CN100448535C - Hydrogenation catalyst containing faujasite, its preparation method and application - Google Patents
Hydrogenation catalyst containing faujasite, its preparation method and application Download PDFInfo
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- CN100448535C CN100448535C CNB2005100475069A CN200510047506A CN100448535C CN 100448535 C CN100448535 C CN 100448535C CN B2005100475069 A CNB2005100475069 A CN B2005100475069A CN 200510047506 A CN200510047506 A CN 200510047506A CN 100448535 C CN100448535 C CN 100448535C
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Abstract
The invention relates to a hydrogen catalyst with silicon faujasite. Wherein, it comprises faujasite at 1-95%, fusion-resistant oxide at 1-90%, and active metal as 0.05-60%; the mol ratio as SiO2/Al2O3 of faujasite is 6-20, the zeolite XRD spectrum analysis proves it is Y-type zeolite, whose particles have sheet shape. The invention can use general method, while the zeolite uses template method, to be composed in water heating condition. The invention uses new molecule screen, with high reaction activity and selectivity, to be used in hydrocracking, etc.
Description
Technical field
The present invention relates to contain a kind of hydrogenation catalyst and preparation method thereof and use, particularly contain hydrogenation catalyst of faujasite and preparation method thereof.
Background technology
Hydrogen addition technology is a kind of important PETROLEUM PROCESSING means, as hydrofinishing, hydrocracking, hydro-upgrading etc.Technology such as hydrofinishing and hydro-upgrading is to improve the important means of hydrocarbon products quality, and hydrocracking is the important method of heavy hydrocarbon lighting.
The carrier that mainly comprises hydrogenation metal component and load hydrogenation metal component in the hydrogenation catalyst, zeolite are one of hydrogenation catalyst common carrier components, particularly in hydrocracking, catalyst for hydro-upgrading, and the zeolite composition that generally is absolutely necessary.For example in hydrocracking catalyst, using zeolite component is a qualitative leap of hydrocracking catalyst technology, it has changed the shortcoming that amorphous type hydrocracking catalyst activity was low in the past, service cycle is short, make that activity of such catalysts stability is better, the life-span is longer, present most hydrocracking commercial plant all uses the hydrocracking catalyst that contains zeolite.Simultaneously, because the pore structure and the acidity of zeolite uniqueness, the hydrogenation catalyst that contains zeolite can improve the quality index of some products, as diesel cetane-number, condensation point etc., product property is greatly improved.
The hydrogenation catalyst that contains zeolite contains two kinds of catalytic active centers, and a kind of is the hydrogenation sites of reactive metal, and a kind of is the acid centre of zeolite.According to different reaction raw materials and reaction condition, the cracking reaction of hydrocarbon raw material can take place on acid centre, isomerization reaction, aromatization, ring-opening reaction etc. further can reach different processing purpose.As in hydrocracking catalyst, mainly utilize the cracking reaction at zeolite acidity center.Hydrocracking catalyst generally selects for use noble metals such as the base metal of VIB and VIII family metal or platinum as hydrogenation component, and acidic components are generally various dissimilar zeolites.In addition, with the supporting hydrocracking process technology of hydrocracking, the using method of catalyst is also to the hydrocracking process important influence in other words.Typical technology generally can be divided into one-stage process and two-stage method, and mode of operation mainly can be divided into cycling and once-through operation.Specific technology and mode of operation thereof all have supporting special-purpose catalyst.
Because faujasite has the supercage structure of big cavity, make faujasite in hydrogenation catalyst, have widely and use.Though belong to faujasite, the X zeolite is too low owing to silica alumina ratio, and not only structural instability, and its acid matter does not reach the catalytic reaction requirement yet, so many as adsorbent or drier, and the zeolite structured component that is used as various catalyst than stablizing of Y.The zeolite that hydrocracking catalyst is commonly used at present mainly is the Y zeolite of handling through modification, and as the main acidic components of catalyst, the higher hydrocabon of feedstock oil can enter in the zeolite pore and transform with it.
The ZSM series zeolite is the cracking component of Chang Zuowei hydrogenation catalyst also, but because the duct is little, reactant can not in time shift out can cause the reactant excessive fragmentation, product selectivity is descended, simultaneously big molecule hydrocarbon is difficult for entering, activity is also lower when treatment of heavy hydrocarbon material, thereby such catalyst range of application generally is confined in the hydro dewaxing technical process of light components comparatively.The β zeolite to the selectivity of alkane relatively other zeolite that is used for hydrocracking catalyst than higher, be characterized in to obtain the pyrolysis product of low condensation point, but because the supercage structure as the Y zeolite not, the open loop activity is relatively poor, and make thus and the easy coking of catalyst also cause catalyst stability bad.
The Y zeolite that synthesizes under alkaline medium comes the balance skeleton electric charge by sodium ion, and sodium ion and aluminium ion number are equivalent in the faujasite skeleton, and synthetic Y zeolite powder is the sodium type, about the about 10w% of sodium oxide content.Because the existence of a large amount of sodium ions, the acidity of sodium type Y zeolite is very low, therefore in the practical application of Y zeolite, convert it into the Hydrogen product, adopts the ammonium salt exchange usually.On the other hand, for the heat endurance that improves the Y zeolite especially hydrothermal stability, usually will further improve the silica alumina ratio of Y zeolite powder, the raising of silica alumina ratio simultaneously also can improve the acid strength of single acid centre and bring better cracking performance and cracking selectivity.
