CN103801368B - A kind of preparation method of the hydrogenation catalyst containing molecular sieve - Google Patents

Abstract

The invention discloses a kind of preparation method of the hydrogenation catalyst containing molecular sieve.The method comprises: add containing the molecular sieve of hydrogenation active metals component and the mixture of organic amine and organic alcohols and/or organic acid in amorphous alumina plastic process, carry out aging after amorphous alumina cemented into bundles, then hydrothermal treatment consists is carried out, after filtration, washing, drying, again through shaping, drying and roasting, obtain hydrogenation catalyst.Molecular sieve and aluminium oxide can combine by the inventive method, there is good conjugation and decentralization, can avoid occurring reuniting between molecular sieve and amorphous alumina even clogging, effectively regulate hydrogenating function and the cracking function of catalyst simultaneously, improve the serviceability of catalyst.Catalyst prepared by the inventive method is applicable in either shallow cracking, deep hydrogenation process.

Description

A kind of preparation method of the hydrogenation catalyst containing molecular sieve

Technical field

The present invention relates to a kind of preparation method of hydrogenation catalyst, especially for the preparation method of the hydrogenation catalyst containing molecular sieve.

Background technology

Hydrocracking technology is one of the important means of crude oil secondary operations, heavy oil lighting.Due to it have that adaptability to raw material is strong, production operation and products scheme flexibly and the feature such as good product quality, therefore become production high-quality lightweight clear gusoline and solved the important channel in industrial chemicals source.

Hydrocracking catalyst is generally bifunctional catalyst, and its lytic activity and hydrogenation activity are provided respectively by the acidic components in catalyst and hydrogenation active component.

Acidic components in catalyst are generally provided by molecular sieve contained in catalyst and/or the refractory inorganic oxides that forms carrier.Refractory inorganic oxides generally comprise in amorphous aluminum silicide, amorphous alumina one or more.Molecular sieve in carrier has inseparable relation with the conjugation between refractory inorganic oxides with between decentralization and its reactivity worth, affects the activity of catalyst and selective to various object product to a great extent.

For hydrocracking catalyst, the difference of mating between cracking function and hydrogenating function can produce different reaction effects, that is for different object products, needs the cracking function and the hydrogenating function that regulate catalyst.

Hydrocracking catalyst disclosed in the patents such as CN200810117102.6, CN200710012770.8, CN00109747.4 is all prepared after mechanical mixture by raw material single to molecular sieve, aluminium oxide etc.Catalyst prepared by the method can be uneven because of various raw material mixing, affects the performance of each component property.

CN1060976A discloses a kind of preparation method of the ultrastable containing amorphous alumina.The method is that in aluminum sulfate solution, add ammoniacal liquor adjust ph be 3.5 ~ 7.5, then NaY zeolite or HNaY zeolite is added, mix, then prepare USY zeolite process by hydro-thermal method and carry out the subsequent treatment such as ammonium ion exchange and hydrothermal treatment consists, obtain the ultrastable containing amorphous alumina.The method is after aluminium oxide plastic, adds zeolite materials, then the composite of modification gained according to a conventional method.There is amorphous alumina and easily occur agglomeration in the method, make amorphous alumina skewness over a molecular sieve, even block the duct of molecular sieve, the specific area of catalyst and pore volume are significantly reduced, and the patency in molecular sieve and aluminium oxide duct is poor, affect the performance of catalyst.The method carries out hydrothermal treatment consists and ammonium exchange process by NaY zeolite again with after amorphous alumina compound, increases treating capacity, reduces the efficiency of process, and in processing procedure, amorphous alumina can be processed together, easily produces ill effect to aluminium oxide.

CN200610134152.6 discloses a kind of preparation method of hydrogenation catalyst, and the method adopts a kind of carrier material containing molecular sieve and amorphous aluminum silicide, adopts infusion process or coprecipitation load hydrogenation active metals component to obtain final catalyst.Wherein carrier material is prepared by the method directly adding molecular sieve in amorphous aluminum silicide plastic process, easily there is agglomeration in such amorphous aluminum silicide, also easily enter the duct of the other side or the aperture of blocking molecular sieve, affect amorphous aluminum silicide distribution over a molecular sieve, the connectivity in molecular sieve and amorphous aluminum silicide duct is poor, the specific area of catalyst and pore volume are reduced, active metal distribution is not easy to control, and then the hydrogenating function of catalyst is not mated with cracking function, affect the performance of catalyst.

Summary of the invention

In order to overcome the deficiencies in the prior art, the invention provides a kind of preparation method of hydrogenation catalyst.Molecular sieve and aluminium oxide can combine by the catalyst prepared by the method, there is good conjugation and decentralization, can avoid occurring reuniting between molecular sieve and amorphous alumina even clogging, effectively regulate hydrogenating function and the cracking function of catalyst simultaneously, improve the serviceability of catalyst.

