CN100421795C - Catalytic cracking catalyst containing faujasite and preparation method thereof - Google Patents
Catalytic cracking catalyst containing faujasite and preparation method thereof Download PDFInfo
- Publication number
- CN100421795C CN100421795C CNB2005100475073A CN200510047507A CN100421795C CN 100421795 C CN100421795 C CN 100421795C CN B2005100475073 A CNB2005100475073 A CN B2005100475073A CN 200510047507 A CN200510047507 A CN 200510047507A CN 100421795 C CN100421795 C CN 100421795C
- Authority
- CN
- China
- Prior art keywords
- faujasite
- zeolite
- catalyst
- rare earth
- catalytic cracking
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a catalytic cracking catalyst with faujasite. Wherein, it comprises high-silicon-aluminum faujasite at 5-95%, and fusion-resistant oxide at 5-90%; the mol ratio as SiO2/Al2O3 of faujasite is 6-20; 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 a kind of hydrocarbon cracking catalyst that is used for catalytic cracking process and preparation method thereof, particularly contain catalytic cracking catalyst of faujasite and preparation method thereof.
Background technology
Reduce day by day to the heavy Fuel Demand in more and more heavier and market along with raw material, and catalytic cracking process has become topmost processing of heavy oil means, is bringing into play more and more important effect in heavy oil transformation.
Catalyst plays key effect to catalytic cracking process, and the exploitation of the discovery raw catelyst of new material has promoted the development of catalytic cracking process, and a kind of good catalyst for heavy oil catalytic cracking should possess following performance: good heavy oil pyrolysis performance; The preventing from heavy metal pollution performance is strong; Coke selectivity is good; Good stripping performance; Hydrothermal stability is high.
Above-mentioned these requirements have all proposed very high request to cracking catalyst component-zeolite, and wherein most important is exactly acidity and pore structure.The Y zeolite is after various modifications, has very strong acidic cleavage function, the Y zeolite belongs to faujasite simultaneously, supercage structure with big cavity, make it have good diffusion to big molecule, be particularly suitable for the catalytic pyrolysis of big molecule heavy oil, thereby the heavy oil catalytic cracking process in the petrochemical technology field is used widely.
Based on the requirement of heavy oil catalytic pyrolysis, in order to improve catalyst performance, people carry out various modifications to the Y zeolite and handle.Continuous heaviness, poor qualityization along with catalytically cracked material, and environment friendly system is to the increase day by day of unleaded high-knock rating gasoline demand, the ultra-steady Y molecular sieve Cracking catalyst development of catalyst trend macromolecule sieve content, because the change of raw material is heavy, new requirement has been proposed also the macromolecular ability of catalytic cracking catalyst cracking simultaneously.
The employing of the high silica alumina ratio molecular sieve little along with structure cell, that the acid centre number is few, hydrogen transfer activity is low, the addition of molecular sieve obviously increases in the catalyst, therefore not only be confined to the modification of Y zeolite, but, also be a key areas of zeolite Study of synthesis method from synthetic initially just being improved of zeolite.
US6160191 discloses a kind of hydrocarbon conversion process that uses zeolite catalyst, and wherein the catalyst zeolite preparation method that relates to use comprises: zeolite seed crystal and/or the template agent of trivalent metal oxide (as aluminium oxide), silica, alkali metal cation and 0-10w% are mixed back synthetic big crystal grain zeolite under static state.
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.
US5273945 discloses a kind of catalytic cracking catalyst, it contains zeolite with faujasite feature and the reactive metal of 1-99w%, wherein related zeolite silica alumina ratio 3-30 has six side's symmetrical structures, and this zeolite building-up process uses severe toxicity and expensive crown ether to do the template agent.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of catalytic cracking catalyst, adopt a kind of novel molecular sieve, improved the serviceability of catalyst.
Catalytic cracking catalyst of the present invention contains high silica alumina ratio faujasite 5-95w%, refractory oxide 5-95w% by weight.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 sheet pattern, Na
2O content is lower than 1w%, preferably is lower than 0.2w%.Faujasite also can be with rare-earth element modified, and as adopting rare-earth element modified faujasites such as lanthanum and/or cerium, the weight of rare earth element in faujasite contains and is generally 1%～15%.
Refractory oxide in the catalytic cracking catalyst of the present invention is selected from one or more material such as aluminium oxide, silica, titanium oxide, zirconia, carclazyte, kaolin, bentonite, sepiolite, other type zeolite.
The preparation process of catalytic cracking catalyst of the present invention can adopt the method for this area routine, as with required mixing of materials, adds binding agent, and moulding, drying, roasting obtain final catalytic cracking catalyst.The faujasite that wherein relates to adopts following process preparation:
(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) filtering crystallization product also, drying obtains zeolite powder; (6) zeolite powder is exchanged 1～5 time to obtaining low sodium h-type zeolite with ammonium salt; Low sodium h-type zeolite can further obtain rare earth modified faujasite with rare earth ion exchanged.