For middle oil type hydrocracking catalyst, except considering activity, need to consider middle distillates oil selectivity especially.Zeolite facies no doubt can increase the lytic activity of catalyst to the stronger acid centre of acid sial, but its strong cracking ability can cause declining to a great extent of middle distillates oil selectivity, therefore need search out a kind of better equilibrium in active and this a pair of contradiction of middle distillates oil selectivity.For middle oil type hydrocracking catalyst, zeolite component needs moderate rather than very strong cracking performance.Generally, by improving acid strength and the sour density that sial recently improves zeolite, these class methods are general main to comprise following two steps: 1. amine is taken off in high-temperature roasting, at 500-600 ℃ of following roasting some hrs to remove the organic formwork agent in the zeolite; 2. acid treatment dealuminzation is sloughed aluminium on the zeolitic frameworks with the effect of raw material zeolite at a certain temperature with certain density inorganic acid, improves its silica alumina ratio.In order further to improve acidity and acid strength, to adapt to the application target of different catalysts.Roasting also can be carried out the pressurized thermal water processing after taking off amine and acid treatment dealuminzation step again, under certain pressure and temperature, further sloughs the aluminium on the zeolitic frameworks, reduces acidity and improves acid strength.As the hydrocracking catalyst of US4517074 patent disclosure, produce the intermediate oil of 300-700 (149-371 ℃), charging is hydrodenitrogeneration and/or hydrodesulfurization charging preferably, this patent example by use a kind of in claim at Υ-Al
2O
3Be dispersed with the component of 75% high sial and cooperate zeolite such as the LZ-10 zeolite.Wherein related zeolite, the EP320247 patent has been described its acid-treated process, with certain density inorganic acid leaching super-hydrophobic Y zeolite LZ-10, improve its surface area and degree of crystallinity, though the zeolite molecular sieve wash-out after the acid treatment most of non-framework aluminum make the duct unobstructed, simultaneously also improved silica alumina ratio, its acidity is very low, when being the hydrocracking catalyst processing heavy oil of acidic components with this kind molecular sieve, activity is lower.
US4820402 discloses a kind of hydrocracking catalyst, the silica molecular proportion at least 50: 1 of the zeolite component in the catalyst, this patent catalyst is used to handle Arabic VGO, under the situation that control 60v% transforms, middle distillates oil selectivity 45-65v%, different high silica alumina ratio zeolite (SiO
2: Al
2O
3=200: 1) middle distillates oil selectivity that is used for this catalyst is in proper order: ZSM-20＞β＞Y type, wherein effect is best contains the ZSM-20 catalyst.But so high silica alumina ratio will be sacrificed the acidity of zeolite significantly, thereby be made catalyst activity very low, can not give full play to the advantage of the big molecule hydrocarbon feed of Y zeolite cracking with supercage structure.
US5716593 discloses a kind of first extrusion molding synthetic zeolite catalyst preparation method of crystallization again, relate to the FAU prepare zeolite, but method is dry again up to the paste that forms a kind of extrusion molding after organic formwork agent, silicon source, aluminium source and water are mixed, and putting into the bottom in the bottle of then it being packed into has the autoclave crystallization of water synthetic.Though the silica alumina ratio that feeds intake of this patent is at 6-15, but this does not also mean that its product has high silica alumina ratio, though patent does not have to disclose the silica alumina ratio of its product, but patent has pointed out not enter in a series of removing molecular sieves the last handling process of the silica of framework of molecular sieve, and the silica alumina ratio that therefore can infer its products molecule sieve should be lower than the silica alumina ratio that feeds intake.Synthetic water/the silica of this patent is low than very, requires to be no more than 6, so can not make amorphous silicon in the raw material be attached in the framework of molecular sieve well and guarantee good degree of crystallinity.The large usage quantity of alkali in this patented method, as the middle M that feeds intake
+/ SiO
2=0.2-1.0 (mol ratio), M
+Be alkali metal, the consumption of alkali is scaled Na
2O/SiO
2Mol ratio be 0.4～2.0, though alkali number is too high by being beneficial to forming of y-type zeolite, but too high meeting causes the rapid decline of product silica alumina ratio, the actual framework si-al ratio of the zeolite product that this method obtains is not high, this patent has only provided a kind of method, the product property data are not provided, and have only about 5 (when feeding intake silica alumina ratio 12) by the zeolite silica alumina ratio of its method preparation.US5549881 discloses a kind of faujasite preparation method, and this patent also adopts synthetic certain of organic formwork agent to have the molecular screen composite of faujasite architectural feature, but its special requirement is added long-time aging sodium silicoaluminate crystal seed under the room temperature.The crystal seed that patent relates to use prepares under the high alkalinity condition, and special requirement at room temperature crystallization time reach 6-16 days.This method is used the template agent merely and auxiliary without crystal seed, and crystallization time can be very long, and production efficiency is very low, but this method should range directing agent method owing to adopted crystal seed, and the zeolite pattern is many ribs shape particle under the Electronic Speculum.
