embodiment 3 prepare), the additional amount of Y type molecular sieve is total by catalyst is accounted for Weight 10wt% is added, and Y type molecular sieve property is shown in Table 6, carries out aging under agitation, and speed of agitator is 420 revs/min, aging Time 3.8 hours, 75 DEG C of aging temperature, aging pH value was controlled 8.2.By the slurries filtering after aging, filter cake is in 80 DEG C of dryings 13 hours, then extruded moulding, was washed with water 4 times, and wet bar is 11 hours dry at 90 DEG C, roasts 5 hours, is obtained most at 520 DEG C Whole catalyst C, composition 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 and boric acid prepare working solution A, and aluminum nitrate, ammonium metatungstate, ammonium dihydrogen phosphate are added into dissolving tank 2, is dissolved in Waterglass is added in deionized water, prepares working solution B, is with Al by weight concentration₂O₃Be calculated as 40g/L sodium aluminate solution and Solution A cocurrent is added in reactor tank, and gelling temperature is maintained at 60 DEG C, and pH value control is 7.4 in cocurrent plastic reaction process, plastic Time controlled at 60 minutes, generated nickeliferous, tungsten, aluminum precipitation object slurries I.The sediment slurries I aging that will be obtained, aging temperature 72 DEG C, aging pH value is controlled 7.3, and aging 0.7 hour, aging carried out under stiring, and speed of agitator is 210 revs/min.Aging terminates It afterwards, is that 9wt% ammonium hydroxide cocurrent is added in slurries I by working solution B and concentration, gelling temperature is maintained at 45 DEG C, the reaction of cocurrent plastic 8.2, gelation time control obtained nickel, tungsten, silicon, aluminum precipitation object slurries at 2.3 hours after reaction for pH value control in the process II, the modified Y type molecular sieve suspension of hydrothermal treatment is added to sediment slurries II and (is made by CN102441411A embodiment 3 It is standby), the additional amount of Y type molecular sieve is added by total catalyst weight 10wt% is accounted for, and Y type molecular sieve property is shown in Table 6, in stirring condition Lower carry out aging, speed of agitator are 380 revs/min, and ageing time 4.0 hours, 72 DEG C of aging temperature, aging pH value was controlled 8.5. By the slurries filtering after aging, filter cake is 14 hours dry at 110 DEG C, and then extruded moulding, is washed with deionized 5 times, wet bar It is 12 hours dry at 80 DEG C, it is roasted 6 hours at 500 DEG C, obtains final catalyst D, composition and main character are shown in Table 1.

Comparative example 1

It is prepared according to method disclosed in CN101239324A, catalyst composition is with example 1 group at identical, the specific steps are as follows:

(1) nickel chloride, aluminium chloride and ammonium metatungstate solution deionized water are mixed in the reactor tank of a 5L respectively, are added The dilution of 1000 ml deionized waters；

(2) it prepares containing with SiO in embodiment 1₂Under agitation (1) is added in (2) by the identical dilute water glass solution of content In；

(3) ammonium hydroxide is added to the mixture of (1) and (2) under agitation until pH value 5.2；

(4) configuration is containing the same as WO in embodiment 1₃The identical sodium tungstate solution of content, and be added under agitation (1)+(2)+ (3) in mixture；

(5) ammonium hydroxide is continuously added until pH value is 7.6；

(6) entire plastic process should be carried out at 60 DEG C；

(7) mixture 75 DEG C standing aging 3.5 hours, at the end of aging pH value control 7.8；The Y type being added before aging point Son sieve suspension (preparing by CN102441411A embodiment 3), the additional amount of Y type molecular sieve is by accounting for total catalyst weight 10wt% It is added, Y type molecular sieve property is shown in Table 6；

(8) filter, 100 DEG C oven drying 12 hours, roll, with 3 millimeters of diameter of orifice plate extruded moulding；PH is used at room temperature =8.8 ammonium acetate solution washing；Then 80 DEG C oven drying 10 hours, 530 DEG C roast 4 hours, obtain reference agent E, be catalyzed Agent composition and main character are shown in Table 1.

