CN103801363A - Preparation method of hydrogenation catalyst containing molecular sieves - Google Patents
Preparation method of hydrogenation catalyst containing molecular sieves Download PDFInfo
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- CN103801363A CN103801363A CN201210450411.1A CN201210450411A CN103801363A CN 103801363 A CN103801363 A CN 103801363A CN 201210450411 A CN201210450411 A CN 201210450411A CN 103801363 A CN103801363 A CN 103801363A
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Abstract
The invention discloses a preparation method of a hydrogenation catalyst containing molecular sieves. The method comprises the following steps: adding a mixture of the molecular sieves containing hydrogenation active metal components and organic amines in the amorphous alumina gel forming process; aging after amorphous alumina gel forming is completed and then carrying out hydrothermal treatment, filtration, washing and drying; then carrying out forming, drying and roasting, thus obtaining the hydrogenation catalyst. By adopting the method, the molecular sieves and alumina can be organically combined together, the catalyst has good combination degree and dispersion degree, agglomeration and even blockage of the molecular sieves and amorphous alumina can be avoided, and meanwhile, the hydrogenation and cracking functions of the catalyst can be effectively adjusted and the usability of the catalyst can be improved. The catalyst prepared by the method is suitable for the shallow cracking and deep hydrogenation processes.
Description
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 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 hydrogenation catalyst.The catalyst of being prepared by the method can combine molecular sieve and aluminium oxide, 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, improve the serviceability of catalyst simultaneously.
The preparation method of hydrogenation catalyst of the present invention, comprising:
(1) preparation is containing the molecular sieve of hydrogenation active metals component, and wherein hydrogenation active metals component is take the content of oxide as 1wt% ~ 50wt%;
(2) molecular sieve of step (1) gained is mixed with organic amine, wherein the addition of organic amine accounts for the 1wt% ~ 40wt% of molecular sieve weight, is preferably 7wt% ~ 40wt%;
(3) mixture that adds step (2) to obtain in amorphous alumina plastic process, the weight ratio that makes amorphous alumina and molecular sieve is 1:19 ~ 19:1;
(4) after amorphous alumina cemented into bundles step (3) Suo Shu, carry out agingly, then carry out hydrothermal treatment consists, then after filtration, washing, dry, obtain catalyst intermediate;
(5) by the catalyst intermediate of step (4) gained through moulding, 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, preferably contains group vib metal and group VIII metal, and wherein the mol ratio of group vib metal and group VIII metal is 3 ~ 8:1, is preferably 4 ~ 6:1.
In step of the present invention (1), preparation adopts infusion process containing the molecular sieve of hydrogenation active metals component, process is as follows: molecular sieve is joined in the maceration extract containing hydrogenation active metals component, adopt saturated infusion process or supersaturation infusion process, after dipping, warp is dried and roasting.Dipping can adopt once, also can adopt repeatedly dipping, after each dipping, need be through super-dry, and then carry out dipping next time, wherein drying condition is as follows: under 60 ~ 180 ℃ of temperature conditions, be dried 2 ~ 24 hours.After dipping hydrogenation active metals, be dried with the condition of roasting as follows: under 60 ~ 180 ℃ of temperature conditions, be dried 2 ~ 24 hours, roasting 2 ~ 12 hours under 300 ~ 600 ℃ of conditions.
In step of the present invention (2), described organic amine be the fatty amine of carbon number more than 10, aromatic amine, in one or more.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 the molecular sieve of step (1) gained being mixed with organic amine in step (2), can be after filtration, can also be after filtration and after dry, then carry out step (3).
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 the mode of two kinds of materials stream neutralization.
In step of the present invention (3), aluminium oxide plastic is to adopt aluminum soluble salt and acidic precipitation agent or alkaline precipitating agent to carry out the process of neutralization reaction, wherein aluminum soluble salt 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.Aluminium oxide plastic also can adopt meta-aluminate (such as sodium metaaluminate and/or potassium metaaluminate) and acid aluminium salt (such as one or more in aluminium chloride, aluminum nitrate, aluminum sulfate) carry out in and the method for plastic.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 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, 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 (3), the introducing mode of the mixture of step (1) gained adopts the one or more combination of following manner: (1), in plastic neutralization reaction process, adds this mixture in plastic cans 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) by this mixture, one or more with plastic material are mixed, then in plastic material and plastic.