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.
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.The synthesizing high-silicon faujasite mainly adopts directing agent method (is directed agents with crystal seed glue) 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 faujasite sample, and abscissa is 2 θ angles.
Fig. 2 is the sem photograph of embodiment 1 faujasite sample.
Fig. 3 is the sem photograph of comparative example 1 method synthetic faujasites sample.
The specific embodiment
Catalytic cracking catalyst of the present invention is preferably by can containing the synthetic faujasite of middle macroporous aluminium oxide, amorphous silicon aluminium, the inventive method, binding agent, clay, kaolin etc. in the following component, and the molecular sieve of other type.Other type has divided sieve mainly to comprise various Modified Zeolite Y (as super steady Y, Rare Earth Y etc.), ZSM-5 molecular sieve, beta-molecular sieve etc.
Binding agent be various can peptization and have the aluminium oxide of adhesive property or through viscosity Ludox, aluminium colloidal sol, sial complex sol, aluminum phosphate colloidal sol, phosphaljel or their compound etc. of special modification.
A kind of concrete preparation method of catalyst of the present invention can be with reference to following process: materials such as clay are mixed making beating add the acidifying of inorganic acid example hydrochloric acid with deionized water, add boehmite, aluminium colloidal sol, zeolite molecular sieve making beating again, promptly get catalyst of the present invention through steps such as moulding, drying, roastings.Detailed preparation process comprises: (1) mixes making beating 20-40 minute according to the proportion of composing of catalyst with clay with deionized water, added hcl acidifying 0.5-20 hour, adds the boehmite stirring to pulp 20-40 minute; (2), add aluminium colloidal sol again and stirred 10-30 minute at 50-80 ℃ of aging 0.5-2 hour; (3) add ground zeolite molecular sieve, continue making beating 20-40 minute; (4) drying and moulding is as spray-drying; (6) obtained product at 500-700 ℃ of roasting 1-4 hour.
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.
When sodium Hydrogen faujasite is hanged down in ammonium salt exchange preparation, can adopt the method for operating of this area routine.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.
Adopt the rare earth exchanged method of this area routine when preparing rare earth modified faujasite.As with rare earths salt exchange 1～5 time in room temperature～100 ℃.Preferably carry out rare earth exchanged again after the ammonium salt exchange.
Further specify Preparation of catalysts method of the present invention, character and effect by the following examples, the scheme among the embodiment is that specific embodiments is not construed as limiting the invention in scope of the invention claim scope.(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 A 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 sem photograph is seen 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 B 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 the h-type zeolite G that sample B process ammonium salt exchanges and the acid treatment dealuminzation obtains.Get the SiO that example 2 synthesizes
2/ Al
2O
37.2, Na
2The sample A50g of O 8.3w%, 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 90～95 ℃, and constant temperature stirred 2 hours, be cooled to 50～60 ℃ 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 ℃ of dryings were warmed up to 540 ℃ in 6 hours, constant temperature 10 hours then in roaster.The ammonium exchange is once more as stated above after crushed for the product that ammonium is taken off in high-temperature roasting.120 ℃ of dryings of product after the exchange are diluted to 1: 10 with water purification with solid-to-liquid ratio after 6 hours again, add hydrochloric acid according to the concentration of 0.6M then, stir and are warming up to 90 ℃, and constant temperature stirred 2 hours, put into drying box after being cooled to 50 ℃ of filtrations, 110 ℃ of dryings 6 hours.Obtain the hydrogen zeolite G of template synthetic method preparation of the present invention shortly.Sample G SiO
2/ Al
2O
3Mol ratio is 9.3, NaO
2Content 0.12%.
Example 8
The rare earth zeolite H that obtains through ammonium salt and rare earth exchanged for sample C.Get the SiO that example 3 synthesizes
2/ Al
2O
39.1, 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, stir, be warming up to 90 ℃, constant temperature stirred 2 hours, was cooled to 50 ℃ of filtrations then, through the zeolite sample of an ammonium salt exchange, wash to pH and reach 5～6, put into 120 ℃ of dryings of drying box then 6 hours.Drying sample is diluted to 1: 10 with water purification with solid-to-liquid ratio again, adds cerium chloride according to 3% concentration then, stirs and is warming up to 90 ℃, and constant temperature stirred 2 hours, was cooled to 50～60 ℃ of filtrations then, put into 120 ℃ of dryings of drying box again 6 hours.In roaster, be warmed up to 540 ℃ then, constant temperature 10 hours.High-temperature roasting is taken off the product of ammonium and handle once with said method more as stated above after crushed, promptly obtain the rare earth modified zeolite H of template synthetic method preparation of the present invention.Sample H SiO
2/ Al
2O
3Mol ratio is 9.8, NaO
2Content 0.15%, content of rare earth 7w%.