Comparative example 2

It is prepared by method disclosed in CN103055923A, catalyst composition is with example 1 group at identical, the specific steps are as follows:

(1) it prepares acid solution A: being formed by 1 catalyst of embodiment, nickel chloride, ammonium metatungstate are mixed in one 5 liters of appearance In device, the dilution of 1000 ml deionized waters is added.It prepares containing with SiO in embodiment 1₂The identical dilute water glass solution of content, It is added under stirring condition in mixing salt solution above.

(2) configure alkaline solution B: configuration is containing the same as Al in embodiment 1₂O₃The identical alkaline sodium aluminate solution of content.

(3) by solution A, solution B and CO₂Plastic in plastic cans is added in gas cocurrent, and gelling temperature is maintained at, and 60 DEG C, pH Value is 7.6.Wherein CO used₂Gas concentration is 45v%, and CO is added₂Al in the total amount and alkaline solution of gas₂O₃Molar ratio 3, A, B solution flow velocity are adjusted, guarantee while being dripped off, to guarantee that it is constant that catalyst distribution uniformly forms.

(4) after cemented into bundles, in the case where being stirred continuously, Y type molecular sieve suspension is added and (presses CN102441411A It is prepared by embodiment 3), the additional amount of Y type molecular sieve is added by total catalyst weight 10wt% is accounted for, and Y type molecular sieve property is shown in Table 6, makes It is dispersed in the mixed serum that plastic obtains, 75 DEG C or so standing aging 3.5 hours.

(5) material filtering for obtaining step (4), filter cake is 12 hours dry at 100 DEG C, rolls, extruded moulding.Room temperature Under be washed with deionized.Then 10 hours dry at 80 DEG C, 530 DEG C roast 4 hours, obtain catalyst F.Catalyst composition and Main character is shown in Table 1.

Comparative example 3

In 3 preparation process of comparative example, active metal, silicon, aluminum solutions and precipitating reagent primary first-order equation generate nickel, tungsten, silicon, aluminum precipitation object Slurries, without stepwise reaction and secondary aging.Catalyst composition is with example 1 group at identical, the specific steps are as follows:

Nickel chloride, aluminium chloride, ammonium metatungstate and waterglass are dissolved in deionized water respectively, are configured to mixed solution, mixed solution The weight concentration of middle NiO is 42g/L, Al₂O₃Weight concentration be 45g/L, WO₃Weight concentration be 31g/L, SiO₂Weight Concentration is 40g/L.500mL deionized water is added in reactor tank, is that 10wt% ammonium hydroxide and mixed solution cocurrent are added instead by concentration It answers in tank, gelling temperature is maintained at 60 DEG C, and 7.6, gelation time control is small 2.5 for pH value control in cocurrent plastic reaction process When, generate nickeliferous, tungsten, silicon and aluminum precipitation object slurries.It is suspended that the modified Y type molecular sieve of hydrothermal treatment is added to sediment slurries Liquid (is prepared) by CN102441411A embodiment 3, and the additional amount of Y type molecular sieve is added by total catalyst weight 10wt% is accounted for, Y type Molecular sieve property is shown in Table 6, after mixing evenly aging, and 75 DEG C of aging temperature, pH value control, will 7.8, ageing time 3.5 hours Slurries filtering after aging, filter cake is 8 hours dry at 120 DEG C, rolls, extruded moulding.It is washed with deionized at room temperature 6 times. Then wet bar is 10 hours dry at 80 DEG C, and 530 DEG C roast 4 hours, obtains catalyst G.Catalyst composition and main character are shown in Table 1。

Comparative example 4

It is prepared by method disclosed in CN104588082A, catalyst composition is with example 1 group at identical, the specific steps are as follows:

