CN103100406B - Method for preparing hydrogenation catalyst - Google Patents
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- CN103100406B CN103100406B CN201110355819.6A CN201110355819A CN103100406B CN 103100406 B CN103100406 B CN 103100406B CN 201110355819 A CN201110355819 A CN 201110355819A CN 103100406 B CN103100406 B CN 103100406B
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Abstract
The invention discloses a method for preparing a hydrogenation catalyst. The method comprises the following steps of preparing a catalyst carrier material, and introducing a hydrogenation active component by an impregnation method or a coprecipitation method to obtain the hydrogenation catalyst. A preparation process of the catalyst carrier material comprises the following steps of adding a mixture of a molecular sieve and an organic amine, and an organic alcohol and/or an organic acid into amorphous silica-alumina in gelling, after amorphous silica-alumina gelling, carrying out aging, and then carrying out filtration, washing and drying to obtain the catalyst carrier powder. The preparation method realizes ordered arrangement and uniform deposition of the silica-alumina on the surface of the molecular sieve, improves the binding strength of the molecular sieve and the silica-alumina, avoids agglomeration of the amorphous silica-alumina and the molecular sieve and channel blocking caused by the agglomeration, realizes mutual communication of channels of the silica-alumina and the molecular sieve, fully develops synergism of the silica-alumina and the molecular sieve, and improves catalyst use performances. The hydrogenation catalyst obtained by the method can be used for various hydrogenation processes.
Description
Technical field
The present invention relates to a kind of method of preparing hydrogenation catalyst, especially for the preparation method of the hydrogenation catalyst containing molecular sieve.
Background technology
Developing rapidly and crude oil variation progressively of World Economics, makes market increase year by year the demand of light-end products and industrial chemicals.Hydrocracking technology is that one of important means of crude oil secondary operations, heavy oil lighting has obtained increasingly extensive application.
The crucial hydrocracking catalyst of hydrocracking technology.Hydrocracking catalyst is a kind of bifunctional catalyst, and its lytic activity and hydrogenation activity are that acidic components and the hydrogenation activity component in catalyst provides respectively.Acidic components in catalyst are generally that molecular sieve and/or amorphous aluminum silicide contained in catalyst provides.The features such as molecular sieve has stronger acidity, is the main cracking component in catalyst, has reaction temperature low, and activity is strong.Amorphous aluminum silicide catalyst reaction temperatures is higher, but reaction comparatively relaxes, and middle distillates oil selectivity is good.It is the main direction of hydrocracking catalyst development that molecular sieve is used in combination with amorphous aluminum silicide and molecular sieve.And there is good activity, selective and stability by molecular sieve and the prepared catalyst of amorphous aluminum silicide, be suitable for long-term operation.
Between conjugation between molecular sieve in carrier and amorphous aluminum silicide and decentralization and its reactivity worth, have inseparable relation, the good dispersion acid site of carrier is evenly distributed, and it is comparatively even that reaction mass reacts in catalyst; Affect to a great extent the active of catalyst and selective to various object products.The dispersiveness how solving between molecular sieve and amorphous silicon alumina supporter is the key that preparation has sound response performance catalyst.
In the patents such as CN201010197869.1, CN200810117102.6, CN00105235.7, disclosed hydrocracking catalyst is all that the single raw materials such as molecular sieve, aluminium oxide are 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 by hydro-thermal method, prepare USY zeolite process 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 to prepare final catalyst.Wherein carrier material is directly to add the method for molecular sieve to prepare in amorphous aluminum silicide plastic process.In the method easily there is agglomeration in amorphous aluminum silicide, 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, catalyst activity Metal Distribution is inhomogeneous, affects the performance of catalyst.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of method of preparing hydrogenation catalyst.The catalyst of being prepared by the method combines molecular sieve and amorphous aluminum silicide, has good conjugation and decentralization, can avoid molecular sieve and and macropore amorphous aluminum silicide between the even clogging that occurs reuniting, improve the serviceability of catalyst.
The present invention prepares the method for hydrogenation catalyst, comprise: the catalyst carrier material that preparation contains molecular sieve and amorphous aluminum silicide, adopt infusion process or coprecipitation to introduce hydrogenation activity component, obtain final hydrogenation catalyst, wherein the preparation process of catalyst carrier material 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 and the organic matter that in amorphous aluminum silicide plastic process, add step (1) to obtain, the weight of final carrier material of take is benchmark, molecular sieve addition is 5wt% ~ 90wt%, organic addition is 1wt% ~ 50wt%, described organic matter for containing the organic alcohols of two or more hydroxyls, contain two or more carboxyls organic acid in one or more;
(3) after amorphous aluminum silicide cemented into bundles step (2) Suo Shu, carry out agingly, then after filtration, washing, dry, obtain catalyst carrier dry glue powder.
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: propylamine, tert-butylamine; Decyl amine, dimethylamine, di-n-propylamine, butylamine, hexylamine, ethamine, 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, can organic amine directly 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).If the addition of organic amine is larger, after needing to filter and be dried, carry out again step (2).
Amorphous aluminum silicide plastic process described in step of the present invention (2) can be undertaken by process well known to those skilled in the art.Amorphous aluminum silicide plastic process is generally the neutralization reaction process of acid material and alkaline material, and plastic process is general adopts two kinds of materials also to flow plastic mode of operation, or a kind of material is placed on the mode of operation that another kind of material in plastic cans adds plastic continuously.Plastic material generally comprises aluminium source (Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3and NaAlO
2deng in one or more), silicon source (one or more in waterglass, Ludox and organic silicon-containing compound etc.), precipitating reagent (NaOH, NH
4oH or CO
2deng), according to the different choice of plastic process, to use, conventional mode of operation mainly contains: (1) acid aluminium salt (Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3) and basic aluminium salt (NaAlO
2) or alkaline precipitating agent (NaOH, NH
4oH) in and plastic, (2) basic aluminium salt (NaAlO
2) and acidic precipitation agent (CO
2) in and plastic.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 basic aluminium salt or alkaline precipitating agent, carry out in and plastic, Ludox add in acid aluminium salt, carry out in and plastic etc.Silicon source also can add in the rear material of aluminium source precipitation.Also can by aforesaid way, two or more be combined with.Said method is all well-known to those skilled in the art.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 hydrogenation catalyst, conventional molecular sieve as Y zeolite, β zeolite, ZSM Series Molecules sieve, SAPO Series Molecules sieve, MCM Series Molecules sieve etc. one or more, these molecular sieves are that those skilled in that art are known.In order to obtain the catalytic performance of hope, various molecular 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 (1), the state that adds of described molecular sieve can be that dry powder-shaped adds, and can be also to add with slurries form.
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 plastic neutralization reaction process, adds in plastic cans by this mixture continuously; (2) this mixture is first joined in plastic cans, then will prepare in the acid material of amorphous aluminum silicide and alkaline material and plastic; (3) by this mixture, one or more with plastic material are mixed, then in plastic material and plastic.
Organic alcohols described in step of the present invention (2) 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.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 ℃, one or more in ethanedioic acid (oxalic acid), malonic acid, citric acid, succinic acid, malic acid, tartaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid for example.
In step of the present invention (2), the described organic one or more combination that adds mode can select following manner: (1) joins in plastic cans at the plastic initial stage in advance, (2) in plastic process, be added drop-wise in plastic cans, (3) with one or more mixing of plastic raw material, with material, add in plastic cans.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, in the time of can selecting making beating washing, filtration, add the modes 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 after washing, filtration or containing the heteroion of seldom measuring, 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, and general drying condition is as follows: at 50 ~ 150 ℃ dry 1 ~ 15 hour.
Carrier material of the present invention also can add other auxiliary agent as required, as one or more in phosphorus, boron, titanium, zirconium etc.
Carrier dry glue powder prepared by the inventive method is a kind of raw material of Kaolinite Preparation of Catalyst carrier, through 450 ~ 650 ℃ of roastings after 2 ~ 10 hours, the character of gained is as follows: the weight of carrier after roasting of take is benchmark, the content of molecular sieve is 5wt% ~ 90wt%, the content of amorphous aluminum silicide is at 10 wt% ~ 95wt%, in amorphous aluminum silicide, SiO
2content is generally 10wt% ~ 50wt%, and after roasting, the character of carrier is as follows: specific area is 200 ~ 1000m
2/ g, pore volume is 0.3 ~ 1.8cm
3/ g, meleic acid amount is 0.1 ~ 2.0mmol/g.
In the inventive method, hydrogenation activity component is generally one or more in group vib and group VIII metal, as one or more in molybdenum, tungsten, nickel, cobalt etc., the content of hydrogenation activity component in catalyst is generally 5% ~ 80%(in oxide, lower same), suitable content is 10% ~ 50%, can specifically determine according to the requirement of using.The introducing method of hydrogenation activity component is generally infusion process, coprecipitation etc., and concrete introducing method is content well known to those skilled in the art.As while adopting infusion process, first by carrier material moulding, dry, roasting, then with the carrier after the solution impregnation moulding that contains active hydrogenation component, then drying, roasting, obtain final hydrogenation catalyst.While adopting coprecipitation, by carrier material making beating, hydrogenation active metals is deposited in carrier material slurries, then, through washing, moulding, dry, roasting, obtains final hydrogenation catalyst.Above-mentioned catalyst preparation process and condition are all well known to those skilled in the art.In carrier forming process, can also add other carrier material or auxiliary agent, as one or more in boron oxide, titanium oxide, zirconia etc.
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 place, aperture of molecular sieve in advance, the pore passage structure of molecular sieve is protected in advance, can be avoided like this in sial plastic process fragment to enter duct, stop up aperture or direct plastic in duct, organic amine has the guide effect to sial duct in sial plastic process simultaneously, and match with the hydroxyl adding in sial plastic process or the organic matter of carboxyl, because the organic matter of hydroxyl or carboxyl is water-soluble, make to have hydrophilic sial orderly at molecular sieve surface alignment, be deposited on equably the surface of molecular sieve, and strengthened the adhesion of molecular sieve and sial, avoided amorphous aluminum silicide with occurring between molecular sieve reuniting, even to stop up the phenomenon in duct, and the duct of sial and molecular sieve is connected mutually, make sial and molecular sieve give full play to synergy, the utilization rate with metal that is uniformly distributed that is conducive to active metal, improved the serviceability of catalyst.Molecular sieve can adopt various suitable methods to process according to its instructions for use before introducing, and the modification process of molecular sieve can not produce adverse influence to composite carrier.
The specific embodiment
Take the preparation process of infusion process as example explanation hydrogenation catalyst of the present invention, specific as follows: catalyst carrier material and other components such as adhesive and auxiliary agent through mixing, roll, the means moulding such as extrusion, then be dried, roasting, obtain catalyst carrier, then adopt conventional dipping method with containing active metallic compound (such as molybdenum and/or tungsten, nickel and/or cobalt compound) solution impregnation metal, then be dried, roasting obtains catalyst prod.Wherein, after catalyst carrier material 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.After impregnation of catalyst carriers supported active metal, the drying condition of catalyst is as follows: be generally at 80 ~ 200 ℃, dry 1 ~ 15 hour, the roasting condition of catalyst was roasting 1 ~ 8 hour at 350 ~ 550 ℃.
In the inventive method, described containing molybdenum and/or tungsten, nickel and/or cobalt compound, can be by be selected from the soluble compound of nickeliferous and/or cobalt metal one or more, as one or more solution prepared in their nitrate, acetate, soluble carbonate salt, chloride, soluble complexes; Can be by being selected from containing one or more in the soluble compound of molybdenum and/or tungsten metal, as one or more solution prepared in molybdate, tungstates, ethyl metatungstate, it can be the mixed solution of being prepared by the soluble compound of nickeliferous and/or cobalt metal and the solubility platform thing of molybdenum and/or tungsten metal; Can also be by nickeliferous and/or the heteropoly acid of cobalt metal and molybdenum and/or tungsten metal or the aqueous solution prepared by salt.According to method provided by the invention, to not restriction of the solvent in solution, can be organic solvent, as alcohol, ether and acid, can be inorganic solvent, as water and their mixture, preferred water.
For hydrocracking catalyst, hydrogenation activity component is molybdenum and/or tungsten and nickel and/or cobalt, and the weight of catalyst of take is benchmark, in oxide, the content of molybdenum and/or tungsten is 5% ~ 40%, is preferably 12% ~ 35%, the content of nickel and/or cobalt is l% ~ 15%, is preferably 5% ~ 13%.
Catalyst preparation process of the present invention is simple, convenient, and easy operating is applicable to industrial production.While selecting suitable molecular sieve (modified Y molecular sieve and modified beta molecular sieve), catalyst is for hydrocracking process, can effectively improve reaction mass at the mass transfer of catalyst, improve the selective of the activity of catalyst and object product, can obtain good result of use.Catalyst of the present invention 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, de-pitch prill oil, catalytic cracking recycle oil, shale oil, coal tar wet goods.Reaction condition generally under hydrogen existence condition, reaction pressure 5 ~ 30MPa, hydrogen to oil volume ratio 100 ~ 5000, volume space velocity 0.1 ~ 5.0h during liquid
-1, 340 ~ 420 ℃ of reaction temperatures.Catalyst of the present invention when processing common VGO, reaction condition generally under hydrogen existence condition, the best 10 ~ 20MPa of reaction pressure, hydrogen to oil volume ratio 500 ~ 2000, volume space velocity 0.5 ~ 1.5h during liquid
-1, 370 ~ 410 ℃ 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.
Below in conjunction with specific embodiment, further illustrate preparation method of the present invention, but scope of the present invention is not only limited to the scope of these embodiment.
embodiment 1
486g solid aluminum chloride is joined in 1 liter of distilled water, heat simultaneously and be stirred to dissolving, obtain liquor alumini chloridi (a).Add appropriate distilled water diluting into about 10% weak aqua ammonia (b) concentrated ammonia liquor, 93g xylitol is dissolved in 500ml water, forms solution (c).Get 10L waterglass (technical grade, modulus is 3.0) and be diluted in 20L deionized water, be configured to solution (d).15g monoethanolamine is dissolved in 100ml water, is heated to 60 ℃, adds 38g Modified Zeolite Y Y-1 (SiO under stirring
2/ Al
2o
3=11.0, lattice constant is 24.42, and relative crystallinity is 95%) pull an oar 2 hours, obtain slurries (e).Get a stainless steel reaction tank, 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, continue to drip (b), open the valve that has (c) and container (e), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes, control the valve of (c) and container (e), 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), according to the content of silica in amorphous aluminum silicide, is that 45wt% calculating added in 10 minutes.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 carrier dry glue powder J-1, and through 550 ℃ of roastings, after 10 hours, the Main physical chemical property of gained is in Table 1.
Get 80 grams of product J-1 carrier dry glue powders, 20 grams of mixing of adhesive, extruded moulding after rolling, dry and roasting is placed in reaction vessel, takes 50 grams of ammonium metatungstates and is dissolved in water into 200 ml solns with 23 grams of nickel nitrates, solution is joined to reaction vessel dipping 3 hours, then dry at 120 ℃, dry after 180 minutes, by dried catalyst 500 ℃ of roastings 4 hours, obtain catalyst A, it forms in Table 2.
embodiment 2
120g solid sulphuric acid aluminium is joined in 1 liter of distilled water, heat simultaneously and be stirred to dissolving, obtain aluminum sulfate solution (a).Add appropriate distilled water diluting into about 10% weak aqua ammonia (b) concentrated ammonia liquor, 18g BDO is dissolved in 500ml water, forms solution (c).Get 10L waterglass (technical grade, modulus is 3.0) and be diluted in 20L deionized water, be configured to solution (d).13g monoethanolamine is dissolved in 100ml water, is heated to 60 ℃, adds 65g Modified Zeolite Y Y-1 (SiO under stirring
2/ Al
2o
3=11.0, lattice constant is 24.42, and relative crystallinity is 95%) pull an oar 2 hours, obtain slurries (e).Get a stainless steel reaction tank, 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, continue to drip (b) and open the valve that has (c) and container (e), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes, control the valve of (c) and container (e), 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), according to the content of silica in amorphous aluminum silicide, is that 45wt% calculating added in 10 minutes.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 carrier dry glue powder J-2, through 500 ℃ of roastings, after 5 hours, the Main physical chemical property of gained is in Table 1.
Get 80 grams of product J-2 carrier dry glue powders, 20 grams of mixing of adhesive, extruded moulding after rolling, dry and roasting is placed in reaction vessel, takes 50 grams of ammonium metatungstates and is dissolved in water into 200 ml solns with 23 grams of nickel nitrates, solution is joined to reaction vessel dipping 3 hours, then dry at 120 ℃, dry after 180 minutes, by dried catalyst 500 ℃ of roastings 4 hours, obtain catalyst B, it forms in Table 2.
embodiment 3
120g 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).36g1,4-succinic acid is dissolved in 1L water, forms solution (c).57g ethylenediamine is dissolved in 500ml water, is heated to 60 ℃, adds 572g Modified Zeolite Y Y-1 (SiO under stirring
2/ Al
2o
3=11.0, lattice constant is 24.42, and relative crystallinity is 95%), continue stirring and obtain slurries (d) after 2 hours.Get 10L waterglass (technical grade, modulus is 3.0) and be diluted in 20L deionized water, be configured to solution (e).Get a steel retort, inserting 2l deionized water and stirring is heated to after 65 ℃, open simultaneously have (a), the valve of (b), (c) and container (d), 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 (e), according to the content 50wt% of silica in amorphous aluminum silicide, calculates and adds in 10 minutes.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 carrier dry glue powder J-3, through 500 ℃ of roastings, after 5 hours, pulverizing and sieving of gained obtains carrier material J-3.Main physical chemical property is in Table 1.
Get 80 grams of product J-3 carrier dry glue powders, 20 grams of mixing of adhesive, extruded moulding after rolling, dry and roasting is placed in reaction vessel, takes 50 grams of ammonium metatungstates and is dissolved in water into 200 ml solns with 23 grams of nickel nitrates, solution is joined to reaction vessel dipping 3 hours, then dry at 120 ℃, dry after 180 minutes, by dried catalyst 500 ℃ of roastings 4 hours, obtain catalyst C, it forms in Table 2.
embodiment 4
654g solid aluminum chloride is joined in 1 liter of distilled water, heat simultaneously and be stirred to dissolving, obtain liquor alumini chloridi (a).Add appropriate distilled water diluting into about 10% weak aqua ammonia (b) concentrated ammonia liquor, 125g sweet mellow wine is dissolved in 1L water, forms solution (c).Get 10L waterglass (technical grade, modulus is 3.0) and be diluted in 20L deionized water, be configured to solution (d).9.5g1,4-butanediamine is dissolved in 100ml water, is heated to 60 ℃, adds the Hydrogen β zeolite (SiO of 24g modification
2/ Al
2o
3=30.0, lattice constant is 12.00, and relative crystallinity is 90%) continue to stir 2 hours, obtain slurries (e).Get a steel retort, 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 that has (c) and container (e), system in tank is added drop-wise to pH=8.0 in controlling 30 minutes, control the valve of (c) and container (e), 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), according to the content 45wt% of silica in amorphous aluminum silicide, calculates and adds in 10 minutes.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 carrier dry glue powder J-4, and through 500 ℃ of roastings, after 5 hours, the Main physical chemical property of gained is in Table 1.
Get 80 grams of product J-4 carrier dry glue powders, 20 grams of mixing of adhesive, extruded moulding after rolling, dry and roasting is placed in reaction vessel, takes 50 grams of ammonium metatungstates and is dissolved in water into 200 ml solns with 23 grams of nickel nitrates, solution is joined to reaction vessel dipping 3 hours, then dry at 120 ℃, dry after 180 minutes, by dried catalyst 500 ℃ of roastings 4 hours, obtain catalyst D, it forms in Table 2.
comparative example 1
Repeat the synthetic of embodiment 2, do not add monoethanolamine and BDO, make comparison vehicle dry glue powder DF-1.Through 500 ℃ of roastings, after 5 hours, the Main physical chemical property of gained is in Table 1.
The process of carrier material DF-1 synthetic catalyst, with embodiment 2, obtains catalyst DA, and it forms in Table 2.
comparative example 2
Repeat the synthetic of embodiment 2, do not add monoethanolamine, make comparison vehicle dry glue powder material DF-2.Through 500 ℃ of roastings, after 5 hours, the Main physical chemical property of gained is in Table 1.
The process of carrier material DF-2 synthetic catalyst, with embodiment 2, obtains catalyst DB, and it forms in Table 2.
comparative example 3
Repeat the synthetic of embodiment 2, do not add Y zeolite and monoethanolamine and BDO, make comparison vehicle dry glue powder DF-3.Through 500 ℃ of roastings, after 5 hours, the Main physical chemical property of gained is in Table 1.
The process of carrier material DF-2 synthetic catalyst, with embodiment 2, obtains catalyst DC, and it forms in Table 2.
comparative example 4
Repeat the synthetic of embodiment 4, do not add organic amine and Organic Alcohol, make comparison vehicle dry glue powder DF-4.Through 500 ℃ of roastings, after 5 hours, the Main physical chemical property of gained is in Table 1.
The process of carrier material DF-4 synthetic catalyst, with embodiment 4, obtains catalyst DD, and it forms in Table 2.
comparative example 5
Repeat the synthetic of embodiment 4, do not add Hydrogen beta-molecular sieve and organic amine and Organic Alcohol, make comparison vehicle dry glue powder DF-5.Through 500 ℃ of roastings, after 5 hours, the Main physical chemical property of gained is in Table 1.
The process of carrier material DF-4 synthetic catalyst, with embodiment 4, obtains catalyst DE, and it forms in Table 2.
Table 1 carrier dry glue powder main character
| Bearer number | J-1 | J-2 | J-3 | DF-1 | DF-2 | DF-3 | Y-1 |
| Specific area, m 2/g | 368 | 536 | 663 | 429 | 477 | 343 | 786 |
| Pore volume, ml/g | 0.72 | 0.56 | 0.43 | 0.47 | 0.52 | 0.80 | 0.37 |
Table 1 continues carrier dry glue powder main character
| Bearer number | J-4 | DF-4 | DF-5 | B-1 |
| Specific area, m 2/g | 336 | 269 | 345 | 553 |
| Pore volume, ml/g | 0.74 | 0.63 | 0.81 | 0.40 |
By table 1 Data Comparison, find out, use this method prepared molecular sieve-amorphous aluminum silicide complex carrier dry glue powder specific area and pore volume to be greatly improved, can effectively solve the problem that the amorphous aluminum silicide that causes even stops up with the reunion between molecular sieve when plastic; Use the prepared carrier dry glue powder of this method on physico-chemical property, to follow the data of the physical mixture of amorphous aluminum silicide and molecular sieve to approach, more illustrated and used this method in the qualitative superiority of individuality that retains molecular sieve and amorphous aluminum silicide.By this method, can prepare the catalyst carrier dry glue powder of a kind of amorphous aluminum silicide and large pore volume Large ratio surface molecular sieve organic composite, high degree of dispersion.
The composition of table 2 catalyst and character
| Catalyst numbering | A | B | C | D | DA | DB | DC | DD | DE |
| WO 3，wt％ | 23.00 | 22.91 | 23.22 | 23.16 | 23.49 | 21.57 | 21.53 | 21.73 | 22.43 |
| NiO，wt％ | 6.01 | 6.61 | 6.15 | 5.69 | 6.90 | 6.60 | 6.09 | 6.86 | 5.65 |
| Than the long-pending face of table, m 2/g | 225 | 311 | 378 | 209 | 251 | 286 | 216 | 173 | 215 |
| Pore volume, ml/g | 0.44 | 0.35 | 0.28 | 0.45 | 0.30 | 0.34 | 0.49 | 0.39 | 0.49 |
The invention described above catalyst and comparative catalyst thereof are evaluated.Evaluating 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 during liquid
-1.Main character is in Table 4.
Table 3 raw material oil properties
| Density, d 4 20 | 0.9024 | Mass spectral analysis, wt% | ? |
| Boiling range, ℃ | ? | Alkane | 19.7 |
| IBP | 321 | Cycloalkane | 36.7 |
| 10% | 393 | Aromatic hydrocarbons | 41.1 |
| 50% | 443 | Colloid | 25 |
| 90% | 497 | S，w% | 1.01 |
| EP | 528 | N，μg/g | 1138 |
| Carbon residue, w% | 0.03 | BMCI value | 40.3 |
Table 4 evaluation result
| Catalyst numbering | B | DA | DB |
| Reaction temperature, ℃ | 362 | 365 | 364 |
| Conversion ratio, wt% | 63 | 59 | 61 |
| (scheelite+boat coal) yield, wt% | 62.52 | 58.91 | 60.99 |
| Heavy naphtha virtue is dived, wt% | 52 | 47 | 49 |
| Boat coal smoke point, mm | 28 | 25 | 27 |
From evaluation result, can find out, the catalyst that uses the inventive method to prepare has good activity and product selectivity.
Claims (17)
1. the preparation method of a hydrogenation catalyst, comprise: the catalyst carrier material that preparation contains molecular sieve and amorphous aluminum silicide, adopt infusion process or coprecipitation to introduce hydrogenation activity component, obtain final hydrogenation catalyst, wherein the preparation process of carrier material comprises:
(1) molecular sieve is mixed with organic amine, wherein the addition of organic amine accounts for the 1wt%～40wt% of molecular sieve weight; Described organic amine is that carbon number is less than one or more in the fatty amine, aromatic amine, hydramine, acid amides of 20;
(2) mixture and the organic matter that in amorphous aluminum silicide plastic process, add step (1) to obtain, the weight of final carrier material of take is benchmark, molecular sieve addition is 5wt%～90wt%, organic addition is 1wt%～50wt%, described organic matter for containing the organic alcohols of two or more hydroxyls, contain two or more carboxyls organic acid in one or more;
(3) after amorphous aluminum silicide cemented into bundles step (2) Suo Shu, carry out agingly, then after filtration, washing, dry, obtain catalyst carrier material.
2. 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 2～10 carbon numbers.
3. in accordance with the method for claim 1, it is characterized in that 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.
4. in accordance with the method for claim 1,, after it is characterized in that step (1) molecular sieve mixes with organic amine, carry out again step (2) after filtration and after dry.
5. in accordance with the method for claim 1, the plastic process that it is characterized in that the amorphous aluminum silicide described in step (2) 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.
6. in accordance with the method for claim 1, it is characterized in that in step (2), amorphous aluminum silicide plastic process is the neutralization reaction process of acid material and alkaline material, plastic process adopts two kinds of materials also to flow plastic mode of operation, or a kind of material is placed on the mode of operation that another kind of material in plastic cans adds plastic continuously.
7. in accordance with the method for claim 6, it is characterized in that in step (2), plastic material comprises that aluminium source is Al
2(SO
4)
3, AlCl
3, Al (NO
3)
3and NaAlO
2in one or more, silicon source be in waterglass, Ludox and organic silicon-containing compound one or more, precipitating reagent is NaOH, NH
4oH, CO
2in one or more.
8. in accordance with the method for claim 1, it is characterized in that the described aging condition of step (3) is as follows: pH is 6.0～10.0, ageing time 0.25～8 hour, aging temperature is room temperature～85 ℃.
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.
10. in accordance with the method for claim 1, it is characterized in that in step (1), the state that adds of described molecular sieve is that dry powder-shaped adds, or adds with slurries form.
11. 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 plastic neutralization reaction process, adds in plastic cans by this mixture continuously; (2) this mixture is first joined in plastic cans, then will prepare in the acid material of amorphous aluminum silicide and alkaline material and plastic; (3) by this mixture, one or more with plastic material are mixed, then in plastic material and plastic.
12. in accordance with the method for claim 1, 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 ℃.
13. in accordance with the method for claim 1, 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.
14. in accordance with the method for claim 1, it is characterized in that described organic acid 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.
15. in accordance with the method for claim 1, 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) joins in plastic cans at the plastic initial stage in advance, (2) in plastic process, be added drop-wise in plastic cans, (3) with one or more mixing of plastic raw material, with material, add in plastic cans.
16. in accordance with the method for claim 1, it is characterized in that described hydrogenation activity component is one or more in group vib and group VIII metal, and the content of hydrogenation activity component in catalyst counts 5%～80% with oxide.
17. according to the method described in claim 1 or 16, it is characterized in that described hydrogenation activity component is one or more in molybdenum, tungsten, nickel, cobalt.
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