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 ℃, and temperature is 95 ~ 105 ℃ preferably, preferably 98 ~ 100 ℃, 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 ℃, 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 (4), 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 (4) 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 (4), described material is after washing, filtering, and filter cake is dried, and that drying mode can adopt is natural drying, oven drying, spraying are dry, microwave drying or infra-red drying, and general drying condition is as follows: at 50 ~ 150 ℃.
In step (5) catalyst intermediate forming process, can add as required shaping assistant as one or more in adhesive, peptization acid, extrusion aid etc.
In step (5), 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.
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 of introducing in hydrogenation catalyst can adopt conventional method, such as introducing in step (3) plastic process, can in step (5) forming process, introduce, and also can adopt infusion process to introduce.
Hydrogenation catalyst prepared by the inventive method, take the weight of hydrogenation catalyst as benchmark, hydrogenation active metals content is counted 3wt% ~ 40wt% with oxide.
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, can avoid like this fragment in aluminium oxide plastic process to enter duct, obstruction aperture or directly plastic in duct, organic amine has the guide effect to aluminium oxide duct in aluminium oxide plastic process simultaneously, organic amine part chain end extends in the outside, duct of molecular sieve, the aluminium oxide that can lead plastic is in the outside, duct of molecular sieve, the direction stretching along chain is wrapped in chain extended end around, avoid amorphous alumina staggered with duct between molecular sieve, the phenomenon in duct is even stopped up in reunion mutually, the duct of aluminium oxide and molecular sieve is connected mutually, aluminium oxide and molecular sieve are given full play to synergy, the aging amorphous alumina colloidal sol that contributes to is assembled gradually, evenly pore-forming, hydrothermal treatment consists contributes to the mesopore of aluminium oxide formation rule.Be conducive to the diffusion of reaction mass between catalyst inner surface and outer surface, be conducive to being uniformly distributed of active metal, improve the utilization rate of active metal, thereby improved the serviceability of catalyst, improved the serviceability of catalyst.Before molecular sieve is metal-modified, preferably according to requirements adopt suitable method to carry out modification, the modification process of molecular sieve can not produce adverse influence to composite carrier like this.Hydrogenation catalyst prepared by the inventive method, partly or entirely hydrogenation active metals component is first incorporated in molecular sieve, make the acid centre of hydrogenation active metals and molecular sieve fully approaching, regulate hydrogenating function and acid function, control reactant and carry out shallow degree cracking, alumina growth is surrounded molecular sieve in the outside 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.Hydrogenation catalyst prepared by the inventive method is specially adapted to acidity to require relatively low, Hydrogenation requires relatively high hydrogenation catalyst, be applicable to shallow degree cracking, in the hydrocracking process of deep hydrogenation, such as middle oil type hydrocracking catalyst, Hydroisomerization Catalysts, Hydrodewaxing catalyst etc.
The specific embodiment
The prepared hydrogenation catalyst 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 hydrogenation catalyst.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
2168g solid aluminum chloride is joined in 2.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain liquor alumini chloridi (a).Add appropriate distilled water diluting into about 10wt% weak aqua ammonia (b) concentrated ammonia liquor, 43.6g Y zeolite Y-1 (SiO
2/ Al
2o
3mol ratio is 11.0, and lattice constant is 24.42, and relative crystallinity is 95%) use containing the dipping solution of 49g sodium tungstate and 43g Nickelous nitrate hexahydrate and carry out saturated dipping, after dipping 120 ℃ dry 180 minutes, 500 ℃ of roastings 4 hours; 17g decyl amine is dissolved in 300ml absolute ethyl alcohol, is heated to 60 ℃, under stirring, adds metallic Y molecular sieve, stirs 2 hours, filters, and filter cake 4h at 100 ℃ is dried to obtain to (c).Get a stainless steel reaction tank, in tank, add (a) and be heated with stirring to after 60 ℃, open the valve of the container that has (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, now in tank, add (c), continue to drip (b), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes.Keeping temperature is 60 ℃, pH=8.0, 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
900g solid sulphuric acid aluminium is joined in 2.5 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a).Add appropriate distilled water diluting into about 10wt% weak aqua ammonia (b) concentrated ammonia liquor, 497.9gY 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 containing the dipping solution of 370g sodium tungstate and 325g Nickelous nitrate hexahydrate and carry out saturated dipping, after dipping 120 ℃ dry 180 minutes, 500 ℃ of roastings 4 hours; 99.6g cetylamine is dissolved in 1L ethanol, is heated to 65 ℃, under stirring, adds metallic molecular sieve, stirs 2h, filters, and filter cake is dried to 12h at 110 ℃ and obtain (c).Get a stainless steel reaction tank, in tank, add (a) and be heated with stirring to after 60 ℃, 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 (d), continue to drip (b), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes.Keeping temperature is 60 ℃, pH=8.0, 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, form paste with the peptization liquid contact containing nitric acid, extruded moulding is dried after 180 minutes at 120 ℃, and dried catalyst, 500 ℃ of roastings 4 hours, is obtained to catalyst B, and its composition is in table 2.
embodiment 3
274g solid sulphuric acid aluminium is joined in 1 liter of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a).It is 20g Al that solid sodium metaaluminate is mixed with to concentration
2o
3/ l sodium aluminate solution (b), 1157.5gY 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 containing the dipping solution of 360g sodium tungstate and 317g Nickelous nitrate hexahydrate and carry out saturated dipping, after dipping 120 ℃ dry 180 minutes, 500 ℃ of roastings 4 hours; 115.8g octadecylamine is dissolved in 4L ethanol, is heated to 65 ℃, under stirring, adds metallic molecular sieve, stirs 2h, obtains slurries (c).Get a stainless steel reaction tank, inserting 1L deionized water and stirring is heated to after 60 ℃, open simultaneously have (a), the valve of (b) and container (c), the pH=8.0 of the hierarchy of control, drips off by (a) with (c) in controlling 45 minutes.Keeping temperature is 60 ℃, PH=8.0, aging 1 hour, material filtering in tank, to contents on dry basis 15wt%, is transferred to material in autoclave, under 180 ℃ of conditions, process 4h, filter, wash to sulfate radical-free ion, filter, filter cake is dried to 10 hours at 110 ℃, pulverizes and sieves 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
2980g solid aluminum chloride is joined in 3 liters of distilled water, heat simultaneously and be stirred to dissolving, obtain liquor alumini chloridi (a).Add appropriate distilled water diluting into about 10wt% weak aqua ammonia (b) concentrated ammonia liquor, 162.8g 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 containing the dipping solution of 81.2g sodium tungstate and 71.6g Nickelous nitrate hexahydrate and carry out saturated dipping, after dipping 120 ℃ dry 180 minutes, 500 ℃ of roastings 4 hours; 63.5g cetylamine is dissolved in 100ml ethanol, is heated to 60 ℃, under stirring, adds metallic molecular sieve, stirs 1h, filters, and obtains filter cake (c).Get a stainless steel reaction tank, in tank, add (a) and be heated with stirring to after 60 ℃, open the valve of the container that has (b), within controlling 10 minutes, system in tank is added drop-wise to pH=4.0, now in tank, add (c), continue to drip (b), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes.Keeping temperature is 60 ℃, pH=8.0, 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, use ethanol to carry out a solvent extraction part organic matter material, filter, washing is extremely without chlorion, 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, form paste with the peptization liquid contact containing nitric acid, extruded moulding is then dried after 180 minutes at 120 ℃, 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-4 synthetic catalyst, with embodiment 4, obtains catalyst DC, and its composition is in table 2.
comparative example 4
Repeat the synthetic of embodiment 2, molecular sieve does not carry out metal-modified, makes 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％ | 3.40 | 21.86 | 12.86 | 3.78 | 22.7 | 21.2 | 4.0 | 21.1 |
| NiO，wt％ | 1.10 | 7.04 | 4.14 | 1.22 | 5.3 | 6.8 | 1.2 | 8.8 |
| Specific area, m 2/g | 325 | 371 | 496 | 324 | 369 | 414 | 329 | 312 |
| Pore volume, ml/g | 0.67 | 0.31 | 0.31 | 0.63 | 0.30 | 0.32 | 0.63 | 0.29 |
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% | 55 | 55 | 55 | 55 |
| Reaction temperature, ℃ | 372 | 375 | 373 | 372 |
| Middle distillates oil selectivity, wt% | 82.2 | 78.7 | 80.9 | 81.5 |
Can find out from evaluation result, the catalyst that uses the inventive method to prepare has good activity and product selectivity.
