CN103801366A - Hydrogenation catalyst composition - Google Patents
Hydrogenation catalyst composition Download PDFInfo
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- CN103801366A CN103801366A CN201210450414.5A CN201210450414A CN103801366A CN 103801366 A CN103801366 A CN 103801366A CN 201210450414 A CN201210450414 A CN 201210450414A CN 103801366 A CN103801366 A CN 103801366A
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Abstract
The invention discloses a hydrogenation catalyst composition. The hydrogenation catalyst composition comprises hydrogenation active metal components, molecular sieves and amorphous alumina, wherein the hydrogenation active metal components are mainly loaded on amorphous alumina; the molecular sieves are coated with amorphous alumina; the hydrogenation active metal components account for 3-100% of amorphous alumina by weight in terms of oxide; the weight ratio of the molecular sieves to amorphous alumina is (1:19)-(19:1). The hydrogenation catalyst composition has the beneficial effects that the hydrogenation catalyst fully isolates the hydrogenation active metals from the acid centers of the molecular sieves and adjusts the hydrogenation and acid functions; the hydrogenation catalyst composition 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 hydrogenating catalyst composition and preparation method thereof, particularly contain hydrogenating catalyst composition of molecular sieve and preparation method thereof.
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 by Kaolinite Preparation of Catalyst carrier after mechanical mixture such as raw material single to molecular sieve, aluminium oxide etc., then by infusion process load hydrogenation active metals component.The prepared catalyst of the method is that hydrogenation active metals is uniformly distributed type catalyst, is unfavorable for like this regulating cracking function and the hydrogenating function of catalyst.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 hydrogenating catalyst composition.This carbon monoxide-olefin polymeric can effectively regulate hydrogenating function and acid function, improves the serviceability of catalyst.
Hydrogenating catalyst composition of the present invention, its composition comprises: hydrogenation active metals component, molecular sieve and amorphous alumina, wherein more than the 95.0wt% of hydrogenation active metals component in element, being generally 95.0wt% ~ 99.5wt% loads on amorphous alumina, the amorphous alumina parcel molecular sieve of load hydrogenation active metals component, hydrogenation active metals component accounts for 3% ~ 100% of amorphous alumina weight in oxide, and the weight ratio of molecular sieve and amorphous alumina is 1:19 ~ 19:1.
In hydrogenating catalyst composition of the present invention, described hydrogenation active metals is at least one in group VIII metal and group vib metal.Described group VIII metal is one or both in Co, Ni, and group vib metal is one or both in Mo, W.Described hydrogenation active metals is preferably group vib metal and group VIII metal, and wherein the weight ratio of group vib metal and group VIII metal is 2 ~ 8:1.
In hydrogenating catalyst composition of the present invention, take the weight of carbon monoxide-olefin polymeric as benchmark, hydrogenation active metals component is take the content of oxide as 3% ~ 40%.
The preparation method of hydrogenating catalyst composition of the present invention, 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 7 wt% ~ 40wt%;
(2) mixture that adopts coprecipitation to prepare aluminium oxide and hydrogenation active metals oxide composite oxides before or add step (1) to obtain in process;
(3) after step (2) coprecipitation reaction finishes, carry out agingly, 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 that carbon number is less than one or more in the fatty amine, aromatic amine, hydramine of 20.Better suited is the amine that contains chain, is preferably one or more in the fatty amines that contains 2 ~ 10 carbon numbers.For example: 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 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 the present invention, described group VIII metal is one or more in Co, Ni, and group vib metal is Mo and/or W.
In step of the present invention (2), employing coprecipitation prepares aluminium oxide 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 (be preferably one or more in molybdenum source, tungsten source, cobalt source, nickel source) to react with precipitating reagent and carry out plastic, wherein aluminium source used is aluminum soluble salt, be generally one or more in aluminium chloride, aluminum sulfate, aluminum nitrate, molybdenum source is molybdenum trioxide, can adopt the form of slurries to add, tungsten source is sodium tungstate, ammonium metatungstate or wolframic acid, and nickel source is one or more in nickel nitrate, nickel chloride, basic nickel carbonate.Cobalt source is one or more in cobalt nitrate, cobalt chloride, 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.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 (3), 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.