Summary of the invention
The invention provides a kind of hydrogenation catalyst that contains the new-type high silicon faujasite, this catalyst has advantages such as good reaction selectivity.
The present invention contains faujasite hydrogenation catalyst composition and comprises by weight: faujasite 1%-95%, and refractory oxide 1%-90%, active metal component 0.05%～60% (in oxide), each constituent content sum is 100%.The SiO of faujasite wherein
2/ Al
2O
3Mol ratio is 6～20, is preferably 6～12, and the XRD spectrum analysis belongs to the y-type zeolite in the faujasite, and crystal grain pattern (ESEM) has the sheet pattern.Faujasite can be na-pretreated zeolite or h-type zeolite, its Na when selecting h-type zeolite
2O content is lower than 1w%, preferably is lower than 0.2w%.
Refractory oxide in the hydrogenation catalyst can be selected from one or more in the various refractory oxides that can be used as catalyst carrier such as aluminium oxide, silica, titanium oxide, zirconia, other zeolite, composite oxides.Reactive metal generally is selected from the reactive metal in group vib and/or the VIII family.The group vib metal oxide generally is selected from one or more in W and/or the Mo oxide, is generally 2%-50% in oxide content.The VIII metal is generally base metals such as Ni and/or Co, or noble metals such as Pt and/or Pd, when adopting base metal, is generally 1%-20% in oxide content, when adopting noble metal, in metal content for being generally 0.05%～5%.Each composition weight percentage composition sum of catalyst is 100%.
Hydrogenization catalyst preparation method of the present invention can various conventional methods, as infusion process, ion-exchange, kneading method, coprecipitation etc.Faujasite wherein adopts following process preparation:
Aluminium source, silicon source, sodium source and template agent are mixed according to a certain percentage, and the molar ratio of various raw materials is in the mixture: 5～50SiO
2: 1.5～15Na
2O: Al
2O
3: 0.05～5.0 template agent: 60～420H
2O.Na wherein
2O/SiO
2Mol ratio is 0.05～0.8, is preferably 0.1～0.4, H
2O/SiO
2Mol ratio is 6～40, is preferably 10～22.
The template agent is organic base compounds and/or organic high molecular compound.Wherein, the organic base compounds mainly is selected from the alkyl ammonium hydroxide compounds, as in TMAH, tetraethyl ammonium hydroxide, TPAOH, the TBAH etc. one or more.Described organic high molecular compound is selected from the polyalcohols compound, is in 200～10000 polyethylene glycol one or more as molecular weight.Two kinds of template agent can be used alone, but also also mix together, and ratio can not limit when mixing use.
Mixture stirs under ℃ condition of room temperature～70 and formed even gel in aging 1-100 hour, and under 90-130 ℃ of condition under the reactor self-generated pressure hydrothermal crystallizing 24-240 hour, preferred 24～120 hours.
The specific surface of hydrogenation catalyst of the present invention is generally 150-300m
2/ g, pore volume is generally 0.2-0.6ml/g.The application of hydrogenation catalyst of the present invention in hydrocracking, hydro-upgrading, hydrotreatment.As be used for the hydrocracking process of heavy hydrocarbon, and hydro-upgrading of various hydro carbons, hydrotreatment process etc.
Hydrogenation catalyst of the present invention has adopted a kind of novel faujasite, and this faujasite has high silica alumina ratio and sheet pattern.High silica alumina ratio helps improving the stable and active of catalyst, and the sheet pattern not only has more reaction surface, and helps the diffusion of reactant molecule, can reduce secondary response, improves selectivity.When being used for heavy hydrocarbons hydrocraking, be improved than existing activity of such catalysts of the same type and selectivity as catalyst of the present invention.The synthesizing high-silicon faujasite mainly adopts directing agent method in the prior art, promptly prepares faujasite seeds under high sodium condition, is the synthetic final faujasite product of directed agents with this crystal seed; Or under high sodium condition direct synthetic faujasites.The present invention adopts template agent method directly to synthesize the faujasite of high silica alumina ratio under hydrothermal condition, by adopting suitable template agent, under the relatively low situation of sodium consumption, need under high sodium condition, not make zeolite seed crystal earlier, can obtain the faujasite of high silica alumina ratio.And the inventive method generated time is short, and when particularly adopting the polyalcohols compound, generated time is shorter, can improve combined coefficient greatly.Faujasite of the present invention has more high silica alumina ratio, more crystalline degree, lower sodium content and bigger acidity.Use crystal seed faujasite grain morphology that synthesizes and the faujasite that synthesizes with the pure method of template of the present invention by obviously different, the former is generally the particle of many ribs, and the latter is the sheet pattern with fragment shape of more flat surfaces, is similar to the expensive hypertoxic crown ether of the employing that has the supercage structure equally and makees the synthetic EMT molecular sieve of template agent.
Description of drawings
Fig. 1 is the XRD figure of embodiment 1 zeolite sample, and abscissa is 2 θ angles.
Fig. 2 is the sem photograph of embodiment 1 zeolite sample.
Fig. 3 is the sem photograph of comparative example 1 method synthetic faujasites sample.