Example 9
Be catalytic cracking catalyst 1,2,3 of the present invention.Kaolin slurry 850Kg (solid content 35%), boehmite 450Kg (solid content 40%), aluminium colloidal sol 150Kg (aluminium content 15%), 500Kg water are made homogeneous slurry, adjusting pH value with hydrochloric acid is 3, under 75 ℃ of temperature, burin-in process 15 hours makes matrix component slurries I; Get embodiment 6,7,8 zeolite molecular sieve F of the present invention, G, H 300Kg, 600Kg again, 900Kg stirs, adjusting pH value with ammoniacal liquor is 6.0, making beating was handled 15 hours, made modified active component slurries II; I, II slurries are mixed, stirred 24 hours, spray-drying makes catalyst; After the catalyst detergent that makes, drying, promptly get catalyst prod 1,2,3, wherein contain high silica alumina ratio faujasite of the present invention and be respectively 35%, 55%, 65%.
Comparative example 3
Be reference catalyst.(Wenzhou catalyst plant is produced, SiO to get a kind of industrial NaY
2/ Al
2O
34.6, Na
2The sample 50g of O10.7w% is diluted to 1: 10 with water purification with solid-to-liquid ratio, and the concentration according to 2.0M adds ammonium nitrate then, stir, be warming up to 90 ℃, constant temperature stirred 2 hours, was cooled to 50 ℃ of filtrations then, after three exchanges, put into 120 ℃ of dryings of drying box 6 hours repeatedly.Drying sample is warmed up to 540 ℃ in roaster, constant temperature 10 hours.The product that high-temperature roasting is taken off ammonium exchanges three times with ammonium nitrate after crushed more as stated above repeatedly, obtains hydrogen zeolite sample HY.Sample HY SiO
2/ Al
2O
3Mol ratio is 5.3, NaO
2Content 0.08%.Further, prepare reference catalyst according to the composition and the preparation method of above-mentioned example 9, unique difference be exactly the zeolite activity component that adopted be the HY (it is identical with catalytic cracking catalyst of the present invention 1 to form content) of above-mentioned preparation.
Example 10
The invention described above catalyst 1,2,3 and reference catalyst be through behind 800 ℃, 20h, 100% steam burin-in process, carries out heavy oil (350～530 ℃ of boiling ranges) micro anti-evaluation under 450 ℃, the condition of oil ratio 5.The result of table 1 shows that catalyst of the present invention is compared with reference catalyst, and unconverted heavy oil reduces 6.7%, 8.2% and 9.3% respectively, and yield of light oil exceeds 4.2%, 5.3% and 6.8% respectively.
Table 1 heavy oil micro anti-evaluation result
| Catalyst | 1 | 2 | 3 | Reference |
| The heavy oil transformation rate, w% | 77.2 | 78.7 | 79.8 | 70.5 |
| Yield of light oil, w% | 77.5 | 78.6 | 80.1 | 73.3 |
Claims (8)
1. a catalytic cracking catalyst that contains faujasite contains high silica alumina ratio faujasite 5%-95% by weight, and refractory oxide 5%-95% is characterized in that the wherein SiO of 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 sheet pattern, Na
2O content is lower than 1w%.
2. according to the described catalyst of claim 1, it is characterized in that the SiO of described faujasite
2/ Al
2O
3Mol ratio is 6～12.
3. according to the described catalyst of claim 1, it is characterized in that described faujasite Na
2O content is lower than 0.2w%.
4. according to the described catalyst of claim 1, it is characterized in that described faujasite is rare earth modified faujasite, the weight content of rare earth element in faujasite is 1%～15%.
5. according to the described catalyst of claim 4, it is characterized in that described rare earth element is cerium and/or lanthanum.
6. described Preparation of catalysts method of claim 1, with required mixing of materials, add binding agent, moulding, drying, roasting obtain final catalytic cracking catalyst, and it is characterized in that the faujasite that wherein relates to adopts following process preparation: mix aluminium source, silicon source, sodium source and template agent according to a certain percentage (1); (2) stir and formed in aging 1-100 hour even gel being no more than under 70 ℃ of conditions; (3) even 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) filtering crystallization product also, drying obtains zeolite powder; (6) zeolite powder is exchanged 1～5 time to obtaining low sodium Hydrogen faujasite with ammonium salt.
7. in accordance with the method for claim 6, it is characterized in that described low sodium Hydrogen faujasite obtains rare earth modified faujasite with rare earth ion exchanged.