Step of the present invention can add organic matter in (2), organic addition accounts for the 1wt% ~ 50wt% of amorphous alumina weight, be preferably 20wt% ~ 50wt%, described organic matter be containing the organic alcohols of two or more hydroxyls, contain two or more carboxyls organic acid in one or more.Described organic alcohols is the organic compound containing two or more hydroxyls, its boiling point is higher than plastic temperature, generally at 100 ℃ ~ 350 ℃, preferably more than 120 ℃, further preferably more than 150 ℃, for example diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, propane diols, glycerine, 1,4-butanediol, butantriol, 2,2-dimethyl-1,3 propane diols, DPG, xylitol, pentanediol, 1, one or more in 6-hexylene glycol, hexitol, sweet mellow wine.Described organic acid is the organic compound containing two or more carboxyls, its boiling point is higher than plastic temperature, generally at 100 ℃ ~ 350 ℃, preferably more than 120 ℃, further preferably more than 150 ℃, for example, 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 (2), the described organic one or more combination that adds mode can select following manner: (1) joined in advance in plastic cans before coprecipitation reaction, (2) in coprecipitation reaction process, be added drop-wise in plastic cans, (3) with one or more mixing of co-precipitation raw material, add in plastic cans with material.Described organic matter can same step (1) gained mixture together add, also can add separately.
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 of the present invention, hydrogenation active metals component is deposited on aluminium oxide, 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, 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.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.
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 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, and match with the hydroxyl adding in aluminium oxide plastic process or the organic matter of carboxyl, because the organic matter of hydroxyl or carboxyl is water-soluble, make to have hydrophilic aluminium oxide orderly at molecular sieve surface alignment, be deposited on equably the surface of molecular sieve, and strengthen the adhesion of molecular sieve and aluminium oxide, avoid aluminium oxide even to stop up the phenomenon in duct with occurring between molecular sieve reuniting, and the duct of aluminium oxide and molecular sieve is connected mutually, make aluminium oxide and molecular sieve give full play to synergy, improve the serviceability of catalyst.
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 can adopt 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 3000g solid aluminum chloride, 266g sodium tungstate, 235g nickel nitrate joins in 10 liters of distilled water, heats simultaneously and is stirred to dissolving, obtains mixed solution (a).Add appropriate distilled water diluting into about 10wt% weak aqua ammonia (b) concentrated ammonia liquor, 230g 1,5-PD is dissolved in 2L water, forms solution (c).49.7g Isosorbide-5-Nitrae-ethylenediamine is dissolved in 300ml absolute ethyl alcohol, is heated to 60 ℃, stirs half an hour, adds 127.5g Y zeolite Y-1 (SiO
2/ Al
2o
3mol ratio is 11.0, and lattice constant is 24.42, and relative crystallinity is 95%), continue to stir 2 hours, after filtration, obtain adsorbing in advance the modified molecular screen (d) of organic amine.Get a plastic cans, 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, adds (d), continue to drip (b), open the valve of the container that has (c), in controlling 30 minutes, system in tank is added drop-wise to pH=8.0, controls the valve of the container of (c), guarantee to be now added dropwise to complete.Keeping temperature is 60 ℃, pH=8.0, and aging 1 hour, material in tank to be filtered, washing, to without chlorion, is filtered, and filter cake is dried to 10 hours at 110 ℃, pulverizes and sieves and obtains 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 2500g solid sulphuric acid aluminium, 1483g sodium tungstate, 1308g nickel nitrate joins in 10 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, 372.3g BDO is dissolved in 1L water, obtains solution (c).316.5g ethylenediamine is dissolved in 5L water, is heated to 60 ℃, stirs half an hour, adds 1582g Y zeolite Y-1 (SiO
2/ Al
2o
3mol ratio is 11.0, and lattice constant is 24.42, and relative crystallinity is 95%) stir after 2 hours and obtain molecular sieve pulp (d).Get a plastic cans, 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, open the valve that has (c) and container (d), continue to drip (b), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes, control the valve of (c) and container (d), guarantee to be now added dropwise to complete.Keeping temperature is 60 ℃, pH=8.0, and aging 1 hour, material in tank is filtered, 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 200g solid sulphuric acid aluminium, 416g sodium tungstate, 367g nickel nitrate joins in 10 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), 71.5g propane diols is dissolved in 1L water, forms solution (c).84.5g diethanol amine is dissolved in 10L water, is heated to 60 ℃, adds 845g Y zeolite Y-1 (SiO under stirring