The preparation method of hydrogenation catalyst of the present invention, comprising:

(1) preparation is containing the molecular sieve of hydrogenation active metals component, wherein hydrogenation active metals component with the content of oxide basis for 1wt% ~ 50wt%;

(2) mixed with organic amine by the molecular sieve of step (1) gained, wherein the addition of organic amine accounts for the 1wt% ~ 40wt% of molecular sieve, is preferably 7wt% ~ 40wt%;

(3) in amorphous alumina plastic process, add mixture and organic matter that step (2) obtains, the weight ratio of amorphous alumina and molecular sieve is made to be 1:19 ~ 19:1, organic addition accounts for the 1wt% ~ 50wt% of amorphous alumina weight, be preferably 20wt% ~ 50wt%, described organic matter is containing the organic alcohols of two or more hydroxyls, containing one or more in the organic acid of two or more carboxyls;

(4) carry out aging after the amorphous alumina cemented into bundles described in step (3), then carry out hydrothermal treatment consists, then after filtration, washing, dry, obtain catalyst intermediate;

(5) by the catalyst intermediate of step (4) gained through shaping, dry and roasting, obtains hydrogenation catalyst.

In step of the present invention (1), described hydrogenation active metals component is at least one in group VIII metal and group vib metal.Described group VIII metal is one or more in Fe, Co, Ni, and group vib metal is Mo and/or W.Described contains in the molecular sieve of hydrogenation active metals component, and preferably containing group vib metal and group VIII metal, wherein the weight ratio of group vib metal and group VIII metal is 2 ~ 8:1.

In step of the present invention (1), preparation adopts infusion process containing the molecular sieve of hydrogenation active metals component, process is as follows: joined by molecular sieve in the maceration extract containing hydrogenation active metals component, adopts saturated infusion process or supersaturation infusion process, through dry and roasting after dipping.Dipping can adopt once, also can adopt and repeatedly flood, and after each dipping, through super-dry, and then need carry out dipping next time, wherein drying condition is as follows: drying 2 ~ 24 hours under 60 ~ 180 DEG C of temperature conditions.Condition that is dry and roasting is carried out as follows: drying 2 ~ 24 hours under 60 ~ 180 DEG C of temperature conditions, roasting 2 ~ 12 hours under 300 ~ 600 DEG C of conditions after dipping hydrogenation active metals.

In step of the present invention (2), described organic amine is fatty amine, aromatic amine, one or more in hydramine that carbon number is less than 20.Better suited is the amine containing chain, is preferably containing one or more in the fatty amines of 2 ~ 10 carbon numbers.Such as: ethamine, propylamine, tert-butylamine; Decyl amine, dimethylamine, di-n-propylamine, butylamine, hexylamine, 2 ethyl hexylamine, diethylamine, diisopropylamine, hexamethylene diamine, 1,2-dimethyl propylamine, sec-butylamine, 1,5-dimethylhexylamine, ethylenediamine, 1, one or more in 2-propane diamine, Putriscine, monoethanolamine, diethanol amine, triethanolamine, 3-Propanolamine, monoisopropanolamine, diisopropanolamine (DIPA), triisopropanolamine, aniline.Organic amine mixes with molecular sieve, organic amine directly can be added in molecular sieve, also organic amine can be dissolved in solvent and add again in molecular sieve, solvent is wherein water, one or more in low-carbon alcohols (namely carbon number is one or more in the monohydric alcohol of 1 ~ 5).After the molecular sieve of step (1) gained being mixed with organic amine in step (2), can after filtration, after filtration and after drying, then step (3) can also be carried out.

The plastic process of the amorphous alumina described in step of the present invention (3) can be undertaken by process well known to those skilled in the art.The plastic process of amorphous alumina is generally the neutralization reaction process of acid material and alkaline material.Plastic process can adopt the mode of the continuous acid-base titration of soda acid, also can adopt two kinds of materials and the mode of stream neutralization.

In step of the present invention (3), aluminium oxide plastic is the process adopting aluminum soluble salt and acidic precipitation agent or alkaline precipitating agent to carry out neutralization reaction, aluminum soluble salt wherein used is one or more in aluminium chloride, aluminum sulfate, aluminum nitrate, acidic precipitation agent used is generally one or several in hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, carbon dioxide etc., and alkaline precipitating agent used is generally one or several in sodium carbonate, sodium acid carbonate, NaOH, potassium hydroxide, ammoniacal liquor etc.During aluminium oxide plastic also can adopt meta-aluminate (such as sodium metaaluminate and/or potassium metaaluminate) and acid aluminium salt (in such as aluminium chloride, aluminum nitrate, aluminum sulfate one or more) to carry out and the method for plastic.Described plastic process is generally carried out at room temperature ~ 85 DEG C, is comparatively suitably for 40 ~ 80 DEG C, is preferably 50 ~ 70 DEG C.Described plastic process is generally carried out under certain pH value condition, and typical pH is 6.0 ~ 10.0, is comparatively suitably for 7.0 ~ 9.5, is preferably 7.5 ~ 9.0.Aging described in step (4), condition is as follows: pH is 6.0 ~ 10.0, and be preferably 7.0 ~ 9.5, ageing time 0.25 ~ 8 hour, is comparatively adapted at 0.5 ~ 5 hour, and be preferably 1 ~ 3 hour, aging temperature is room temperature ~ 85 DEG C, is preferably 40 ~ 80 DEG C.Temperature time aging and pH with in time temperature preferably identical with pH.

In step of the present invention (1), described molecular sieve is known any one or several molecular sieve, one or several in best modified molecular screen.In hydrogenation catalyst, conventional molecular sieve as Y zeolite, β zeolite, ZSM Series Molecules sieve, SAPO Series Molecules sieve, MCM Series Molecules sieve etc. one or more, these molecular sieves are that those skilled in that art are known.In order to obtain the catalytic performance of hope, various molecular sieve can carry out suitable modifying process, the process that method of modifying is well known to those skilled in the art, as one or more method modifications in hydrothermal treatment consists, acid treatment, ion-exchange, various solvent process etc.

In step of the present invention (3), the incorporation way of the mixture of step (2) gained adopts the one or more combination of following manner: this mixture, in plastic neutralization reaction process, adds in plastic cans by (1) continuously; (2) this mixture is first joined in plastic cans, then will prepare in the acid material of amorphous alumina and alkaline material and plastic; (3) one or more with plastic material of this mixture are mixed, then in plastic material and plastic.

Organic alcohols described in step of the present invention (3) is the organic compound containing two or more hydroxyls, its boiling point is higher than gelling temperature, generally at 100 DEG C ~ 350 DEG C, preferably more than 120 DEG C, preferably more than 150 DEG C further, such as diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, propane diols, glycerine, 1,4-butanediol, butantriol, 2,2-dimethyl-1, one or more in 3 propane diols, DPG, xylitol, pentanediol, 1,6-hexylene glycol, pentitol, hexitol, sweet mellow wine.Described organic acid is the organic compound containing two or more carboxyls, its boiling point is higher than gelling temperature, general at 100 DEG C ~ 350 DEG C, preferably more than 120 DEG C, preferably more than 150 DEG C further, such as, in ethanedioic acid (oxalic acid), malonic acid, citric acid, succinic acid, malic acid, tartaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid one or more.

In step of the present invention (3), described organic feed postition can select the one or more combination of following manner: (1) joined in advance in plastic cans before plastic, (2) be added drop-wise in plastic cans in plastic process, (3) with one or more mixing of plastic raw material, add in plastic cans with material.Described organic matter can the mixture of same step (2) gained together add, and also can add separately.

In step of the present invention (4), before hydrothermal treatment consists, preferably after filtration or heating concentration, remove excessive moisture and organic matter.Wherein said heating simmer down to is heating steps (3) products obtained therefrom at 90 ~ 110 DEG C, and good temperature is 95 ~ 105 DEG C, preferably 98 ~ 100 DEG C, is heated to immobilising paste shape.

In step of the present invention (4), described hydrothermal treatment consists is carried out in closed container, and the temperature of hydrothermal treatment consists is 90 ~ 300 DEG C, preferably 100 ~ 250 DEG C, be preferably 150 ~ 210 DEG C, described hydrothermal treatment consists is carried out under the pressure condition of self that produces when material treatment temperature.Described hydrothermal conditions is 0.5 ~ 48h, is 1 ~ 36h, preferably 2 ~ 24h preferably.

In step of the present invention (4), the mode of washing of described material is known in those skilled in the art, can select to add the mode such as water washing, lower alcohols washing when making beating washing, filtration, the temperature of washing should in the scope of room temperature ~ 90 DEG C temperature, preferably 50 ~ 70 DEG C.The washing of described material is generally carried out in the scope that pH is 1.0 ~ 9.0, and preferred pH is 4.0 ~ 8.5.Material described in step of the present invention (4) should not contain or contain the heteroion of seldom amount after washing, filtration, and heteroion comprises Na ⁺, Cl ^-, SO ₄ ^2-, NO ₃ ^-, K ⁺deng in one or more.

In step of the present invention (4), described material is after washing, filtering, and filter cake carries out drying, and drying mode can adopt natural drying, oven drying, spraying dry, microwave drying or infra-red drying, and general drying condition is as follows: at 50 ~ 150 DEG C.

In step (5) catalyst intermediate forming process, shaping assistant can be added as required as one or more in adhesive, peptization acid, extrusion aid etc.

In step (5), after catalyst intermediate is shaping, drying condition is generally at 80 ~ 200 DEG C, and dry 1 ~ 15 hour, sintering temperature was generally 450 ~ 700 DEG C, and roasting time is generally 1 ~ 10 hour.

Hydrogenation catalyst prepared by the inventive method also can add other auxiliary agent, as required as one or more in phosphorus, boron, titanium, zirconium etc.The mode introduced in hydrogenation catalyst can adopt conventional method, such as can introduce in step (3) plastic process, can introduce, infusion process also can be adopted to introduce in step (5) forming process.

Hydrogenation catalyst prepared by the inventive method, with the weight of hydrogenation catalyst for benchmark, hydrogenation active metals content take oxide basis as 3wt% ~ 40wt%.

In the preparation process of hydrogenation catalyst of the present invention, molecular sieve mixes with organic amine in advance, organic amine can be adsorbed onto duct and the aperture place of molecular sieve in advance, the pore passage structure of molecular sieve is protected in advance, fragment in aluminium oxide plastic process can be avoided like this to enter duct, blocking aperture or direct plastic in duct, organic amine has the guide effect to aluminium oxide duct in aluminium oxide plastic process simultaneously, and match with the organic matter of the hydroxyl added in aluminium oxide plastic process or carboxyl, because the organic matter of hydroxyl or carboxyl is water-soluble, preferentially form chemical bond or hydrogen bond with organic amine, directly extend in solvent from the duct of molecular sieve, there is hydrophilic aluminium oxide in molecular sieve surface arrangement in order, be deposited on the surface of molecular sieve equably, and enhance the adhesion of molecular sieve and aluminium oxide, avoid amorphous alumina and even block the phenomenon in duct with occurring between molecular sieve reuniting, and make the duct of aluminium oxide and molecular sieve mutually through, aluminium oxide and molecular sieve is made to give full play to synergy, the aging amorphous Alumina gel that contributes to is assembled gradually, even pore-forming, and hydrothermal treatment consists contributes to the mesopore of aluminium oxide formation rule, improves the serviceability of catalyst.Generally, hydrothermal treatment consists temperature is higher, the processing time is longer, and the ratio shared by the mesopore formed is higher.Before molecular sieve is metal-modified, preferably according to requirements adopt suitable method to carry out modification, the modification process of such molecular sieve can not produce adverse influence to composite carrier.Hydrogenation catalyst prepared by the inventive method, part or all of hydrogenation active metals component is first incorporated in molecular sieve, make the acid centre of hydrogenation active metals and molecular sieve fully close, regulate hydrogenating function and acid function, control reactant and carry out either shallow cracking, alumina growth surrounds molecular sieve in the outside of molecular sieve on the other hand, for product provides unobstructed diffusion admittance, making product can be diffused into reaction center outside timely, providing good reaction environment for reaching desirable object product.Hydrogenation catalyst prepared by the inventive method is specially adapted to acid requirement relatively low, Hydrogenation requires relatively high hydrogenation catalyst, be applicable to either shallow cracking, in the hydrocracking process of deep hydrogenation, such as middle oil type hydrocracking catalyst, Hydroisomerization Catalysts, Hydrodewaxing catalyst etc.

Detailed description of the invention

Hydrogenation catalyst obtained by the inventive method can directly use as hydrogenation catalyst, also can supplement part hydrogenation active metals component as required, to meet the needs of differential responses.Amount according to the performance of catalyst and supplementary hydrogenation active metals component selects suitable method, such as can to adopt in infusion process, physical mixed method, coprecipitation method one or more, preferably adopt infusion process.Supplement after dip loading hydrogenation active metals, after drying and roasting, obtain hydrogenation catalyst.Wherein drying condition is as follows: be generally at 80 ~ 200 DEG C, dry 1 ~ 15 hour, and roasting condition is roasting 1 ~ 8 hour at 350 ~ 550 DEG C.

In the inventive method, preparation adopts conventional method preparation containing the maceration extract of hydrogenation active metals, such as nickel source, cobalt source are selected from one or more in nitrate, acetate, chloride, soluble complexes, molybdenum source is selected from one or more in molybdate, molybdenum trioxide, tungsten source is selected from one or more in tungstates, ethyl metatungstate, also can adopt solution prepared by heteropoly acid or its salt containing hydrogenation active metals component.According to method provided by the invention, not limiting the solvent in solution, can be organic solvent, as alcohol, ether and acid, can be inorganic solvent, as water.

Catalyst preparation process of the present invention is simple, convenient, is easy to operation, is applicable to industrial production.

The inventive method is particularly useful for preparing hydrocracking catalyst, select suitable molecular sieve (Y molecular sieve and/or beta-molecular sieve), the cracking function of adjustment catalyst and hydrogenating function, improve the activity of catalyst and the selective of object product, can obtain good result of use.This hydrocracking catalyst is particularly suitable for treatment of heavy hydrocarbon material, the boiling range scope of heavy hydrocarbon material is at 250 ~ 600 DEG C, general at 300 ~ 550 DEG C, there is the feedstock oil of These characteristics as gas oil, vacuum distillate, deasphalted oil, catalytic cracking recycle oil, shale oil, coal tar wet goods.Reaction condition generally under hydrogen existence condition, reaction pressure 5 ~ 30MPa, hydrogen to oil volume ratio 100 ~ 5000, volume space velocity 0.1 ~ 5.0h during liquid ^-1, reaction temperature 340 ~ 420 DEG C.

The specific area of product of the present invention and pore volume adopt low temperature liquid nitrogen physisorphtion to measure, and relative crystallinity and cell parameter adopt X-ray diffraction method to measure.Sodium content adopts By Icp-aes.In the present invention, wt% is mass fraction.

Further illustrate preparation method of the present invention below in conjunction with specific embodiment, but scope of the present invention is not only limited to the scope of these embodiments.

embodiment 1

1164g solid aluminum chloride is joined in 3 liters of distilled water, heat simultaneously and be stirred to dissolving, obtaining liquor alumini chloridi (a).Concentrated ammonia liquor being added appropriate distilled water diluting is dissolved in 300ml water into about 10wt% weak aqua ammonia (b), 89g sweet mellow wine, forms solution (c).78.6gY type molecular sieve Y-1 (SiO ₂/ Al ₂o ₃mol ratio is 11.0, and lattice constant is 24.42, and relative crystallinity is 95%) use the dipping solution containing 36g sodium tungstate and 32g Nickelous nitrate hexahydrate to carry out saturated dipping, 120 DEG C of dryings 180 minutes after dipping, 500 DEG C of roastings 4 hours; 30.6g ethylenediamine is dissolved in 300ml absolute ethyl alcohol, is heated to 60 DEG C, stirs half an hour, adds metallic Y molecular sieve, continues stirring 2 hours, is adsorbed the modified molecular screen (d) of organic amine after filtration in advance.Get a plastic cans, (a) is added and after being heated with stirring to 60 DEG C in tank, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.0, now in tank, add (d), continue to drip (b), open the valve of the container having (c), control, in 30 minutes, system in tank is added drop-wise to pH=8.0, control the valve of the container of (c), ensure now to be added dropwise to complete.Temperature is kept to be 60 DEG C, pH=8.0, aging 1 hour, by material in tank at 100 DEG C at baking oven inner drying to contents on dry basis 15wt%, material is transferred in autoclave, process 18h under 165 DEG C of conditions, then used by material ethanol to carry out solvent extraction and remove a part of organic matter, filter, washing is extremely without chlorion, filter, by filter cake at 110 DEG C dry 10 hours, pulverize and sieve and obtain catalyst intermediate J-1.

Get catalyst intermediate J-1100 gram, form paste, extruded moulding with the peptization liquid comes into contact containing nitric acid, then dry at 120 DEG C, after dry 180 minutes, by dried catalyst 500 DEG C of roastings 4 hours, obtain catalyst A, its composition is in table 2.

embodiment 2

1074g Solid aluminum sulfate is joined in 3 liters of distilled water, heat simultaneously and be stirred to dissolving, obtaining aluminum sulfate solution (a).Concentrated ammonia liquor is added appropriate distilled water diluting to be dissolved in 1L water into about 10wt% weak aqua ammonia (b), 160g1,4-butanediol, obtain solution (c).391gY type molecular sieve Y-1 (SiO ₂/ Al ₂o ₃mol ratio is 11.0, and lattice constant is 24.42, and relative crystallinity is 95%) use the dipping solution containing 405g sodium tungstate and 357.3g Nickelous nitrate hexahydrate to carry out saturated dipping, 120 DEG C of dryings 180 minutes after dipping, 500 DEG C of roastings 4 hours; 78g1,4 butanediamine are dissolved in 1L water, are heated to 60 DEG C, stir half an hour, add metallic molecular sieve, stir and obtain molecular sieve pulp (d) after 2 hours.Get a plastic cans, (a) is added and after being heated with stirring to 60 DEG C in tank, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.0, open the valve of the container having (c) and (d), continue to drip (b), control, in 30 minutes, system in tank is added drop-wise to pH=8.0, control the valve of the container of (c) and (d), ensure now to be added dropwise to complete.Temperature is kept to be 60 DEG C, pH=8.0, aging 1 hour, by material in tank at 100 DEG C at baking oven inner drying to contents on dry basis 15wt%, material is transferred in autoclave, process 4h under 180 DEG C of conditions, used by material ethanol to carry out solvent extraction part organic matter, filter, washing is to sulfate radical-free ion, filter, by filter cake at 110 DEG C dry 10 hours, pulverize and sieve and obtain catalyst intermediate J-2.

Get catalyst intermediate J-2100 gram, form paste, extruded moulding, at 120 DEG C after dry 180 minutes, by dried catalyst 500 DEG C of roastings 4 hours, obtain catalyst B with the peptization liquid comes into contact containing nitric acid, its composition is in table 2.

embodiment 3

187g Solid aluminum sulfate is joined in 7L distilled water, heats simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a).Solid sodium metaaluminate being mixed with concentration is 20gAl ₂o ₃/ l sodium aluminate solution (b), 66.8g1, ammediol is dissolved in 300ml water, forms solution (c).39.3gY type molecular sieve Y-1 (SiO ₂/ Al ₂o ₃mol ratio is 11.0, and lattice constant is 24.42, and relative crystallinity is 95%) use the dipping solution containing 54.7g sodium tungstate and 48.2g Nickelous nitrate hexahydrate to carry out saturated dipping, 120 DEG C of dryings 180 minutes after dipping, 500 DEG C of roastings 4 hours; 3.93g diethanol amine is dissolved in 6L water, is heated to 60 DEG C, under stirring, add metallic molecular sieve, continues to keep temperature to stir 2 hours, filters and obtains processing rear molecular sieve (d).Get a plastic cans, insert after 2l deionized water and stirring is heated to 60 DEG C and add (d), open the valve of container having (a), (b) and (c) simultaneously, the pH=8.0 of the hierarchy of control, control in 45 minutes, (a) and (c) to be dripped off, valve-off.Temperature is kept to be 60 DEG C, pH=8.0, aging 1 hour, by material filtering in tank to contents on dry basis 15wt%, material is transferred in autoclave, 4h is processed under 180 DEG C of conditions, filter, wash to sulfate radical-free ion, filter, by filter cake at 110 DEG C dry 10 hours, pulverize and sieve and obtain catalyst intermediate J-3.

Get catalyst intermediate J-3100 gram, form paste, extruded moulding with the peptization liquid comes into contact containing nitric acid, then dry at 120 DEG C, after dry 180 minutes, by dried catalyst 500 DEG C of roastings 4 hours, obtain catalyst C, its composition is in table 2.

embodiment 4

1538g solid aluminum chloride is joined in 3L water, heats simultaneously and be stirred to dissolving, obtain liquor alumini chloridi (a).Concentrated ammonia liquor being added appropriate distilled water diluting is dissolved in 1L water into about 10wt% weak aqua ammonia (b), 235.3g adipic acid, forms solution (c).103.8g Hydrogen β zeolite B-1 (SiO ₂/ Al ₂o ₃mol ratio is 30.0, and lattice constant is 12.00, and relative crystallinity is 90%) use the dipping solution containing 35g sodium tungstate and 31g Nickelous nitrate hexahydrate to carry out saturated dipping, 120 DEG C of dryings 180 minutes after dipping, 500 DEG C of roastings 4 hours; 40.5g monoethanolamine is dissolved in 50ml water, is heated to 60 DEG C, adds metallic molecular sieve under stirring, continues to keep temperature to stir 2 hours, filters and obtains pretreatment molecular sieves (d).Get a plastic cans, (a) is added and after being heated with stirring to 60 DEG C in tank, open the valve of the container having (b), control, within 10 minutes, system in tank is added drop-wise to pH=4.5, now in tank, add (d), continue to drip (b), open the valve of the container having (c), control, in 30 minutes, system in tank is added drop-wise to pH=8.0, control the valve of the container of (c), ensure now to be added dropwise to complete.Temperature is kept to be 60 DEG C, pH=8.0, aging 1 hour, by material in tank at 100 DEG C at baking oven inner drying to contents on dry basis 15wt%, material is transferred in autoclave, process 18h under 165 DEG C of conditions, used by material ethanol to carry out solvent extraction part organic matter, filter, washing is extremely without chlorion, filter, by filter cake at 110 DEG C dry 10 hours, pulverize and sieve and obtain catalyst intermediate J-4.

Get catalyst intermediate J-4100 gram, form paste, extruded moulding with the peptization liquid comes into contact containing nitric acid, then at 120 DEG C, after dry 180 minutes, by dried catalyst 500 DEG C of roastings 4 hours, obtain catalyst D, its composition is in table 2.

comparative example 1

Repeat the synthesis of embodiment 2, do not carry out hydrothermal treatment consists, obtained comparative catalyst's intermediate DF-1.

The process of catalyst intermediate DF-1 synthetic catalyst, with embodiment 2, obtains catalyst DA, and its composition is in table 2.

comparative example 2

Repeat the synthesis of embodiment 2, do not add Putriscine and pentitol, do not carry out hydrothermal treatment consists, obtained comparative catalyst's intermediate DF-2.

The process of catalyst intermediate DF-2 synthetic catalyst, with embodiment 2, obtains catalyst DB, and its composition is in table 2.

comparative example 3

Repeat the synthesis of embodiment 2, do not add Putriscine, obtained comparative catalyst's intermediate DF-3.

The process of catalyst intermediate DF-3 synthetic catalyst, with embodiment 2, obtains catalyst DC, and its composition is in table 2.

comparative example 4

Repeat the synthesis of embodiment 4, do not carry out hydrothermal treatment consists, obtained comparative catalyst's intermediate DF-4.

The process of catalyst intermediate DF-4 synthetic catalyst, with embodiment 4, obtains catalyst DD, and its composition is in table 2.

comparative example 5

Repeat the synthesis of embodiment 2, molecular sieve does not carry out metal-modified, obtained comparative composite DF-5.

Get product DF-5 carrier material 100 grams, paste is formed with the peptization liquid comes into contact containing nitric acid, extruded moulding, after drying roasting, the same maceration extract containing W-Ni metal component contacts 3 hours, then at 120 DEG C after dry 180 minutes, by dried catalyst 500 DEG C of roastings 4 hours, obtain catalyst DE, its composition is in table 2.

Table 1 raw molecule sieve main character

	Y-1	B-1
			Specific area, m 2/g	786	553
Pore volume, ml/g	0.37	0.40

The composition of table 2 catalyst and character

Catalyst is numbered	A	B	C	D	DA	DB	DC	DD	DE
										WO 3，wt％	4.16	24.58	11.34	3.03	21.2	21.3	21.8	3.1	21.5
NiO，wt％	1.34	7.92	3.66	0.97	7.4	6.3	8.9	1.0	7.9
										Specific area, m 2/g	357	321	311	336	318	294	330	335	277
Pore volume, ml/g	0.64	0.32	0.57	0.66	0.31	0.29	0.31	0.64	0.30

The invention described above catalyst and comparative catalyst thereof are evaluated.Evaluation feedstock oil is Iranian VGO, and character is in table 3, and appreciation condition is as follows: reaction pressure 14MPa, hydrogen to oil volume ratio 1500, volume space velocity 1.5h during liquid ^-1.Main character is in table 4.

Table 3 raw material oil properties

Density, d 4 20	0.9024	Mass spectral analysis, wt%
				Boiling range, DEG C		-alkane	19.7
IBP	321	-cycloalkane	36.7
				10%	393	-aromatic hydrocarbons	41.1
50%	443	-colloid	25
				90%	497	S，wt%	1.01
EP	528	N，μg/g	1138
				Carbon residue, wt%	0.03	BMCI value	40.3

Table 4 evaluation result

Catalyst is numbered	B	DA	DB	DE
					Reaction temperature, DEG C	360	360	360	360
Conversion ratio, wt%	65	64	55	65
					Middle distillates oil selectivity, wt%	82.2	78.7	65.8	80.7

As can be seen from evaluation result, the catalyst using the inventive method to prepare has active and product selectivity preferably.

Claims (27)

1. a preparation method for hydrogenation catalyst, comprising:

(1) preparation is containing the molecular sieve of hydrogenation active metals component, wherein hydrogenation active metals component with the content of oxide basis for 1wt% ~ 50wt%;

(2) mixed with organic amine by the molecular sieve of step (1) gained, wherein the addition of organic amine accounts for the 1wt% ~ 40wt% of molecular sieve;

(3) in amorphous alumina plastic process, add mixture and organic matter that step (2) obtains, the weight ratio of amorphous alumina and molecular sieve is made to be 1:19 ~ 19:1, organic addition accounts for the 1wt% ~ 50wt% of amorphous alumina weight, and described organic matter is containing the organic alcohols of two or more hydroxyls, containing one or more in the organic acid of two or more carboxyls;

(4) carry out after the amorphous alumina cemented into bundles described in step (3) aging, after hydrothermal treatment consists, more after filtration, washing, dry, obtain catalyst intermediate;

(5) by the catalyst intermediate of step (4) gained through shaping, dry and roasting, obtains hydrogenation catalyst.

2. in accordance with the method for claim 1, it is characterized in that in step (1), described hydrogenation active metals is at least one in group VIII metal and group vib metal.

3. in accordance with the method for claim 2, it is characterized in that described group VIII metal is one or more in Fe, Co, Ni, group vib metal is Mo and/or W.

4. in accordance with the method for claim 2, it is characterized in that described hydrogenation active metals is group vib metal and group VIII metal, wherein the weight ratio of group vib metal and group VIII metal is 2 ~ 8:1.

5. in accordance with the method for claim 1, it is characterized in that, in step (2), the addition of organic amine accounts for the 7wt% ~ 40wt% of molecular sieve.

6. in accordance with the method for claim 1, it is characterized in that in step (1), preparation adopts containing the method for the molecular sieve of hydrogenation active metals component the saturated dipping of maceration extract or supersaturation impregnated zeolite that contain hydrogenation active component, through dry and roasting after dipping, wherein condition that is dry and roasting is as follows: drying 2 ~ 24 hours under 60 ~ 180 DEG C of temperature conditions, roasting 2 ~ 12 hours under 300 ~ 600 DEG C of conditions.

7. in accordance with the method for claim 1, it is characterized in that in step (2), described organic amine is fatty amine, aromatic amine, one or more in hydramine that carbon number is less than 20.

8. in accordance with the method for claim 1, it is characterized in that in step (2), described organic amine is containing one or more in the fatty amines of 2 ~ 10 carbon numbers.

9. in accordance with the method for claim 1, it is characterized in that described organic amine and molecular sieve mixed method: directly added in molecular sieve by organic amine, or be dissolved in by organic amine in solvent and add in molecular sieve again, solvent is wherein one or more in water, low-carbon alcohols; Described low-carbon alcohols to be carbon number be in the monohydric alcohol of 1 ~ 5 one or more.

10. in accordance with the method for claim 1, after it is characterized in that step (2) molecular sieve mixes with organic amine, after filtration or after filtration and after drying, then carry out step (3).