Claims (22)
1. a preparation method for hydrogenation catalyst, comprising:
(1) preparation is containing the molecular sieve of hydrogenation active metals component, and wherein hydrogenation active metals component is take the content of oxide as 1wt% ~ 50wt%;
(2) molecular sieve of step (1) gained is mixed with organic amine, wherein the addition of organic amine accounts for the 1wt% ~ 40wt% of molecular sieve weight;
(3) mixture that adds step (2) to obtain in amorphous alumina plastic process, the weight ratio that makes amorphous alumina and molecular sieve is 1:19 ~ 19:1;
(4) after amorphous alumina cemented into bundles step (3) Suo Shu, carry out agingly, then carry out hydrothermal treatment consists, after filtration, washing, dry, obtain catalyst intermediate;
(5) by the catalyst intermediate of step (4) gained through moulding, 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 weight.
6. in accordance with the method for claim 1, it is characterized in that in step (1), preparation adopts the saturated dipping of maceration extract or the supersaturation impregnated zeolite containing hydrogenation activity component containing the method for the molecular sieve of hydrogenation active metals component, after dipping, warp is dried and roasting, wherein condition dry and roasting is as follows: under 60 ~ 180 ℃ of temperature conditions, be dried 2 ~ 24 hours, roasting 2 ~ 12 hours under 300 ~ 600 ℃ of conditions.
7. in accordance with the method for claim 1, it is characterized in that in step (2), described organic amine is one or more in fatty amine, the aromatic amine of carbon number more than 10.
8. in accordance with the method for claim 1, it is characterized in that in step (2), described organic amine is one or more in the fatty amines that contains 10 ~ 20 carbon numbers.
9. in accordance with the method for claim 1, it is characterized in that in step (2), 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.
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 dry, then carry out step (3).
11. in accordance with the method for claim 1, the plastic process that it is characterized in that 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 the mode of two kinds of materials stream neutralization.
12. in accordance with the method for claim 1, it is characterized in that in step (3), aluminium oxide plastic is to adopt aluminum soluble salt and acidic precipitation agent or alkaline precipitating agent to carry out the process of neutralization reaction, wherein aluminum soluble salt 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), aluminium oxide plastic adopt meta-aluminate and acid aluminium salt carry out in the method for plastic.
14. 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.
15. in accordance with the method for claim 1, it is characterized in that in step (3), the introducing mode of the mixture of step (1) gained adopts the one or more combination of following manner: (1), in plastic neutralization reaction process, adds this mixture in plastic cans 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) by this mixture, one or more with plastic material are mixed, then in plastic material and plastic.
16. 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 ℃, is heated to immobilising paste shape.
17. 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 ℃, 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.
18. 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 ℃, 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.
19. in accordance with the method for claim 1, it is characterized in that in step (5), and 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.
20. 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.
21. in accordance with the method for claim 20, 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 ℃.
22. according to the method described in claim 1 or 20, 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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| WO2004002623A1 (en) * | 2002-06-28 | 2004-01-08 | Haldor Topsoe A/S | Catalyst comprising zeolite beta and its use in hydrocarbon conversion process |
| CN101167451A (en) * | 2007-09-17 | 2008-04-30 | 苏州科技学院 | Zeolite base composite antibiotic material and its preparation method |
| CN101172260A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst |
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| WO2004002623A1 (en) * | 2002-06-28 | 2004-01-08 | Haldor Topsoe A/S | Catalyst comprising zeolite beta and its use in hydrocarbon conversion process |
| CN101172260A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst |
| CN101167451A (en) * | 2007-09-17 | 2008-04-30 | 苏州科技学院 | Zeolite base composite antibiotic material and its preparation method |
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