2/ Al
2o
3mol ratio is 11.0, and lattice constant is 24.42, and relative crystallinity is 95%), continue to keep temperature to stir 2 hours, filter and obtain processing rear molecular sieve (d).Get a plastic cans, insert after 2l deionized water and stirring is heated to 60 ℃ and add (d), open simultaneously have (a), the valve of (b) and container (c), the pH=8.0 of the hierarchy of control, in controlling 45 minutes, drip off valve-off by (a) with (c).Keeping temperature is 60 ℃, pH=8.0, and aging 1 hour, material in tank is filtered, 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 650g solid aluminum chloride, 174g sodium tungstate, 153g nickel nitrate joins in 1L water, heats simultaneously and is stirred to dissolving, obtains solution (a).Add appropriate distilled water diluting into about 10% weak aqua ammonia (b) concentrated ammonia liquor, 99.5g adipic acid is dissolved in 1L water, forms solution (c).5.1g monoethanolamine is dissolved in 50ml ethanol, is heated to 60 ℃, adds 13.1g Hydrogen β zeolite B-1 (SiO under stirring
2/ Al
2o
3mol ratio is 30.0, and lattice constant is 12.00, and relative crystallinity is 90%), continue to keep temperature to stir 2 hours, filter and obtain pretreatment molecular sieves (d).Get the steel retort of one 20 liters, 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, adds (d), continue to drip (b), open the valve of the container that has (c), in controlling 30 minutes, system in tank is added drop-wise to pH=8.0, controls the valve of the container of (c), guarantee to be now added dropwise to complete.Keeping temperature is 60 ℃, pH=8.0, and aging 1 hour, material in tank to be filtered, washing, to without chlorion, is filtered, and filter cake is dried to 10 hours at 110 ℃, pulverizes and sieves and obtains 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.
embodiment 5
By 2600g solid sulphuric acid aluminium, 703g ammonium molybdate, 744g nickel nitrate joins in 10 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, 387g 1, 4-succinic acid is dissolved in 1L water, obtains solution (c).329g ethylenediamine is dissolved in 5L water, is heated to 60 ℃, stirs half an hour, adds 1646g Y zeolite Y-1 (SiO
2/ Al
2o
3mol ratio is 11.0, and lattice constant is 24.42, and relative crystallinity is 95%) stir after 2 hours and obtain molecular sieve pulp (d).Get a plastic cans, 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, open the valve that has (c) and container (d), continue to drip (b), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes, control the valve of (c) and container (d), guarantee to be now added dropwise to complete.Keeping temperature is 60 ℃, pH=8.0, and aging 1 hour, material in tank is filtered, wash to sulfate radical-free ion, filter, filter cake is dried to 10 hours at 110 ℃, pulverize and sieve and obtain catalyst intermediate J-5.
Get catalyst intermediate J-5100 gram, 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 E, and its composition is in table 2.
comparative example 1
Repeat the synthetic of embodiment 2, do not add ethylenediamine and BDO, 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 add ethylenediamine, 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 2, in plastic process, do not add active metal component, make comparative composite DF-3.
Get 100 grams of product DF-3 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 DC, and its composition is in table 2.
comparative example 4
Repeat the synthetic of embodiment 5, in plastic 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 Mo-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 | E | DA | DB | DC | DD |
| WO 3，wt％ | 11.34 | 26.47 | 18.53 | 27.23 | - | 21.5 | 22.9 | 22.0 | - |
| NiO，wt％ | 3.66 | 8.53 | 5.97 | 8.77 | 6.04 | 6.3 | 7.4 | 5.4 | 5.87 |
| MoO 3，wt％ | - | - | - | - | 18.30 | - | - | - | 18.54 |
| Molecular sieve, wt% | 8.50 | 44.20 | 58.89 | 3.20 | 51.68 | 44.20 | 44.20 | 44.20 | 51.68 |
| Amorphous alumina, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| Specific area, m 2/g | 332 | 385 | 473 | 215 | 377 | 310 | 345 | 308 | 396 |
| Pore volume, ml/g | 0.62 | 0.28 | 0.29 | 0.47 | 0.28 | 0.24 | 0.26 | 0.26 | 0.29 |
In the present invention, the surface-element of molecular sieve, carrier or catalyst distributes and is measured by X ray electronic spectroscopy.The element composition of catalyst adopts Elements method and obtains.