The specific embodiment
The synthetic detailed process of the high silica alumina ratio faujasite that hydrogenation catalyst of the present invention relates to can comprise the steps:
(1) aluminium source, silicon source, sodium source and template agent are mixed according to a certain percentage;
(2) stir and formed in aging 1-100 hour even gel being no more than under 70 ℃ of conditions;
(3) mixed gel is moved into reactor and airtight:
(4) under 90-130 ℃ of condition under the reactor self-generated pressure hydrothermal crystallizing 24-240 hour;
(5) will obtain zeolite powder after crystallization product filtration and the drying.
In hydrothermal crystallization process, after needed proportioning is mixed aluminium source, silicon source, sodium source and template agent according to a certain percentage according to synthetic zeolite, the ageing process that also needs certain hour, purpose is to make mixed system form even gel, help follow-up crystallization process, for example reduce crystallization induction period, improve degree of crystallinity etc.According to the present invention, related zeolite under 90-130 ℃ of condition under the reactor self-generated pressure hydrothermal crystallizing 24-240 hour.
The various raw materials of this area routine can be adopted in aluminium source, silicon source, sodium source.One or more of aluminium source such as aluminum sulfate, aluminium chloride, aluminum nitrate.In silicon source such as waterglass, silica gel and the Ludox one or more, preferred Ludox.The sodium source can be one or more of sodium aluminate (also being one of aluminium source simultaneously), NaOH.
Hydrothermal crystallization process involved in the present invention can be a kind of dynamic process of following stirring, or does not have the static process of stirring.Best, according to the hydrothermal crystallization process of process of the present invention be stir does not earlier have then stir dynamically and static state in conjunction with hydrothermal crystallization process.Statically advantageous is in nucleation, and the dynamic crystallization process promotes mass-and heat-transfer and helps obtaining uniform product, also can adopt the mode of dynamic and static combination, and when adopting dynamic and static combination, both time scales can be 1: 0.1～10.Adopt dynamically and static in conjunction with the time, synthetic under static state earlier, then dynamically synthetic down, operate like this and help improving crystallization rate, and obtain uniform product.No matter take any mode, all be scope of the present invention, and specifically adopt what mode, be decided by the actual conditions of synthetic scale or production-scale size and equipment.
The zeolite that the supercage structure is arranged of the synthetic tool of template hydrothermal crystallization method that catalyst of the present invention is related, it has higher silica alumina ratio, and sodium ion is also lower, and the relative NaY of acidity obviously improves, and therefore can directly use in hydrotreating catalyst.On the other hand,, Preparation of Catalyst of the present invention the Hydrogen product had better be become, generally the ammonium ion exchange method can be adopted in order to improve the reactivity worth of catalyst better.The ion-exchange preparation process adopts conventional method in the prior art, and general step is as follows: with crystallization completely zeolite slurry exchange to Na with the ammonium salt solution of 0.5～5.0M
2O content is not more than the Y zeolite product of 3.0w%; Zeolite after the ammonium salt exchange after filtration, wash, be dried to and carry out roasting behind butt 〉=80w% and take off ammonium and handle; Product exchanged by above-mentioned ion-exchange process and ammonium salt solution again repeatedly obtain Na
2O content is lower than 1w% or is lower than the zeolite product of 0.2w%.Roasting is taken off the ammonium condition and is generally 300～600 ℃ of roastings 1～20 hour.Because the characteristics of synthetic zeolite of the present invention, the complexity that its preparation becomes the Hydrogen product will greatly reduce than prior art NaY, outstanding behaviours reduces at its ammonium salt exchange number of times, and NaY will exchange more than five times usually, and zeolite of the present invention just can reach requirement general two to three times.Ammonium salt exchange solid-to-liquid ratio is 1: 8～1: 15, and concentration is 0.1～10.0M, the preferably ammonium salt solution of 0.5～5.0M exchange, and used ammonium salt can be nitrate, chlorate, sulfate etc.Fully stir during exchange, and holding temperature is in room temperature to 100 ℃ scope 0.5～5 hour time, preferably 1.0～3.0 hours.
Below in conjunction with infusion process, specify Preparation of catalysts method of the present invention.If adopt other method preparation, can be with reference to this area general operation method.
Hydrogenation catalyst of the present invention normally has the solid catalyst of definite shape, and the typical preparation process of infusion process comprises: (1) high silica alumina ratio faujasite, refractory oxide that the inventive method is synthetic mixes in the required ratio of catalyst; (2) add suitable amount of adhesive or directly add an amount of dilute acid soln and mix and pinch into paste; (3) with above-mentioned paste extruded moulding, obtain shaping carrier; (4) carrier with above-mentioned moulding descended dry 1-20 hour at 80-150 ℃; (5) drying is good carrier is at 400-600 ℃ of following roasting 1-8 hour, the shaping carrier that obtains activating; (6) dipping solution that contains required reactive metal of preparation suitable concentration; (7) adopt saturated dipping or excess solution dipping method that above-mentioned dipping solution once/successively is being carried on the good shaping carrier of activation simultaneously/respectively; (8) carrier that above-mentioned dipping is good 80-150 ℃ dry 1-20 hour down, then 400-600 ℃ following roasting 1-8 hour, obtain the final catalyst product.
Hydrogenation catalyst of the present invention is used for hydro-upgrading or hydrocracking process, is particularly suitable for treatment of heavy hydrocarbon material, and the boiling range scope of heavy hydrocarbon material is at 250-600 ℃, generally at 300-550 ℃.As can being used for the hydrocracking process of VGO, or the processes such as hydro-upgrading of cut such as diesel oil.Hydrogenation conditions generally is under the hydrogen existence condition, reaction pressure 2-20MPa, hydrogen to oil volume ratio 400-4000, air speed 0.1-8.0hr
-1, reaction temperature 350-450 ℃.
Further specify Preparation of catalysts method of the present invention, character and effect by the following examples, the scheme among the embodiment is the specific embodiments in scope of the invention claim scope, is not construed as limiting the invention.(percentage wherein, w% are all represented percentage by weight)
Embodiment 1
With waterglass is the silicon source, and sodium aluminate is the aluminium source, and Macrogol 6000 is the template agent, and hydrothermal crystallizing synthesizes zeolite of the present invention.Reactant batching mol ratio: n (SiO
2): n (template agent): n (Na
2O): n (Al
2O
3): n (H
2O)=and 6: 0.16: 2.0: 1: 130.Synthetic method: press reactant batching mol ratio, NaOH and sodium aluminate are dissolved in water, stir and add Macrogol 6000 after 30 minutes, add Ludox again after continuing to be stirred to dissolving.Stirring is after 12 hours down at 30 ℃ with said mixture, and room temperature moves in the autoclave of band polytetrafluoroethylene (PTFE) after placing a night, and is airtight, (100 rev/mins) 110 ℃ of crystallization 120h under stirring.After crystallization finishes, product is filtered, the washing back obtains sample B at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.The SiO of B
2/ Al
2O
3Mol ratio is 10.6, and XRD figure is seen accompanying drawing one, and Electronic Speculum figure sees figure two.
Embodiment 2
With the Ludox is the silicon source, and sodium aluminate is the aluminium source, and tetraethyl ammonium hydroxide is the template agent, and hydrothermal crystallizing synthesizes zeolite of the present invention.Reactant batching mol ratio: n (SiO
2): n (template agent): n (Na
2O): n (Al
2O
3): n (H
2O)=and 8: 0.8: 3.5: 1: 140.Synthetic method: press the reactant charge ratio in the tetraethyl ammonium hydroxide solution of NaOH and sodium aluminate adding 20%, add Ludox after mixing again.With said mixture 40 ℃ down stir 6 hours after again aged at room temperature 24 hours, move in the autoclave, airtight, adopt static at 110 ℃ of crystallization 120h.After crystallization finishes, product is filtered, the washing back obtains sample A at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.The SiO of A
2/ Al
2O
3Mol ratio is 7.2.
Embodiment 3
With waterglass is the silicon source, and aluminium chloride is the aluminium source, and tetraethyl ammonium hydroxide is the template agent, and hydrothermal crystallizing synthesizes zeolite of the present invention.Reactant batching mol ratio: n (SiO
2): n (template agent): n (Na
2O): n (Al
2O
3): n (H
2O)=and 15: 0.5: 6.0: 1: 170.Synthetic method: press reactant batching mol ratio, NaOH and sodium aluminate are joined in the 20% TPAOH solution, add Ludox after mixing again.With said mixture 40 ℃ down stir 6 hours after again aged at room temperature 24 hours, move in the autoclave, airtight, be 110 ℃ of crystallization 24h in static state earlier, dynamically be 110 ℃ of crystallization 48h (200 rev/mins of mixing speeds) then.After crystallization finishes, product is filtered, the washing back obtains sample C at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.The SiO of C
2/ Al
2O
3Mol ratio is 9.1.
Embodiment 4
With the solid silicone is the silicon source, and aluminum nitrate is the aluminium source, and tetraethyl ammonium hydroxide is the template agent, and hydrothermal crystallizing synthesizes zeolite of the present invention.Reactant batching mol ratio: n (SiO
2): n (template agent): n (Na
2O): n (Al
2O
3): n (H
2O)=and 45: 3.0: 15: 1: 320.Synthetic method: press reactant batching mol ratio, NaOH and sodium aluminate are joined in the 20% tetraethyl ammonium hydroxide solution, add Macrogol 2000, add Ludox after mixing again, two kinds of template agent consumption mol ratios are 1: 1.With said mixture 65 ℃ down stir 12 hours after again aged at room temperature 12 hours, move in the autoclave, airtight, (100 rev/mins) are at 120 ℃ of crystallization 72h under the stirring.After crystallization finishes, product is filtered, the washing back obtains sample D at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.The SiO of D
2/ Al
2O
3Mol ratio is 12.6.
With waterglass is the silicon source, and sodium aluminate and aluminium chloride are the aluminium source, and PEG400 is the template agent, and hydrothermal crystallizing synthesizes zeolite of the present invention.Reactant batching mol ratio: n (SiO
2): n (template agent): n (Na
2O): n (Al
2O
3): n (H
2O)=and 24: 2.0: 2.0: 1: 230.Synthetic method: press the reaction mass mol ratio, NaOH, sodium aluminate are added to the water, stir and add PEG400 after 30 minutes, (addition is total Al to add aluminium chloride again
2O
330%), add waterglass again after continuing to stir.Stirring is after 12 hours down at 30 ℃ with said mixture, and room temperature moves in the autoclave of band polytetrafluoroethylene (PTFE) after placing a night, and is airtight, (50 rev/mins) 110 ℃ of crystallization 96h under stirring.After crystallization finishes, product is filtered, the washing back obtains sample E at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.The SiO of E
2/ Al
2O
3Mol ratio is 11.3.
Comparative example 1
Press the US5549881 method.At first prepare crystal seed: charge ratio 12.5 (SiO
2): 13.33 (Na
2O): (Al
2O
3): 267 (H
2O); Process for aluminium hydroxide is joined in the water that is dissolved with NaOH to sodium aluminate colloidal sol, and then slowly add sodium metasilicate, supply behind the water vigorous stirring evenly after, place under the room temperature and used in 16 days.
Secondly, be the silicon source with the Ludox, TBAH is for being the template agent, hydrothermal crystallizing synthesizes zeolite of the present invention, reactant batching mol ratio: n (SiO
2): n (template agent): n (Na
2O): n (Al
2O
3): n (H
2O)=and 18: 3.6: 1.2: 1: 275.Method: successively 59g NaOH and 75g aluminium hydroxide are joined in the 100g water, supply water again up to 250g after the heating stirring and dissolving, obtain sodium aluminate solution; In addition, 135g is arrived in 42.5g Ludox (silica content 40%), 16 days crystal seed of the above-mentioned aged at room temperature of 11.9g, 63.7g TBAH and the above-mentioned sodium aluminate solution 5.17g that obtains, 7.44g aluminum sulfate solution (50% aluminum sulfate concentration) and moisturizing; Stirring is after 12 hours down at 30 ℃ with said mixture, and room temperature moves in the autoclave of band polytetrafluoroethylene (PTFE) after placing a night, and is airtight, 110 ℃ of crystallization difference 120h, 240h under static state.120h crystallization product is unformed, and 240h obtains the crystallization product, and product is filtered, and the washing back obtains sample F at 550 ℃ of roasting removed template methods then 110 ℃ of dryings.The SiO of F
2/ Al
2O
3Mol ratio is 6.5.Electronic Speculum figure sees Fig. 3, and the pattern of its crystal grain is irregular multiple edge body particle as can be seen, and grain diameter is bigger.
Comparative example 2
Press the US5716593 method, the 51.6g sodium aluminate is joined in the 150.2g Ludox to mix stir that (SiO fed intake in 10 minutes
2/ Al
2O
3Mol ratio is 12), add 11.3g NaOH and 349.6g tetraethyl ammonium hydroxide then successively and continue to mix stirring 4 hours, add 60g water then and become paste, heating makes that volatile matter loss of weight 50% is that gross weight reduces 230g in the mixture under 66 degree again, put into crucible after the airtight night under the room temperature, crucible being put into the bottom has the autoclave of 12ml water again, at 110 degree difference crystallization 160h.After crystallization finishes, product is filtered, the washing back obtains comparative sample G at 550 ℃ of roasting removed template methods, the SiO of G then 110 ℃ of dryings
2/ Al
2O
3Mol ratio is 5.2.
Example 6
Be the sample A h-type zeolite F that exchange obtains through ammonium salt.Get the SiO that example 1 synthesizes
2/ Al
2O
310.6, Na
2The sample B50g of O 6.2w%, with water purification solid-to-liquid ratio is diluted to 1: 10, concentration according to 2.0M adds ammonium nitrate then, stirs, is warming up to 90 ℃, and constant temperature stirred 2 hours, be cooled to 50 ℃ of filtrations then, through the zeolite sample of twice ammonium salt exchange, wash to pH and reach 5～6, put into drying box then, 110～120 ℃ of dryings were warmed up to 540 ℃ in 6 hours, constant temperature 10 hours then in roaster.The product that ammonium is taken off in high-temperature roasting after crushed as stated above again the ammonium exchange once promptly obtain the h-type zeolite F of template synthetic method preparation of the present invention.Sample F SiO
2/ Al
2O
3Mol ratio is 11.2, NaO
2Content 0.15%.
Example 7
Be hydrocracking catalyst 1 of the present invention.Get example 1 prepared zeolite A22.2g and a kind of macroporous aluminium oxide (specific area 420m
2/ g, pore volume are 0.9ml/g) 14.5g mixes, and adds molten little porous aluminum oxide (the specific area 240m of 30g of dilute nitric acid solution glue by the concentration 5% of 70ml
2/ g, pore volume are 0.42ml/g) adhesive that obtains, continue to mix and pinch up to becoming paste, extruded moulding, institute's moulding bar that obtains be 110 ℃ of dryings 8 hours down, 500 ℃ activate 4 hours and make activated carrier after.With the dissolving of 27.5g ammonium metatungstate and 31g nickel nitrate and demarcate, obtain the W-Ni co-impregnated solution again, flood the carrier of above-mentioned preparation with this maceration extract to 42ml, again 110 ℃ of dryings 8 hours, and 500 ℃ activate 3 hours after, obtain hydrocracking catalyst 1.Catalyst finally consists of: zeolite component 40w%, macroporous aluminium oxide 12w%, aperture aluminium oxide 19w%, nickel oxide 7w%, tungsten oxide 22w%.
Example 8
Be hydrocracking catalyst 2 of the present invention.Get example 1 prepared zeolite B 21.1g and a kind of amorphous aluminum silicide (SiO
2Content 40w%, specific area 510m
2/ g, pore volume are 1.1ml/g) 92.9g mixes, and adds the dilute nitric acid solution that is diluted in 63ml distilled water by 7.5ml (concentration 40%), continue to mix and pinch up to becoming paste, extruded moulding, the moulding bar that obtains 110 ℃ dry 12 hours down, after 500 ℃ of activation made the activation carrier in 4 hours.With the dissolving of 25g ammonium metatungstate and 25g nickel nitrate and demarcate, obtain the W-Ni co-impregnated solution again, flood the carrier of above-mentioned preparation with this maceration extract to 64ml, again 110 ℃ of dryings 8 hours, and 500 ℃ activate 3 hours after, obtain hydrocracking catalyst 2.Catalyst finally consists of: zeolite component 20w%, sial 54w%, nickel oxide 6w%, tungsten oxide 20w%.
Example 9
Be hydrocracking catalyst 3 of the present invention.According to the method preparation of embodiment 8, select zeolite F.
Example 10
Be catalyst for hydro-upgrading 4 of the present invention.According to the method preparation of embodiment 7, select zeolite C.
Example 11
Be catalyst for hydro-upgrading 5 of the present invention.According to the method preparation of embodiment 7, select zeolite D.
Example 12
Be hydrotreating catalyst 6 of the present invention.Get example 1 prepared zeolite E 15.5g and a kind of aluminium oxide (specific area 380m
2/ g, pore volume are 0.7ml/g) 38.5g mixes, and adds molten little porous aluminum oxide (the specific area 240m of 14.3g of dilute nitric acid solution glue by the concentration 5% of 70ml
2/ g, pore volume are 0.42ml/g) adhesive that obtains, continue to mix and pinch up to becoming paste, extruded moulding, institute's moulding bar that obtains be 110 ℃ of dryings 8 hours down, 500 ℃ activate 4 hours and make activated carrier after.Again the 4.2g chloroplatinic acid is diluted in the 36ml water back and floods the carrier of above-mentioned preparation with this maceration extract, again 110 ℃ of dryings 8 hours, and 500 ℃ activate 3 hours after, obtain hydrocracking catalyst 1.It is 0.4% in element content that catalyst finally consists of precious metals pt, and zeolite content is 30w%, and surplus is an aluminium oxide.
Example 13
It below is the comparing result of hydrocracking catalyst 1,2,3 of the present invention and a kind of commercial reference hydrocracking catalyst (the industrial trade mark 3974, the Fushun Petrochemical Company catalyst plant is produced).Feedstock oil character sees Table 1, the appreciation condition that embodiment is related: reaction pressure is 15MPa, and hydrogen to oil volume ratio is 1500, and air speed is 1.5hr
-1Feedstock oil enters the cracking zone cracking through giving after refining, and middle distillates oil selectivity calculates by (jet fuel+diesel oil/＜370 ℃ conversion ratio), weighs its activity level by reaching the needed reaction temperature of same conversion 60w%.The evaluating catalyst data of table 2 show, hydrocracking catalyst of the present invention uses the synthetic zeolite with faujasite feature of template that the present invention relates to, last handling process is simple, and catalytic performance comprises that activity or middle distillates oil selectivity all meet or exceed the prior art level.
Table 1 raw material oil properties
Table 2 evaluating catalyst result
Example 14
Catalyst for hydro-upgrading 4 is used for the diesel modifying technical process.With coker gas oil, catalytic diesel oil and straight-run diesel oil (atmosphere 3rd side cut) miscella is that raw material (1: 2: 1) carries out upgrading, feed sulphur content 8000 μ g/g, 5 ℃ of condensation points.At hydrogen dividing potential drop 8.0MPa, volume of hydrogen oil ratio 400: 1, volume space velocity 1.2h
-1, under 370 ℃ of conditions of reaction temperature, miscella is carried out hydrotreatment, product property obviously improves: sulphur content of diesel fraction is reduced to 235.8 μ g/g, and desulfurization degree reaches 97m%, and condensation point is reduced to 0 ℃, reaches 0# light diesel fuel index request.
Example 15
The application of hydrotreating catalyst 5.With straight-run diesel oil is that this raw material of distillate feedstock contacts at first section hydro-upgrading reactor with hydrogen, catalyst for hydro-upgrading 4 earlier, at hydrogen dividing potential drop 8MPa, 360 ℃ of temperature, hydrogen to oil volume ratio 500: 1, liquid hourly space velocity (LHSV) 1.2h
-1React under the condition, first section hydro-upgrading reactor effluent directly enters high pressure hot separator.The bottom stripping of hot high score is removed impurity such as the hydrogen sulfide of one section reaction in the logistics, ammonia, and cooling obtains diesel oil distillate and part respectively to hot high score stripping gas through two steps.First section diesel oil distillate enters secondary hydrogenation and takes off the aromatic hydrocarbons reactor.Exist under the situation at above-mentioned hydrotreatment dearomatization catalyst 5 and hydrogen, at hydrogen dividing potential drop 8MPa, 280 ℃ of temperature, hydrogen to oil volume ratio 500: 1, liquid hourly space velocity (LHSV) 2h
-1Condition under carry out deeply hydrodearomatized reaction.Product property shows that total aromatic hydrocarbons of the relative raw material of total arene content of diesel product is reduced to 8% from reducing by 42%, and the arene engaging scraping rate reaches 81%.
Claims (12)
1, a kind of hydrogenation catalyst that contains faujasite, comprise by weight: faujasite 1%-95%, refractory oxide 1%-90%, in oxide active metal component 0.05%～60%, each constituent content sum is 100%, and described reactive metal is selected from the reactive metal in group vib and/or the VIII family; The SiO that it is characterized in that described faujasite
2/ Al
2O
3Mol ratio is 6～20, and X zeolite RD spectrum analysis belongs to the y-type zeolite in the faujasite, and the crystal grain pattern has the sheet pattern.
2,, it is characterized in that the SiO of described faujasite according to the described catalyst of claim 1
2/ Al
2O
3Mol ratio is 6～12.
3,, it is characterized in that described faujasite is na-pretreated zeolite or h-type zeolite according to claim 1 or 2 described catalyst.
4, the described hydrogenization catalyst preparation method of a kind of claim 1, adopt infusion process, ion-exchange, kneading method or coprecipitation preparation, it is characterized in that faujasite wherein adopts following process preparation: aluminium source, silicon source, sodium source and template agent are mixed according to a certain percentage, and the molar ratio of various raw materials is in the mixture: 5～50SiO
2: 1.5～15Na
2O: Al
2O
3: 0.05～5.0 template agent: 60～420H
2O; Na wherein
2O/SiO
2Mol ratio is 0.05～0.8, H
2O/SiO
2Mol ratio is 6～40; Mixture stirs under ℃ condition of room temperature～70 and formed even gel in aging 1-100 hour, under 90-130 ℃ of condition under the reactor self-generated pressure hydrothermal crystallizing 24-240 hour.
5, in accordance with the method for claim 4, it is characterized in that described Na
2O/SiO
2Mol ratio is 0.1～0.4, H
2O/SiO
2Mol ratio is 10～22.
6, in accordance with the method for claim 4, it is characterized in that described template agent is organic base compounds and/or organic high molecular compound; Wherein, the organic base compounds is selected from the alkyl ammonium hydroxide compound, and it is in 200～10000 the polyethylene glycol one or more that described organic high molecular compound is selected from molecular weight.
7, in accordance with the method for claim 6, it is characterized in that described alkyl ammonium hydroxide compound is one or more in TMAH, tetraethyl ammonium hydroxide, TPAOH and the TBAH.
8, in accordance with the method for claim 4, it is characterized in that described aluminium source is one or more in aluminum sulfate, aluminium chloride, aluminum nitrate and the sodium aluminate; The silicon source is one or more in waterglass, silica gel and the Ludox; The sodium source is one or more of sodium aluminate, NaOH.
9, in accordance with the method for claim 4, it is characterized in that described synthetic faujasite carries out ammonium ion exchange and handles.
10, the application of the described catalyst of claim 1 in various hydrotreating process of hydrocarbons.
11, the application of the described catalyst of claim 1 in the hydrocracking process of heavy hydrocarbon.
12, the application of the described catalyst of claim 1 in the hydro-upgrading process of various hydro carbons.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5192520A (en) * | 1989-09-13 | 1993-03-09 | Societe National Elf Aquitaine | Synthesis of aluminosilicate zeolites of faujasite structure |
| WO1998022389A1 (en) * | 1996-11-22 | 1998-05-28 | Nyfotek As | Method for production of hexagonal faujasite with low consumption of organic additive, and use of this as a catalyst for alkylation |
| CN1226875A (en) * | 1996-07-31 | 1999-08-25 | 切夫里昂美国公司 | Preparation of Y-type faujasite using organic template |
| CN1164719C (en) * | 2001-10-30 | 2004-09-01 | 中国石油化工股份有限公司 | Cracking catalyst with hydrogen being added for noble metal and its prepn. method |
-
2005
- 2005-10-19 CN CNB2005100475069A patent/CN100448535C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5192520A (en) * | 1989-09-13 | 1993-03-09 | Societe National Elf Aquitaine | Synthesis of aluminosilicate zeolites of faujasite structure |
| CN1226875A (en) * | 1996-07-31 | 1999-08-25 | 切夫里昂美国公司 | Preparation of Y-type faujasite using organic template |
| WO1998022389A1 (en) * | 1996-11-22 | 1998-05-28 | Nyfotek As | Method for production of hexagonal faujasite with low consumption of organic additive, and use of this as a catalyst for alkylation |
| CN1164719C (en) * | 2001-10-30 | 2004-09-01 | 中国石油化工股份有限公司 | Cracking catalyst with hydrogen being added for noble metal and its prepn. method |
Non-Patent Citations (2)
| Title |
|---|
| 沸石催化与分离技术. 高滋等，9，85，88，中国石化出版社. 1999 |
| 沸石催化与分离技术. 高滋等，9，85，88，中国石化出版社. 1999 * |
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