Nickel nitrate and liquor alumini chloridi are added into dissolving tank 1, prepares working solution A, aluminium chloride, partially is added into dissolving tank 2 Ammonium tungstate and dilute waterglass prepare working solution B.Solution A is added in ammonium hydroxide under stiring, gelling temperature is maintained at 60 DEG C, terminates When pH value control 7.6, gelation time control generated nickeliferous and aluminum precipitation object slurries I at 30 minutes.By 500mL deionized water It is added in reactor tank, ammonium hydroxide and solution B cocurrent is added in reactor tank, gelling temperature is maintained at 60 DEG C, and cocurrent plastic was reacted 7.8, gelation time control generated tungstenic, silicon, aluminum precipitation object slurries II at 2 hours for pH value control in journey.Contain above two The modified Y type of hydrothermal treatment is added to two kinds of mixing of slurries containing sediment in the case where being stirred continuously in sediment slurry mixing Molecular sieve suspension (is prepared) by CN102441411A embodiment 3, and the additional amount of Y type molecular sieve is by accounting for total catalyst weight 10wt% is added, and Y type molecular sieve property is shown in Table 6, is dispersed in it in mixed serum that plastic obtains, in 75 DEG C of agings 3.5 Hour, filtering is 12 hours dry at 100 DEG C, rolls, extruded moulding.Ion water washing is used at room temperature.Then at 80 DEG C dry 10 Hour, 530 DEG C roast 4 hours, obtain catalyst H.Catalyst composition and main character are shown in Table 1.

Embodiment 5

The present embodiment is WS in sulphided state catalyst₂The measurement of average wafer length and the average tap pile number of plies.To prepared The TEM photo of bulk phase catalyst is statisticallyd analyze, and statistics area is about 20000nm², the WS of statistics₂Lamella sum is more than 400.According to calculation formula (1) and (2) to bulk phase catalyst WS₂Lamella average length and the average tap pile number of plies are counted It calculates, is as a result listed in table 3.

(1)

(2)

In formula (1), (2),L _AFor WS₂Lamella average length,L _iFor WS₂Lamella length, nm；n _iIt is for lengthL _iWS₂The piece number of plies Mesh,N _AFor WS₂The average tap number of plies；N _iFor WS₂The number of plies is accumulated,m _iIt is for the accumulation number of pliesN _iWS₂Piece 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: volume space velocity 2.0h when 350 DEG C of temperature, Hydrogen Vapor Pressure 6.0MPa, liquid^-1, time 10h.

Embodiment 6

The present embodiment is catalyst activity evaluation experimental of the present invention, and is compared with comparative example catalyst.Using A of the present invention, B, C, D catalyst and Comparative Example E, F, G, H catalyst carry out comparative evaluation's test on 200mL small hydrogenation device, evaluate item Part are as follows: reaction stagnation pressure 14.7MPa, hydrogen to oil volume ratio 1200, volume space velocity 1.5h when liquid^-1, evaluation is Saudi Arabia's VGO heavy with raw material Distillate, main character are shown in Table 4, and table 5 lists the evaluating catalyst result after operating 500 hours.

From table 2 it can be seen that catalyst of the present invention does not change substantially in active metal amount compared with comparative example catalyst In the case where, WS₂The accumulation number of plies increase, lamella average length reduces, and hydrogenation sites number increased significantly.It is tied from evaluation Fruit table 5, which is found out, is better than reference agent using the activity and middle distillates oil selectivity of catalyst A, B, C, D prepared by the present invention, illustrates this hair The catalyst activity metal utilization of bright method preparation is high, and catalyst reaction activity significantly improves.

Using catalyst A of the present invention, continuously run under the operating conditions described above 2500 hours, product yield and property are basic No change has taken place, illustrates that hydrocracking catalyst of the present invention has good activity and stability to processing high-nitrogen stock.And Using comparative example catalyst E, F, G, H in the case where guaranteeing initial product yield and property, it is required to that reaction temperature is continuously improved Degree, but because catalyst inactivation is serious, even if improving reaction temperature after continuously running 2500 hours, product yield and property have It is decreased obviously.