8. in accordance with the method for claim 6, 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 one or more in TMAH, tetraethyl ammonium hydroxide, TPAOH and the TBAH; It is in 200～10000 polyethylene glycol one or more that described organic high molecular compound is selected from molecular weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100475073A CN100421795C (en) | 2005-10-19 | 2005-10-19 | Catalytic cracking catalyst containing faujasite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100475073A CN100421795C (en) | 2005-10-19 | 2005-10-19 | Catalytic cracking catalyst containing faujasite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1951566A CN1951566A (en) | 2007-04-25 |
| CN100421795C true CN100421795C (en) | 2008-10-01 |
Family
ID=38058237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100475073A Active CN100421795C (en) | 2005-10-19 | 2005-10-19 | Catalytic cracking catalyst containing faujasite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100421795C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658193A (en) * | 2012-03-31 | 2012-09-12 | 山东多友科技有限公司 | Preparation method of hydrocarbon cracking catalyst |
| CN103894220B (en) * | 2012-12-25 | 2017-06-16 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst without mercury for acetylene hydrochlorination reaction and preparation method thereof |
| CN115353296B (en) * | 2022-08-30 | 2024-03-01 | 武汉思越新材料有限公司 | Water repellent composition and preparation method thereof |
Citations (5)
| 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 |
| US5716593A (en) * | 1996-07-31 | 1998-02-10 | Chevron U.S.A. Inc. | Preparation of Y-type faujasite using an organic template |
| CN1382631A (en) * | 2001-04-28 | 2002-12-04 | 中国石油化工股份有限公司 | Rare-earth Y-type zeolite |
| CN1415704A (en) * | 2001-10-30 | 2003-05-07 | 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 |
| CN1676577A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Petroleum hydrocarbon cracking catalys containing rare earth superstable Y-type zeolite |
-
2005
- 2005-10-19 CN CNB2005100475073A patent/CN100421795C/en active Active
Patent Citations (5)
| 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 |
| US5716593A (en) * | 1996-07-31 | 1998-02-10 | Chevron U.S.A. Inc. | Preparation of Y-type faujasite using an organic template |
| CN1382631A (en) * | 2001-04-28 | 2002-12-04 | 中国石油化工股份有限公司 | Rare-earth Y-type zeolite |
| CN1415704A (en) * | 2001-10-30 | 2003-05-07 | 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 |
| CN1676577A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Petroleum hydrocarbon cracking catalys containing rare earth superstable Y-type zeolite |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1951566A (en) | 2007-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2014082587A1 (en) | Zsm-5 type molecular sieve synthesis method | |
| CN100586854C (en) | Small crystal grain molecular sieve preparation method | |
| CN102910645A (en) | Isomorphous phase compound molecular sieve and preparation method thereof | |
| CN110217804B (en) | ZSM-5 molecular sieve and preparation method thereof, hydrogen type ZSM-5 molecular sieve and application thereof, and methanol conversion method | |
| CN101619228A (en) | Method for quick in situ synthesis of catalytic cracking catalyst | |
| CN100390060C (en) | High-silica octagonal zeolite and synthesizing method thereof | |
| US4879103A (en) | Composition and process for preparing ECR-30 | |
| CN100390059C (en) | High silica/ aluminum ratio octagonal zeolite synthesizing method | |
| CN1267345C (en) | Preparation method of NaY molecular sieve | |
| CN106946268B (en) | A kind of MOR/ZSM-35 composite molecular screen and its synthetic method | |
| CN100421795C (en) | Catalytic cracking catalyst containing faujasite and preparation method thereof | |
| CN1096417C (en) | Synthesis method for beta zeolite | |
| CN102050466B (en) | Method for in-suit synthesis of Y-type molecular sieve by taking silicon-aluminum as base material | |
| CN103771439A (en) | Method for preparing Beta zeolite molecular sieve from diatomite | |
| CN102701232B (en) | Preparation method of NaY molecular sieve | |
| CN1020039C (en) | Synthesis of mercerized zeolite with high silicon content | |
| CN101723395B (en) | Method for preparing double-micropore composite molecular sieve | |
| CN104649294B (en) | Method for improving relative crystallinity of synthetic NaY zeolite | |
| CN102050465B (en) | Method for preparing Y-type molecular sieve through solid-phase in-situ synthesis | |
| CN106946270B (en) | A kind of Beta/EU-1 composite molecular screen and its synthetic method | |
| CN1161274C (en) | Process for preparing EMT zeolite with inorganic emulsifier as assistant | |
| CN100431961C (en) | Octagonal zeolite synthesizing method | |
| CN1151067C (en) | process for preparing cubic mesoporous Si-Al molecular sieve with strong acidic site | |
| CN105621439B (en) | A kind of synthetic method of Beta zeolites | |
| CN103449468B (en) | Synthesis method of NaY molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |