CN103801372A - Preparation method of hydrogenation catalyst composition containing molecular sieves and amorphous silica-alumina - Google Patents
Preparation method of hydrogenation catalyst composition containing molecular sieves and amorphous silica-alumina Download PDFInfo
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- CN103801372A CN103801372A CN201210450421.5A CN201210450421A CN103801372A CN 103801372 A CN103801372 A CN 103801372A CN 201210450421 A CN201210450421 A CN 201210450421A CN 103801372 A CN103801372 A CN 103801372A
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Abstract
The invention discloses a preparation method of a hydrogenation catalyst composition containing molecular sieves and amorphous silica-alumina. The method comprises the following steps: adding a mixture of the molecular sieves and organic amines before or in the process of preparing an amorphous silica-alumina-hydrogenation active metal oxide composite oxide by a coprecipitation method; carrying out aging after gel forming is completed and then carrying out hydrothermal treatment, filtration, washing and drying; then forming, drying and roasting, thus obtaining the hydrogenation catalyst composition. A catalyst prepared by the method can organically combine the molecular sieves and amorphous silica-alumina together with good combination degree and dispersion degree, thereby avoiding agglomeration and even blockage of the molecular sieves and amorphous silica-alumina, simultaneously controlling the distribution of hydrogenation components on various acidic components effectively and improving the usability of the catalyst. The hydrogenation catalyst composition prepared by the method is especially suitable for hydrogenation catalysts with relatively high requirements for acidity and relatively low requirements for hydrogenation properties.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogenating catalyst composition, especially for the preparation method of the hydrogenating catalyst composition containing molecular sieve and amorphous aluminum silicide.
Background technology
Hydrocracking technology is one of important means of crude oil secondary operations, heavy oil lighting.Because it has that adaptability to raw material is strong, production operation and product solution 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 to be provided respectively by the acidic components in catalyst and hydrogenation activity component.
Acidic components in catalyst are generally to be provided by molecular sieve contained in catalyst and/or the refractory inorganic oxides that forms carrier.Refractory inorganic oxides generally comprises one or more in amorphous aluminum silicide, amorphous alumina.Between conjugation between molecular sieve and refractory inorganic oxides in carrier and decentralization and its reactivity worth, there is inseparable relation, affect to a great extent the active of catalyst and selective to various object products.
For hydrocracking catalyst, the difference of mating between cracking function and hydrogenating function can produce different reaction effects, that is for different object products, need to regulate cracking function and the hydrogenating function of catalyst.
In the patents such as CN200810117102.6, CN200710012770.8, CN00109747.4, disclosed hydrocracking catalyst is all that raw material single to molecular sieve, aluminium oxide etc. is prepared after mechanical mixture.The prepared catalyst of the method can be inhomogeneous because of various raw materials 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, to add ammoniacal liquor to regulate pH value be 3.5～7.5, then add NaY zeolite or HNaY zeolite, 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 raw material, then the composite of modification gained according to a conventional method.The method exists amorphous alumina easily to occur agglomeration, make the skewness of amorphous alumina on molecular sieve, even stop up the duct of molecular sieve, specific area and the pore volume of catalyst are significantly reduced, and the patency in molecular sieve and aluminium oxide duct is poor, affect the performance of catalyst.After the method is compound with amorphous alumina by NaY zeolite, carry out hydrothermal treatment consists and ammonium exchange process again, strengthened treating capacity, reduced the efficiency of processing, in processing procedure, amorphous alumina can be processed together, easily aluminium oxide produced to ill effect.
CN200610134152.6 discloses a kind of preparation method of hydrogenation catalyst, and the method is to adopt a kind of carrier material that contains molecular sieve and amorphous aluminum silicide, adopts infusion process or coprecipitation load hydrogenation active metals component to make final catalyst.Wherein carrier material is directly to add the method for molecular sieve to prepare in amorphous aluminum silicide plastic process, easily there is agglomeration in amorphous aluminum silicide like this, also easily enter the other side's duct or the aperture of obstruction molecular sieve, affect the distribution of amorphous aluminum silicide on molecular sieve, the connectivity in molecular sieve and amorphous aluminum silicide duct is poor, specific area and the pore volume of catalyst are reduced, active metal distributes and 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 hydrogenating catalyst composition.The catalyst of being prepared by the method can combine molecular sieve and amorphous aluminum silicide, there is good conjugation and decentralization, can avoid occurring reuniting between molecular sieve and amorphous aluminum silicide even clogging, effectively control the distribution of hydrogenation component on each acidic components simultaneously, the quantity at adjustment of acidity center and ratio, the serviceability of raising catalyst.
The preparation method of hydrogenating catalyst composition of the present invention, hydrogenation active metals component is selected from least one in group vib metal and group VIII metal, comprising:
(1) molecular sieve is mixed with organic amine, wherein the addition of organic amine accounts for the 1wt% ~ 40wt% of molecular sieve weight, is preferably 7wt% ~ 40wt%;
(2) mixture that adopts coprecipitation to prepare amorphous aluminum silicide and hydrogenation active metals oxide composite oxides before or add step (1) to obtain in process, the weight ratio that makes amorphous aluminum silicide and molecular sieve is 1:19 ~ 19:1, and hydrogenation active metals accounts for 3% ~ 50% of amorphous aluminum silicide weight in the addition of oxide;
(3) after step (2) coprecipitation reaction finishes, carry out agingly, then carry out hydrothermal treatment consists, then after filtration, washing, dry, obtain catalyst intermediate;
(4) catalyst intermediate of step (3) gained is through moulding, and dry and roasting, obtains hydrogenating catalyst composition.
In step of the present invention (1), described organic amine is one or more in fatty amine, the aromatic amine of carbon number more than 10.Better suited is the amine that contains chain, is preferably one or more in the fatty amines that contains 10 ~ 20 carbon numbers, for example: decyl amine, lauryl amine, cetylamine, octadecylamine, 1,10-decamethylene diamine, to one or more in butylaniline.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 in molecular sieve again, solvent is wherein one or more in water, low-carbon alcohols (being that carbon number is one or more in 1 ~ 5 monohydric alcohol).After molecular sieve being mixed with organic amine in step (1), can after filtration, after can also being also dried after filtration, then carry out step (2).
In step of the present invention (2), described group VIII metal is one or more in Fe, Co, Ni.Group vib metal is Mo and/or W.
In step of the present invention (2), employing coprecipitation prepares amorphous aluminum silicide and hydrogenation active metals oxide composite oxides can be undertaken by process well known to those skilled in the art.Generally in acid material and alkaline material and plastic process.Plastic process can adopt the mode of the continuous acid-base titration of soda acid, also can adopt the mode of two kinds of materials stream neutralization.
In step of the present invention (2), coprecipitation is to adopt aluminium source and hydrogenation active metals source (to be preferably molybdenum source, tungsten source, cobalt source, in nickel source one or more) react with precipitating reagent and carry out plastic, wherein aluminum soluble salt used is aluminium chloride, aluminum sulfate, one or more in aluminum nitrate, molybdenum source is molybdenum trioxide, can adopt the form of molybdenum trioxide slurries to add, tungsten source is sodium tungstate, ammonium metatungstate or wolframic acid, nickel source is nickel nitrate, nickel chloride, one or more in basic nickel carbonate, cobalt source is cobalt nitrate, cobalt chloride, one or more in basic cobaltous carbonate.Precipitating reagent used is generally one or several in sodium carbonate, sodium acid carbonate, NaOH, potassium hydroxide, ammoniacal liquor etc., preferably ammoniacal liquor.Plastic cans is generally introduced in silicon source in plastic process, also can with aluminium source or precipitant mix after again in and plastic, as waterglass add in aluminium salt or precipitating reagent, carry out in and plastic etc., silicon source also can add after the precipitation of aluminium source in material.Also can by aforesaid way, two or more be combined with.Described plastic process is generally carried out at room temperature ~ 85 ℃, is suitably for 40 ~ 80 ℃, is preferably 50 ~ 70 ℃.Described plastic process is generally carried out under certain pH value condition, and typical pH is 6.0 ~ 10.0, is suitably for 7.0 ~ 9.5, is preferably 7.5 ~ 9.0.Described aging of step (4), condition is as follows: pH is 6.0 ~ 10.0, is preferably 7.0 ~ 9.5, and ageing time 0.25 ~ 8 hour, is adapted at 0.5 ~ 5 hour, is preferably 1 ~ 3 hour, and aging temperature is room temperature ~ 85 ℃, is preferably 40 ~ 80 ℃.Temperature when aging and pH with in and time temperature and pH preferably identical.
In step of the present invention (1), described molecular sieve is known any or several molecular sieves, preferably one or several in modified molecular screen.In hydrogenating catalyst composition, 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 sieves 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 processing etc.
In step of the present invention (2), the introducing mode of the mixture of step (1) gained adopts the one or more combination of following manner: (1), in coprecipitation reaction process, adds this mixture in plastic cans continuously; (2) this mixture is first joined in plastic cans, then carry out coprecipitation reaction; (3) by this mixture, one or more with coprecipitate material are mixed, and then carry out coprecipitation reaction.
In step of the present invention (3), 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 (2) products obtained therefrom at 90 ~ 110 ℃, and temperature is 95 ~ 105 ℃ preferably, preferably 98 ~ 100 ℃, is heated to immobilising paste shape.
In step of the present invention (3), described hydrothermal treatment consists is carried out in closed container, and the temperature of hydrothermal treatment consists is 90 ~ 300 ℃, preferably 100 ~ 250 ℃, be preferably 150 ~ 210 ℃, described hydrothermal treatment consists is for carrying out under self the pressure condition producing when the material treatment temperature.The described hydrothermal treatment consists time is 0.5 ~ 48h, is 1 ~ 36h, preferably 2 ~ 24h preferably.
In step of the present invention (3), the mode of washing of described material is known in those skilled in the art, can select making beating washing, filtration time, add the mode such as water washing, lower alcohols washing, the temperature of washing should be in the scope of room temperature ~ 90 ℃ temperature, preferably 50 ~ 70 ℃.In the scope that the washing of described material is generally 1.0 ~ 9.0 at pH, carry out, preferably pH is 4.0 ~ 8.5.Material described in step of the present invention (3) should not contain or contain the seldom heteroion of 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 (3), described material is after washing, filtering, filter cake is dried, and that drying mode can adopt is natural drying, oven drying, spraying are dry, microwave drying or infra-red drying, drying condition: generally at 50 ~ 150 ℃ dry 1 ~ 15 hour.
In step (4) catalyst intermediate forming process, can add as required shaping assistant as one or more in adhesive, peptization acid, extrusion aid etc.
In step (4), after catalyst intermediate moulding, drying condition is generally at 80 ~ 200 ℃, and dry 1 ~ 15 hour, sintering temperature was generally 450 ~ 700 ℃, and roasting time is generally 1 ~ 10 hour.
Hydrogenating catalyst composition 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 of introducing in hydrogenating catalyst composition can adopt conventional method, such as introducing in step (2) plastic process, can in step (5) forming process, introduce, and also can adopt infusion process to introduce.
Hydrogenating catalyst composition prepared by the inventive method, take the weight of hydrogenating catalyst composition as benchmark, hydrogenation active metals content is counted 3wt% ~ 40wt% with oxide.In catalyst of the present invention, the weight ratio of group vib metal and VIII family metal is 2 ~ 8:1.
In the preparation process of hydrogenating catalyst composition 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, can avoid like this fragment in amorphous aluminum silicide plastic process to enter duct, obstruction aperture or directly plastic in duct, organic amine has the guide effect to amorphous aluminum silicide duct in amorphous aluminum silicide plastic process simultaneously, make to have hydrophilic amorphous aluminum silicide orderly at molecular sieve surface alignment, be deposited on equably the surface of molecular sieve, and strengthen the adhesion of molecular sieve and amorphous aluminum silicide, avoid amorphous aluminum silicide even to stop up the phenomenon in duct with occurring between molecular sieve reuniting, and the duct of amorphous aluminum silicide and molecular sieve is connected mutually, make amorphous aluminum silicide and molecular sieve give full play to synergy, improve the serviceability of catalyst.Hydrogenating catalyst composition prepared by the inventive method, partly or entirely hydrogenation active metals component is deposited on amorphous aluminum silicide, the acid centre of hydrogenation active metals and molecular sieve is fully isolated, regulate hydrogenating function and acid function, control reactant and carry out deep pyrolytic, amorphous aluminum silicide is grown in the outside encirclement molecular sieve of molecular sieve on the other hand, for product provides unobstructed diffusion admittance, make product can be diffused into timely reaction center outside, provide good reaction environment for reaching desirable object product.Hydrogenating catalyst composition prepared by the inventive method is specially adapted to acidity to require relatively high, and Hydrogenation requires relatively low hydrogenation catalyst, is applicable to drastic cracking, in the hydrocracking process of shallow degree hydrogenation, such as light oil type hydrogen cracking etc.
The specific embodiment
The prepared hydrogenating catalyst composition of the inventive method can directly use as hydrogenation catalyst, also can supplement as required partial hydrogenation active metal component, to meet the needs of differential responses.Select suitable method according to the amount of the performance of catalyst and supplementary hydrogenation active metals component, such as adopting 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 hydrogenating catalyst composition.Wherein drying condition is as follows: be generally at 80 ~ 200 ℃, dry 1 ~ 15 hour, roasting condition was roasting 1 ~ 8 hour at 350 ~ 550 ℃.
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 the solution of preparing containing heteropoly acid or its salt of hydrogenation active metals component.According to method provided by the invention, the solvent in solution is not limited, 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, and easy operating 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), adjust cracking function and the hydrogenating function of catalyst, improve the selective of the activity of catalyst and 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 ℃, generally, at 300 ~ 550 ℃, 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 when liquid
-1, 340 ~ 420 ℃ of reaction temperatures.
The specific area of product of the present invention and pore volume are to 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 embodiment.
embodiment 1
By 129g solid aluminum chloride, 86.5g sodium tungstate, 76.3g nickel nitrate joins in 2 liters of distilled water, heats simultaneously and is stirred to dissolving, obtains solution (a).Add appropriate distilled water diluting into about 10wt% weak aqua ammonia (b) concentrated ammonia liquor, 4.3g cetylamine is dissolved in 200ml absolute ethyl alcohol, adds 11gY 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%) formation solution (c).Get 10L waterglass (technical grade, modulus is 3.0) and be diluted in 20L deionized water, be configured to solution (d).Get a plastic cans, in tank, add (a) and be heated with stirring to after 65 ℃, open the valve of the container that has (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.5, now in tank, add 250ml solution (c), continue to drip (b), system in tank is added drop-wise to PH=8.0 in controlling 30 minutes.Keeping temperature is 65 ℃, and pH=8.0, stopped after 20 minutes, in system, added solution (d), and the amount of the waterglass that the part by weight that is 50/50 according to silica/alumina in amorphous aluminum silicide calculates added in 10 minutes.Aging 1 hour, by material in tank at 100 ℃ at baking oven inner drying to contents on dry basis 15wt%, material is transferred in autoclave, under 165 ℃ of conditions, process 18h, then material is used ethanol to carry out solvent extraction and remove a part of organic matter, filter, washing is extremely without chlorion, filter, filter cake is dried to 10 hours at 110 ℃, pulverize and sieve and obtain catalyst intermediate J-1.
Get 100 grams of catalyst intermediate J-1, the same contact of the peptization liquid containing nitric acid forms paste, and extruded moulding is then dry at 120 ℃, is dried after 180 minutes, and dried catalyst, 500 ℃ of roastings 4 hours, is obtained to catalyst A, and its composition is in table 2.
embodiment 2
By 129g solid sulphuric acid aluminium, 93g sodium tungstate, 82g nickel nitrate joins in 2 liters of distilled water, heats simultaneously and is stirred to dissolving, obtains solution (a).Add appropriate distilled water diluting into about 10wt% weak aqua ammonia (b) concentrated ammonia liquor, 23g cetylamine is dissolved in 200ml absolute ethyl alcohol, adds 115.3gY 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%) making beating formation slurries (c).Get 10L waterglass (technical grade, modulus is 3.0) and be diluted in 20L deionized water, be configured to solution (d).Get a plastic cans, in tank, add (a) and be heated with stirring to after 65 ℃, open the valve of the container that has (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.5, open the valve of the container that has (c), continue to drip (b), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes, control the valve of the container of (c), guarantee to be now added dropwise to complete.Keeping temperature is 65 ℃, and pH=8.0, stopped after 20 minutes, in system, added solution (d), and the amount of the waterglass that the part by weight that is 50/50 according to silica/alumina in amorphous aluminum silicide calculates added in 10 minutes.Aging 1 hour, by material in tank at 100 ℃ at baking oven inner drying to contents on dry basis 15wt%, material is transferred in autoclave, under 180 ℃ of conditions, process 4h, use ethanol to carry out a solvent extraction part organic matter material, filter, wash to sulfate radical-free ion, filter, filter cake is dried to 10 hours at 110 ℃, pulverize and sieve and obtain catalyst intermediate J-2.
Get 100 grams of catalyst intermediate J-2, the same contact of the peptization liquid containing nitric acid forms paste, and extruded moulding is then dry at 120 ℃, is dried after 180 minutes, and dried catalyst, 500 ℃ of roastings 4 hours, is obtained to catalyst B, and its composition is in table 2.
embodiment 3
By 129g solid sulphuric acid aluminium, 551g sodium tungstate, 486g nickel nitrate joins in 2 liters of distilled water, heats simultaneously and is stirred to dissolving, obtains solution (a).It is 20g Al that solid sodium metaaluminate is mixed with to concentration
2o
3/ l sodium aluminate solution (b), 109g lauryl amine is dissolved in 2.5L absolute ethyl alcohol, adds wherein 1090gY 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%) making beating, make slurries (c).Get 10L waterglass (technical grade, modulus is 3.0) and be diluted in 20L deionized water, be configured to solution (d).Get a plastic cans, inserting 2l deionized water and stirring is heated to after 65 ℃, open simultaneously have (a), (b) and (c) valve of container, the pH=8.0 of the hierarchy of control, (c) He (d) drips off (a) in controlling 45 minutes.Keeping temperature is 65 ℃, and pH=8.0, stopped after 20 minutes, in system, added solution (d), and the amount of the waterglass that the part by weight that is 50/50 according to silica/alumina in amorphous aluminum silicide calculates added in 10 minutes.Aging 1 hour, by material in tank at 100 ℃ at baking oven inner drying to contents on dry basis 15wt%, material is transferred in autoclave, under 180 ℃ of conditions, process 4h, use ethanol to carry out a solvent extraction part organic matter material, filter, wash to sulfate radical-free ion, filter, filter cake is dried to 10 hours at 110 ℃, pulverize and sieve and obtain catalyst intermediate J-3.
Get 100 grams of catalyst intermediate J-3, the same contact of the peptization liquid containing nitric acid forms paste, and extruded moulding is then dry at 120 ℃, is dried after 180 minutes, and dried catalyst, 500 ℃ of roastings 4 hours, is obtained to catalyst C, and its composition is in table 2.
embodiment 4
By 129g solid aluminum chloride, 7g sodium tungstate, 6g nickel nitrate joins in 2 liters of distilled water, heats simultaneously and is stirred to dissolving, obtains solution (a).Add appropriate distilled water diluting into about 10wt% weak aqua ammonia (b) concentrated ammonia liquor, 2g octadecylamine is dissolved in 60ml absolute ethyl alcohol, adds 5.2g Hydrogen β zeolite (SiO
2/ Al
2o
3mol ratio is 30.0, and lattice constant is 12.00, and relative crystallinity is 90%) making beating, form slurries (c).Get 10L waterglass (technical grade, modulus is 3.0) and be diluted in 20L deionized water, be configured to solution (d).Get a plastic cans, in tank, add (a) and be heated with stirring to after 65 ℃, open the valve of the container that has (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, continue to drip (b), open the valve of the container that has (c), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes, control the valve of the container of (c), guarantee to be now added dropwise to complete.Keeping temperature is 65 ℃, and pH=8.0, stopped after 20 minutes, in system, added solution (d), and the amount of the waterglass that the part by weight that is 50/50 according to silica/alumina in amorphous aluminum silicide calculates added in 10 minutes.Aging 1 hour, by material in tank at 100 ℃ at baking oven inner drying to contents on dry basis 15wt%, material is transferred in autoclave, under 180 ℃ of conditions, process 4h, use ethanol to carry out a solvent extraction part organic matter material, filter, wash to sulfate radical-free ion, filter, filter cake is dried to 10 hours at 110 ℃, pulverize and sieve and obtain catalyst intermediate J-4.
Get 100 grams of catalyst intermediate J-4, the same contact of the peptization liquid containing nitric acid forms paste, and extruded moulding is dry at 120 ℃, is dried after 180 minutes, and dried catalyst, 500 ℃ of roastings 4 hours, is obtained to catalyst D, and its composition is in table 2.
comparative example 1
Repeat the synthetic of embodiment 2, do not add organic amine, make 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 synthetic of embodiment 2, do not carry out hydrothermal treatment consists, make 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 synthetic of embodiment 4, do not carry out hydrothermal treatment consists, make comparative catalyst's intermediate DF-3.
The process of catalyst intermediate DF-3 synthetic catalyst, with embodiment 4, obtains catalyst DC, and its composition is in table 2.
comparative example 4
Repeat the synthetic of embodiment 2, in coprecipitation process, do not add active metal component, make comparative composite DF-4.Get 100 grams of product DF-4 carrier materials, form paste with the peptization liquid contact containing nitric acid, extruded moulding, the same contact of the maceration extract containing W-Ni metal component 3 hours after drying roasting, then dry after 180 minutes at 120 ℃, dried catalyst, 500 ℃ of roastings 4 hours, is obtained to catalyst DD, and 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 numbering | A | B | C | D | DA | DB | DC | DD |
| WO 3，wt％ | 30.25 | 21.93 | 18.91 | 3.78 | 21.0 | 21.1 | 3.9 | 21.0 |
| NiO，wt％ | 9.75 | 7.07 | 6.09 | 1.22 | 7.9 | 8.2 | 1.2 | 7.2 |
| Specific area, m 2/g | 250 | 399 | 469 | 425 | 356 | 395 | 428 | 306 |
| Pore volume, ml/g | 0.50 | 0.34 | 0.28 | 0.37 | 0.31 | 0.33 | 0.38 | 0.31 |
The invention described above catalyst and comparative catalyst thereof are evaluated.Evaluation is Iranian VGO with feedstock oil, and character is in table 3, and appreciation condition is as follows: reaction pressure 14MPa, hydrogen to oil volume ratio 1500, volume space velocity 1.5 h when 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, ℃ | ? | -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 numbering | B | DA | DB | DD |
| Conversion ratio, wt% | 75 | 75 | 75 | 75 |
| Reaction temperature, ℃ | 367 | 370 | 369 | 367 |
| Heavy naphtha yield, wt% | 39.3 | 37.5 | 38.2 | 38.6 |
| Boat yield of coal, wt% | 18.1 | 16.5 | 16.8 | 17.3 |
Can find out from evaluation result, the catalyst that uses the inventive method to prepare has good activity and product selectivity.
Claims (17)
1. a preparation method for hydrogenating catalyst composition, hydrogenation active metals component is selected from least one in group vib metal and group VIII metal, comprising:
(1) molecular sieve is mixed with organic amine, wherein the addition of organic amine accounts for the 1wt% ~ 40wt% of molecular sieve weight;
(2) mixture that adopts coprecipitation to prepare amorphous aluminum silicide and hydrogenation active metals oxide composite oxides before or add step (1) to obtain in process, the weight ratio that makes amorphous aluminum silicide and molecular sieve is 1:19 ~ 19:1, and hydrogenation active metals accounts for 3% ~ 50% of amorphous aluminum silicide weight in the addition of oxide;
(3) after step (2) coprecipitation reaction finishes, carry out aging, after hydrothermal treatment consists, more after filtration, washing, dry, obtain catalyst intermediate;
(4) catalyst intermediate of step (3) gained is through moulding, and dry and roasting, obtains hydrogenating catalyst composition.
2. in accordance with the method for claim 1, 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.
3. in accordance with the method for claim 1, 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.
4. in accordance with the method for claim 1, it is characterized in that in step (1), the addition of organic amine accounts for the 7wt% ~ 40wt% of molecular sieve weight.
5. in accordance with the method for claim 1, it is characterized in that in step (1), described organic amine is that carbon number is one or more in 10 above fatty amines, aromatic amine, hydramine, acid amides, naphthylamines.
6. in accordance with the method for claim 1, it is characterized in that in step (1), described organic amine is one or more in the fatty amines that contains 10 ~ 20 carbon numbers.
7. in accordance with the method for claim 1, it is characterized in that in step (1), described organic amine and molecular sieve mixed method: organic amine is directly added in molecular sieve, or organic amine is dissolved in solvent and is added in molecular sieve again, and solvent is wherein one or more in water, low-carbon alcohols; Described low-carbon alcohols is that carbon number is one or more in 1 ~ 5 monohydric alcohol.
8. in accordance with the method for claim 1,, after it is characterized in that step (1) molecular sieve mixes with organic amine, after being also dried after filtration or after filtration, then carry out step (2).
9. in accordance with the method for claim 1, it is characterized in that in step (1), described molecular sieve is one or more in Y zeolite, β zeolite, ZSM Series Molecules sieve, SAPO Series Molecules sieve, MCM Series Molecules sieve and above-mentioned modified molecular screen.
10. in accordance with the method for claim 1, it is characterized in that in step (2), the introducing mode of the mixture of step (1) gained adopts the one or more combination of following manner: (1), in coprecipitation reaction process, adds this mixture in plastic cans continuously; (2) this mixture is first joined in plastic cans, then carry out coprecipitation reaction; (3) by this mixture, one or more with coprecipitate material are mixed, and then carry out coprecipitation reaction.
11. it is characterized in that in step (3), before hydrothermal treatment consists in accordance with the method for claim 1,, after filtration or heating concentration, remove excessive moisture and organic matter, described heating simmer down to is heating steps (2) products obtained therefrom at 90 ~ 110 ℃, is heated to immobilising paste shape.
12. in accordance with the method for claim 1, it is characterized in that in step (3), described hydrothermal treatment consists is carried out in closed container, the temperature of hydrothermal treatment consists is 90 ~ 300 ℃, described hydrothermal treatment consists is for carrying out under self the pressure condition producing when the material treatment temperature, and the described hydrothermal treatment consists time is 0.5 ~ 48h.
13. in accordance with the method for claim 1, it is characterized in that in step (3), described hydrothermal treatment consists is carried out in closed container, the temperature of hydrothermal treatment consists is 100 ~ 250 ℃, described hydrothermal treatment consists is for carrying out under self the pressure condition producing when the material treatment temperature, and the described hydrothermal treatment consists time is 1 ~ 36h.
14. in accordance with the method for claim 1, it is characterized in that in step (4), after catalyst intermediate moulding, drying condition is at 80 ~ 200 ℃, and dry 1 ~ 15 hour, sintering temperature was 450 ~ 700 ℃, and roasting time is 1 ~ 10 hour.
15. in accordance with the method for claim 1, it is characterized in that the hydrogenation catalyst of gained supplements partial hydrogenation active metal component as required.
16. in accordance with the method for claim 15, 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 ℃, dry 1 ~ 15 hour, roasting condition was roasting 1 ~ 8 hour at 350 ~ 550 ℃.
17. according to the method described in claim 1 or 15, it is characterized in that described hydrogenation catalyst, and take the weight of hydrogenation catalyst as benchmark, hydrogenation active metals content is counted 3wt% ~ 40wt% with oxide.
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