11. in accordance with the method for claim 1, it is characterized in that the plastic process of the amorphous alumina described in step (3) is the neutralization reaction process of acid material and alkaline material, plastic process adopts the mode of the continuous acid-base titration of soda acid, or adopts two kinds of materials and the mode of stream neutralization.

12. in accordance with the method for claim 1, it is characterized in that in step (3), aluminium oxide plastic is the process adopting aluminum soluble salt and acidic precipitation agent or alkaline precipitating agent to carry out neutralization reaction, aluminum soluble salt wherein used is one or more in aluminium chloride, aluminum sulfate, aluminum nitrate, acidic precipitation agent used is one or several in hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, carbon dioxide, and alkaline precipitating agent used is one or several in sodium carbonate, sodium acid carbonate, NaOH, potassium hydroxide, ammoniacal liquor.

13. in accordance with the method for claim 1, it is characterized in that in step (3), with the method for plastic during aluminium oxide plastic adopts meta-aluminate and acid aluminium salt to carry out.

14. in accordance with the method for claim 1, it is characterized in that in step (1), and described molecular sieve is one or more in Y zeolite, β zeolite, ZSM Series Molecules sieve, SAPO Series Molecules sieve, MCM Series Molecules sieve.

15. in accordance with the method for claim 1, it is characterized in that in step (3), the incorporation way of the mixture of step (2) gained adopts the one or more combination of following manner: this mixture, in plastic neutralization reaction process, adds in plastic cans by (1) continuously; (2) this mixture is first joined in plastic cans, then will prepare in the acid material of amorphous alumina and alkaline material and plastic; (3) one or more with plastic material of this mixture are mixed, then in plastic material and plastic.

16. in accordance with the method for claim 1, it is characterized in that in step (3), organic addition accounts for the 20wt% ~ 50wt% of amorphous alumina weight.

17. in accordance with the method for claim 1, it is characterized in that the boiling point of the organic alcohols described in step (3) is 100 DEG C ~ 350 DEG C; The boiling point of described organic acid is 100 DEG C ~ 350 DEG C.

18. in accordance with the method for claim 1, it is characterized in that the organic alcohols described in step (3) is diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, propane diols, glycerine, 1,4-butanediol, butantriol, 2,2-dimethyl-1, one or more in 3 propane diols, DPG, xylitol, pentanediol, 1,6-hexylene glycol, hexitol.

19. in accordance with the method for claim 1, it is characterized in that the organic acid described in step (3) is one or more in ethanedioic acid, malonic acid, citric acid, succinic acid, malic acid, tartaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid.

20. in accordance with the method for claim 1, it is characterized in that in step (3), described organic feed postition selects the one or more combination of following manner: (1) joined in advance in plastic cans before plastic, (2) be added drop-wise in plastic cans in plastic process, (3) with one or more mixing of plastic raw material, add in plastic cans with material.

21. in accordance with the method for claim 1, it is characterized in that in step (4), before hydrothermal treatment consists, after filtration or heating concentration, remove excessive moisture and organic matter, described heating simmer down to is heating steps (3) products obtained therefrom at 90 ~ 110 DEG C, is heated to immobilising paste shape.

22. in accordance with the method for claim 1, it is characterized in that in step (4), described hydrothermal treatment consists is carried out in closed container, the temperature of hydrothermal treatment consists is 90 ~ 300 DEG C, described hydrothermal treatment consists is carried out under the pressure condition of self that produces when material treatment temperature, and described hydrothermal conditions is 0.5 ~ 48h.

23. in accordance with the method for claim 1, it is characterized in that in step (4), described hydrothermal treatment consists is carried out in closed container, the temperature of hydrothermal treatment consists is 100 ~ 250 DEG C, described hydrothermal treatment consists is carried out under the pressure condition of self that produces when material treatment temperature, and described hydrothermal conditions is 1 ~ 36h.

24. in accordance with the method for claim 1, it is characterized in that in step (5), and after catalyst intermediate is shaping, drying condition is at 80 ~ 200 DEG C, and dry 1 ~ 15 hour, sintering temperature was 450 ~ 700 DEG C, and roasting time is 1 ~ 10 hour.

25. in accordance with the method for claim 1, it is characterized in that the hydrogenation catalyst of gained needs supplementary part hydrogenation active metals component according to the Hydrogenation of catalyst.

26. in accordance with the method for claim 25, it is characterized in that: adopt infusion process to supplement load hydrogenation active metals component, again after drying and roasting, obtain hydrogenation catalyst, wherein drying condition is as follows: at 80 ~ 200 DEG C, dry 1 ~ 15 hour, roasting condition was roasting 1 ~ 8 hour at 350 ~ 550 DEG C.

27. in accordance with the method for claim 25, it is characterized in that described hydrogenation catalyst, and with the weight of hydrogenation catalyst for benchmark, hydrogenation active metals content take oxide basis as 3wt% ~ 40wt%.