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

Catalyst number	A	B	C	D	E	F	G	H
									Catalyst composition
NiO, wt%	19	20	18	22	19	19	19	19
									WO₃, wt%	28	30	32	30	28	28	28	28
SiO₂, wt%	24	23	22	20	27	27	27	27
									Al₂O₃, wt%	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus	Surplus
P₂O₅, wt%	12	-	6	4	-	-	-	-
									B₂O₃, wt%	-	13	6	6	-	-	-	-
Catalyst property
									Specific surface area, m²/g	397	395	390	396	354	391	365	375
Kong Rong, mL/g	0.408	0.402	0.399	0.401	0.365	0.415	0.381	0.389
									Mechanical strength, N/mm	20.5	20.1	19.8	19.4	17.7	17.8	17.1	17.3
Pore size distribution, %
									< 4nm	11.37	11.65	11.18	11.12	56.12	13.46	45.35	44.02
4nm~10nm	69.45	68.87	69.25	69.43	30.12	46.08	38.05	38.39
									10nm~15nm	9.34	9.68	9.46	9.23	8.11	36.06	8.38	9.13
> 15nm	9.84	9.80	10.11	10.22	5.65	4.40	8.22	8.46

WS in catalyst obtained by 2 embodiment of table and comparative example₂The average tap number of plies and average platelet length

Catalyst number	Average tap number of plies N_A	Average platelet length L_A, nm
			A	6.17	4.82
B	6.09	4.80
			C	6.10	4.78
D	6.14	4.81
			E	4.02	6.68
F	4.18	6.89
			G	3.98	7.01
H	4.05	6.92

WS in 3 bulk phase catalyst of table₂The 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, %
3 layers of <	3.01	2.98	3.06	2.88	15.35	13.25	14.93	14.85
									3 to less than 5 layers	11.29	11.11	11.97	11.23	76.25	75.95	75.99	75.26
5 ~ 7 layers	74.86	74.52	74.07	74.93	7.38	9.05	8.11	7.91
									7 layers of >	10.84	11.39	10.90	10.96	1.02	1.75	1.87	1.98
Distribution of lengths, %
									< 4nm	18.76	18.58	18.01	18.15	5.69	5.26	6. 08	4.99
4~6nm	73.81	74.22	74.89	74.51	12.36	13.95	14.02	14.21
									Greater than 6 to 8nm	6.45	6.24	6.21	6.41	71.25	72.22	71.94	72.08
> 8nm	0.98	0.96	0.89	0.93	10.70	8.57	7.96	8.72

4 feedstock oil main character of table

Project	Analyze result
		Density (20 DEG C), g/cm³	0.9205
Boiling range range, DEG C	314-539
		S, μ g/g	10100
N, μ g/g	1920
		Carbon residue, wt%	0.18
Condensation point, DEG C	33

5 evaluating catalyst result of table

Catalyst number	A	B	C	D
					Reaction temperature, DEG C	390	390	390	390
Nitrogen content in charging, μ g/g	98.2	103.1	91.4	102.4
					Product distribution and property, wt%
Heavy naphtha (82 ~ 138 DEG C)
					Yield, wt%	8.3	7.8	8.4	8.2
Virtue is latent, wt%	52.6	52.8	52.5	52.1
					Jet fuel (138 DEG C ~ 249 DEG C)
Yield, wt%	28.1	28.2	28.3	27.8
					Smoke point, mm	32	32	31	32
Diesel oil (249 DEG C ~ 371 DEG C)
					Yield, wt%	28.3	28.6	28.4	28.5
Cetane number	70.3	70.9	70.5	70.5
					Tail oil (> 371 DEG C)
Yield, wt%	31.0	30.7	30.8	31.2
					BMCI value	5.9	6.0	6.2	6.4
Middle distillates oil selectivity, wt%	81.7	81.9	81.9	81.8

Continued 5

Catalyst number	E	F	G	H
					Reaction temperature, DEG C	396	396	395	396
Nitrogen content in charging, μ g/g	90.6	105.9	102.7	89.4
					Product distribution, wt%
Heavy naphtha (82 ~ 138 DEG C)
					Yield, wt%	9.8	10.0	9.9	9.7
Virtue is latent, wt%	63.6	62.1	63.3	62.8
					Jet fuel (138 DEG C ~ 249 DEG C)
Yield, wt%	18.2	18.8	19.0	18.9
					Smoke point, mm	22	24	24	23
Diesel oil (249 DEG C ~ 371 DEG C)
					Yield, wt%	20.4	20.2	19.9	20.1
Cetane number	61.5	61.9	60.8	61.1
					Tail oil (> 371 DEG C)
Yield, wt%	42.0	42.2	42.1	42.5
					BMCI value	18.5	20.9	19.1	21.6
Middle distillates oil selectivity, wt%	66.5	67.5	67.1	67.8

The property of Modified Zeolite Y involved in 6 embodiment of table and comparative example

Relative crystallinity, %	95
		Cell parameter, nm	2.439
SiO₂/Al₂O₃, mol/mol	12.05
		Specific surface area, m²/g	839
Kong Rong, mL/g	0.506
		1.7 ~ 10nm secondary pore accounts for total pore volume, %	48.0
Infrared total acid, mmol/g	0.999
		Na₂O, wt%	0.093

Claims

1. a kind of hydrocracking catalyst, which is bulk phase catalyst, and composition includes hydrogenation active metals Component, adjuvant component and carrier component, the hydrogenation active metal component are WO₃And NiO, after vulcanizing, WS₂Average tap layer Number be 5.0 ~ 7.0 layers, preferably 5.5 ~ 6.5 layers, WS₂Lamella average length is 4.0 ~ 6.0nm, preferably 4.5 ~ 5.5nm.

2. a kind of hydrocracking catalyst, which is sulphided state bulk phase catalyst, and composition includes plus hydrogen is living Property metal component, adjuvant component and carrier component, hydrogenation active metal component be W and Ni, WS₂The average tap number of plies be 5.0 ~ 7.0 layers, preferably 5.5 ~ 6.5 layers, WS₂Lamella average length is 4.0 ~ 6.0nm, preferably 4.5 ~ 5.5nm.

3. catalyst according to claim 1 or 2, it is characterised in that: the adjuvant component is one of phosphorus, boron or two Kind.

4. catalyst according to claim 1 or 2, it is characterised in that: with the weight of the hydrocracking catalyst of oxidation state On the basis of, content of the adjuvant component in terms of oxide is 2wt%~25wt%, preferably 3wt%~20wt%.

5. catalyst according to claim 1 or 2, it is characterised in that: with the weight of the hydrocracking catalyst of oxidation state On the basis of, content of the W in terms of oxide is 10wt%~50wt%, the content of preferably 15wt%~45wt%, Ni in terms of oxide For 3wt%~45wt%, preferably 5wt%~35wt%.

6. catalyst according to claim 5, it is characterised in that: W/Ni molar ratio be 0.05~1.2, preferably 0.1~ 1.0。

7. catalyst according to claim 1 or 2, it is characterised in that: the carrier component includes molecular sieve and without fixed Shape oxide, the molecular sieve are Y type molecular sieve, and property is preferably as follows: specific surface area is 750~900m²/ g, cell parameter In 2.423nm~2.545nm, relative crystallinity is 95%~110%, SiO₂/Al₂O₃Molar ratio is 7~60；Amorphous oxide For aluminium oxide and silica.

8. catalyst according to claim 1 or 2, it is characterised in that: with the weight of the hydrocracking catalyst of oxidation state On the basis of, the content of molecular sieve is 3wt%~30wt%, preferably 5wt%~25wt%；The content of amorphous oxide be 10wt% ~ 67wt%, preferably 20wt% ~ 63wt%.

9. catalyst according to claim 8, it is characterised in that: in amorphous oxide the content of silica be 3wt%~ 45wt%, preferably 5wt%~40wt%.

10. catalyst according to claim 1 or 2, it is characterised in that: the vulcanization, be by active metal component W, The oxide of Ni is converted into corresponding sulfide, obtains sulphided state hydrocracking catalyst, each active metal in the catalyst Sulphidity be not less than 80%.

11. catalyst according to claim 1 or 2, it is characterised in that: the pore-size distribution of the hydrocracking catalyst is such as Under: diameter is that Kong Rong shared by the hole below 4nm accounts for the 5% ~ 20% of total pore volume, and diameter is the total hole Kong Rong Zhan shared by the hole of 4 ~ 10nm 55% ~ 80% held, diameter are that Kong Rong shared by the hole of 10 ~ 15nm accounts for the 7% ~ 20% of total pore volume, and diameter is the Kong Rong of 15nm or more Accounting for total pore volume is 7% ~ 15%；Preferred pore-size distribution is as follows: diameter is that Kong Rong shared by the hole below 4nm accounts for the 8% of total pore volume ~ 18%, diameter is that account for total pore volume be 60% ~ 75% to Kong Rong shared by the hole of 4 ~ 10nm, and diameter is Kong Rong shared by the hole of 10 ~ 15nm The 8% ~ 15% of total pore volume is accounted for, it is 8% ~ 13% that the Kong Rong that diameter is 15nm or more, which accounts for total pore volume,.

12. catalyst according to claim 1 or 2, it is characterised in that: the hydrocracking catalyst is after vulcanizing, WS₂ Accumulation number of plies distribution is as follows: the piece number of plies that the accumulation number of plies is 5.0 ~ 7.0 accounts for the total tablet number of plies 55% ~ 85%, preferably 60% ~ 80%；WS₂ Lamella 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 60.0% ~ 85.0%, preferably 65.0% ~80.0%。

13. catalyst according to claim 1 or 2, it is characterised in that: the hydrocracking catalyst is after vulcanizing, WS₂ Accumulation number of plies distribution is as follows: the piece number of plies of the number of plies less than 3.0 accounts for the total tablet number of plies 1% ~ 8%, the lamella that the number of plies is 3.0 to less than 5.0 Number accounts for the total tablet number of plies 3% ~ 15%, and the piece number of plies that the number of plies is 5.0 ~ 7.0 accounts for the total tablet number of plies 55% ~ 85%, and the number of plies is greater than the 7.0 piece number of plies Account for the total tablet number of plies 8% ~ 25%；Preferred accumulation number of plies distribution is as follows: the piece number of plies of the number of plies less than 3.0 accounts for the total tablet number of plies 1% ~ 5%, layer Number accounts for the total tablet number of plies 5% ~ 15% for the 3.0 to less than 5.0 piece numbers of plies, the piece number of plies that the number of plies is 5.0 ~ 7.0 account for the total tablet number of plies 60% ~ 80%, the piece number of plies of the number of plies greater than 7.0 accounts for the total tablet number of plies 10% ~ 20%.

14. catalyst according to claim 1 or 2, it is characterised in that: the hydrocracking catalyst is after vulcanizing, WS₂ Lamella distribution of lengths is as follows: the piece number of plies of the length less than 4.0nm accounts for the total tablet number of plies 5.0% ~ 25.0%, and length is 4.0 ~ 6.0nm's The piece number of plies accounts for the total tablet number of plies 60.0% ~ 85.0%, and length is that the piece number of plies greater than 6.0 to 8.0nm accounts for the total tablet number of plies 1.0% ~ 15.0%, The piece number of plies of the length greater than 8.0nm accounts for the total tablet number of plies 0.5% ~ 4.0%；Preferred lamella distribution of lengths is as follows: length is less than 4.0nm The piece number of plies account for the total tablet number of plies 8.0% ~ 20.0%, length is that the piece number of plies of 4.0 ~ 6.0nm accounts for the total tablet number of plies 65.0% ~ 80.0%, long Degree accounts for the total tablet number of plies 3.0% ~ 10.0% for the piece number of plies greater than 6.0 to 8.0nm, and length is greater than the total lamella of piece number of plies Zhan of 8.0nm Number 0.7% ~ 3.0%.

15. catalyst according to claim 1 or 2, it is characterised in that: the property of the hydrocracking catalyst is as follows: Specific surface area is 250~650m²0.20~0.90mL/g of/g, Kong Rongwei.

16. according to the preparation method of any hydrocracking catalyst of claim 1 ~ 15, comprising:

17. preparation method according to claim 16, it is characterised in that: by step (4) resulting hydrocracking catalyst Vulcanized, sulphided state hydrocracking catalyst is made.

18. preparation method according to claim 16, it is characterised in that: in the mixed solution A of step (1), Ni is with NiO The weight concentration of meter is 5~100g/L, and preferably 10~80g/L, W is with WO₃The weight concentration of meter be 2~60g/L, preferably 10 ~50g/L, weight concentration of the auxiliary agent in terms of oxide are 1~30g/L, preferably 5~25g/L；In mixed solution B, W is with WO₃ The weight concentration of meter is 2~50g/L, and preferably 4~40g/L, Si is with SiO₂Weight concentration be 10~100g/L, preferably 20~ 80g/L, Al are with Al₂O₃The weight concentration of meter is 2~60g/L, preferably 2~50g/L, weight concentration of the auxiliary agent in terms of oxide For 1~30g/L, preferably 3~25g/L.

19. preparation method according to claim 16, it is characterised in that: step (2) is introduced by mixed solution A and is catalyzed W in agent accounted in terms of oxide in catalyst obtained by step (4) total W with the 40%~80% of oxide weight calculation amount, preferably 51%~ 75%；The adjuvant component being introduced into catalyst by mixed solution A accounts in catalyst auxiliary agent in terms of oxide with oxide weight calculation amount 20%~80%, preferably 35%~65%；Step (3) as the mixed solution B W being introduced into catalyst account for step (4) obtained by urge The 20%~60% of the weight of W, preferably 25%~49% in agent；By mixed solution B be introduced into the adjuvant component in catalyst with Oxide meter accounts in catalyst auxiliary agent with the 20%~80% of oxide weight calculation amount, preferably 35%~65%.

20. preparation method according to claim 16, it is characterised in that: introduced and be catalyzed by sodium metaaluminate in step (2) Al in agent accounts in catalyst obtained by step (4) that Al is with 10wt%~75wt% of oxide weight calculation amount in terms of oxide, preferably 20wt%~70wt%.

21. preparation method according to claim 16, it is characterised in that: introduce catalysis by mixed solution B in step (3) Si, Al in agent account in catalyst obtained by step (4) Si, Al in terms of oxide with 20wt%~75wt% of oxide weight calculation amount, Preferably 25wt%~65wt%, wherein Si accounts for Si, Al that mixed solution B is introduced into catalyst in terms of oxide in terms of silica 5wt% ~ 80wt% of total weight, preferably 20wt% ~ 75wt%.

22. preparation method according to claim 16, it is characterised in that: sodium metaaluminate alkaline solution described in step (2) Concentration with Al₂O₃It is calculated as 15 ~ 100g/L, preferably 20 ~ 80g/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, preferably 0.3 ~ 1.5 hour.

23. preparation method according to claim 16, it is characterised in that: the weight concentration of ammonium hydroxide described in step (3) is 5%~15%；Plastic reaction condition in step (3) 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.

24. preparation method according to claim 16, it is characterised in that: aging condition described in step (2) is as follows: old Changing temperature is 40~90 DEG C, and preferably 50~80 DEG C, pH value control is 6.0 ~ 8.0, preferably 6.5 ~ 7.5 when aging, when aging Between be 0.1 ~ 1.0 hour, preferably 0.2 ~ 0.8 hour；Aging carries out under stiring, and preferred stirring condition is as follows: stirring turns Speed is 100~300 revs/min, preferably 150~250 revs/min.

25. according to preparation method described in claim 16 or 24, it is characterised in that: aging condition described in step (3) is such as Under: 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 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 is 300~500 revs/min, preferably 300~450 revs/min.

26. according to the preparation method described in claim 25, it is characterised in that: the pH value of step (3) described aging is than step (2) The pH value of the aging is at least high by 0.5, preferably at least high by 1.0.

27. preparation method according to claim 16, it is characterised in that: step (4) drying condition before the forming It is as follows: it is 1 ~ 48 hour dry at 50 ~ 250 DEG C, preferably 80 ~ 180 DEG C drying 4 ~ 36 hours；Step (4) after formation, is adopted Drying condition is as follows: 1 ~ 48 hour dry at 50 ~ 250 DEG C, roasting condition is as follows: it is roasted 1 ~ 24 hour at 350 ~ 650 DEG C, It is preferred that drying condition is as follows: 4 ~ 36 hours dry at 80 ~ 180 DEG C, roasting condition is as follows: roasting 2 ~ 12 hours at 400 ~ 600 DEG C.

28. preparation method according to claim 17, it is characterised in that: the vulcanization process is vulcanized using wet process, sulphur Agent is organic sulfur-containing species and/or inorganic sulphur-containing substance, is selected from one of sulphur, carbon disulfide, dimethyl disulfide or more Kind, sulfurized oil is hydro carbons and/or distillate, and wherein hydro carbons is one of hexamethylene, pentamethylene, cycloheptane or a variety of, fraction Oil is kerosene, normal line diesel oil, one of normal two wires diesel oil or a variety of；The dosage of vulcanizing agent is to make in hydrocracking catalyst The sulphidity of each active metal is not less than 80%；Presulfurization condition are as follows: 230 ~ 400 DEG C of temperature, 2.0 ~ 10MPa of Hydrogen Vapor Pressure, liquid When volume space velocity 0.3 ~ 6.0h^-1, vulcanization time 3 ~ for 24 hours, preferably are as follows: 250 ~ 370 DEG C of temperature, 3.0 ~ 8.0MPa of Hydrogen Vapor Pressure, liquid When volume space velocity 1.0 ~ 3.0h^-1, 5 ~ 16h of vulcanization time.

29. a kind of hydrocracking process, it is characterised in that: use any hydrocracking catalyst of claim 1 ~ 15.

30. according to the hydrocracking process described in claim 29, it is characterised in that: be used in one-stage serial once by adding hydrogen Process, hydrocracking operation condition are as follows: reaction temperature is 300~500 DEG C, and pressure is 6~20MPa, and volume is empty when liquid Speed is 0.5~3.0 h^-1, hydrogen to oil volume ratio is 400~2000:1；Preferred operations condition is as follows: reaction temperature is 350~450 ℃；Pressure is 13~17MPa；Volume space velocity is 0.8~2.0 h when liquid^-1, hydrogen to oil volume ratio is 800~1500:1.

31. according to the hydrocracking process described in claim 29, it is characterised in that: the heavy charge of hydrocracked, treated includes Vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, in catalytic cracking recycle oil It is one or more；Nitrogen content is further 10 μ g/g or more less than 150 μ g/g in the charging of hydrocracking catalyst conversion zone, Even 50 μ g/g or more.