Choose without metal-modified Modified Zeolite Y Y-1, carrier DF-3, catalyst B, carrier DF-4, catalyst E and carry out the analysis of XPS surface-element, the surface-element molar distribution that the data obtained is sample.Catalyst B, catalyst E are carried out to Elements, and the data obtained converts the molar distribution of element to.Analysis result is in table 3.
Table 3 element distributes
| Element | Y-1 surface, At.% | Carrier DF-3 surface, At.% | Catalyst B surface, At.% | Catalyst B, At.% |
| Al2p | 5.26 | 40.00 | 23.92 | 13.40 |
| Ni2p | 0.00 | 0.00 | 6.70 | 2.92 |
| O1s | 65.79 | 60.00 | 62.68 | 64.43 |
| Si2p | 28.95 | 0.00 | 0.00 | 16.32 |
| W4f | 0.00 | 0.00 | 6.70 | 2.92 |
The continuous element of table 3 distributes
| Element | Y-1 surface, At.% | Carrier DF-4, At.% | Catalyst E surface, At.% | Catalyst E, At.% |
| Al2p | 5.26 | 40.00 | 25.64 | 13.80 |
| Ni2p | 0.00 | 0.00 | 4.39 | 1.84 |
| O1s | 65.79 | 60.00 | 63.19 | 64.70 |
| Si2p | 28.95 | 0.00 | 0.00 | 16.81 |
| Mo3d | 0.00 | 0.00 | 6.78 | 2.84 |
Can be found out by table 3 data, the outer surface gained Si of Y-1 molecular sieve and the distribution of Al approach the SiO of this molecular sieve substantially
2/ Al
2o
3mol ratio; The surface of carrier DF-3, DF-4 has no Si element, illustrates that the aluminium oxide in carrier wraps up molecular sieve completely and is evenly distributed; By relatively the surface of catalyst and the element of body phase distribute and can find, the W(Mo on catalyst B and E surface) and the content of Ni element carry out comparison with the amount of the contained amorphous alumina of this catalyst, the metal of this catalyst is substantially all distributed on the amorphous alumina in catalyst.
The invention described above catalyst and comparative catalyst thereof are evaluated.Evaluation is Iranian VGO with feedstock oil, and character is in table 4, 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 5.
Table 4 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 | 25.0 |
| 90% | 497 | S，wt% | 1.01 |
| EP | 528 | N，μg/g | 1138 |
| Carbon residue, wt% | 0.03 | BMCI value | 40.3 |
Table 5 evaluation result
| Catalyst numbering | B | E | DA | DB | DC | DD |
| Reaction temperature, ℃ | 360 | 360 | 365 | 362 | 360 | 360 |
| Conversion ratio, wt% | 65 | 65 | 64 | 65 | 65 | 65 |
| Middle distillates oil selectivity, wt% | 81.5 | 81.2 | 75.7 | 77.8 | 80.2 | 79.5 |
Can find out from evaluation result, the catalyst that uses the inventive method to prepare has good activity and product selectivity.
Claims (21)
1. a hydrogenating catalyst composition, its composition comprises: hydrogenation active metals component, molecular sieve and amorphous alumina, wherein hydrogenation active metals component loads on amorphous alumina above in the 95.0wt% of element, the amorphous alumina parcel molecular sieve of load hydrogenation active metals component, hydrogenation active metals component accounts for 3% ~ 100% of amorphous alumina weight in oxide, and the weight ratio of molecular sieve and amorphous alumina is 1:19 ~ 19:1.
2. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: hydrogenation active metals component loads on amorphous alumina in the 95.0wt% ~ 99.5wt% of element.
3. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that described hydrogenation active metals is at least one in group VIII metal and group vib metal.
4. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that described group VIII metal is one or both in Co, Ni, group vib metal is one or both in Mo, W.
5. according to carbon monoxide-olefin polymeric claimed in 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.
6. according to carbon monoxide-olefin polymeric claimed in claim 1, it is characterized in that: take the weight of carbon monoxide-olefin polymeric as benchmark, hydrogenation active metals component is take the content of oxide as 3% ~ 40%.
7. according to carbon monoxide-olefin polymeric claimed in claim 1, the catalyst described in it is characterized in that is prepared by following method, and process comprises:
(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 aluminium oxide and hydrogenation active metals oxide composite oxides before or add step (1) to obtain in process;
(3) after step (2) coprecipitation reaction finishes, carry out agingly, 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.
8. according to carbon monoxide-olefin polymeric claimed in claim 7, it is characterized in that in step (1), described organic amine is that carbon number is less than one or more in the fatty amine, aromatic amine, hydramine, acid amides, naphthylamines of 20.
9. according to carbon monoxide-olefin polymeric claimed in claim 7, it is characterized in that in step (1), described organic amine is one or more in the fatty amines that contains 2 ~ 10 carbon numbers.
10. according to the carbon monoxide-olefin polymeric described in claim 7,8 or 9, it is characterized in that in step (1), the addition of organic amine accounts for the 7wt% ~ 40wt% of molecular sieve weight.
11. according to carbon monoxide-olefin polymeric claimed in claim 7, 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.
12. according to carbon monoxide-olefin polymeric claimed in claim 7, after it is characterized in that step (1) molecular sieve mixes with organic amine, after being also dried after filtration or after filtration, then carries out step (2).
13. according to carbon monoxide-olefin polymeric claimed in 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.
14. according to carbon monoxide-olefin polymeric claimed in claim 7, 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 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.
15. according to carbon monoxide-olefin polymeric claimed in claim 7, it is characterized in that in step (2), and employing coprecipitation prepares aluminium oxide and hydrogenation active metals oxide composite oxides add organic matter before or in process; Organic addition accounts for the 1wt% ~ 50wt% of alumina weight, described organic matter be containing the organic alcohols of two or more hydroxyls, contain two or more carboxyls organic acid in one or more.
16. according to carbon monoxide-olefin polymeric claimed in claim 7, it is characterized in that in step (2), and employing coprecipitation prepares aluminium oxide and hydrogenation active metals oxide composite oxides add organic matter before or in process; Organic addition accounts for the 20wt% ~ 50wt% of alumina weight, described organic matter be containing the organic alcohols of two or more hydroxyls, contain two or more carboxyls organic acid in one or more.
17. according to the carbon monoxide-olefin polymeric described in claims 14 or 15, it is characterized in that the boiling point of the organic alcohols described in step (2) is higher than plastic temperature, and boiling point is 100 ℃ ~ 350 ℃; The boiling point of described organic acid is higher than plastic temperature, and boiling point is 100 ℃ ~ 350 ℃.
18. according to the carbon monoxide-olefin polymeric described in claims 14 or 15, it is characterized in that the organic alcohols described in step (2) is diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, propane diols, glycerine, 1,4-butanediol, butantriol, 2,2-dimethyl-1,3 propane diols, DPG, xylitol, pentanediol, 1, one or more in 6-hexylene glycol, hexitol, sweet mellow wine.
19. according to the carbon monoxide-olefin polymeric described in claims 14 or 15, it is characterized in that the organic acid described in step (2) 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. according to the carbon monoxide-olefin polymeric described in claims 14 or 15, it is characterized in that in step (2), the described organic mode that adds is selected the one or more combination of following manner: (1) joined in plastic cans in advance at the plastic initial stage, (2) in plastic process, be added drop-wise in plastic cans, (3) with one or more mixing of plastic raw material, add in plastic cans with material.
21. according to carbon monoxide-olefin polymeric claimed in claim 7, it is characterized in that in step (4), 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.
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| CN107138127A (en) * | 2017-05-10 | 2017-09-08 | 武汉理工大学 | A kind of bar-shaped Al of three-dimensional manometer2O3Shell-nuclear compounded material of@molecular sieves and preparation method thereof |
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| 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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