CN1388064A - Prepn of high-silicon Y-Zeolite - Google Patents
Prepn of high-silicon Y-Zeolite Download PDFInfo
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- CN1388064A CN1388064A CN 01118446 CN01118446A CN1388064A CN 1388064 A CN1388064 A CN 1388064A CN 01118446 CN01118446 CN 01118446 CN 01118446 A CN01118446 A CN 01118446A CN 1388064 A CN1388064 A CN 1388064A
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Abstract
The preparation of high-silicon Y-zeolite with unit cell constant of 2.420-2.440 nm includes once or multiple ammonium exchange, hydrothermal treatment and/or chemical dealuminization of NaY-zeolite or stabilizing processed Y-zeolite. The preparation features that at least the first ammonium exchange is selective one at RM-60 deg.c and the other ammonium exchange may be selective one at RM-60 deg.c or conventional one at 60-90 deg.c. Compared with Y-zeolite prepared through available process, the Y-zeolite prepared through process of the present invention has relatively higher crystal reserving degree at small unit cell constant and more secondary pores and is suitable for use as intermediate fraction oil hydrocracking catalyst.
Description
The present invention relates to the preparation method of new a kind of type-Y high silicon zeolite.
In order to improve refining of petroleum activity of such catalysts and selectivity, use the molecular sieve of modification in the molecular sieve type catalyst usually.To hydrocracking catalyst, particularly the intermediate oil hydrocracking catalyst for improving the selectivity of intermediate oil, requires the consumption of molecular sieve in the catalyzer to lack, the acid site density of molecular sieve is low, and molecular sieve pore volume particularly secondary pore pore volume is big as far as possible.Owing to wish that the molecular sieve consumption is few, the crystallization reservation degree of molecular sieve will be high as far as possible; The silica alumina ratio height of low acid site density requirements molecular sieve, for Y zeolite, i.e. lattice constant a
0Low, wish a
0Less than 2.440 nanometers even lower.Under the very low situation of acid site density, the aperture of molecular sieve is big more, and the utilization ratio in acid site is high more, and for actual oil product, necessary is not only primary hole, it is also important that so-called secondary pore, wishes that the secondary pore pore volume is big.
Existing Y zeolite method of modifying comprises: the positively charged ion by ion-exchange conversion zeolite and improve the silica alumina ratio of zeolite by the framework modification of zeolite, wherein low, the lattice constant of aluminium content reduces in a kind of method of modifying gained zeolite in back, the zeolite framework silica alumina ratio improves, thereby reduced sour density, improved strength of acid, improved thermostability and hydrothermal stability, the molecular sieve of some of them method gained also can produce secondary pore simultaneously in addition.
The treatment process that can improve the silica alumina ratio of zeolite in prior art has hydrothermal dealumination and chemical dealuminization; The former is high-temperature roasting NH in the presence of water vapour
4The NaY zeolite makes high-silicon Y-Zeolite, is called overstable gamma zeolite (USY) (consulting US3,293,192,4,036,739); The latter is with silicofluoride for example ammonium silicofluoride or fluorine-containing other salts or use SiCl
4As dealumination agent, remove NH
4Aluminium in Y or the NaY zeolite framework makes silicon move in the skeleton on the room behind the dealuminzation simultaneously, is called skeleton rich silicon Y zeolite (FSEY) and (consults EP82111; US4,503,023); Perhaps use acid or complexing agent such as EDTA etc. as dealumination agent, the high-silicon Y-Zeolite that makes is called sealumination modified Y zeolite (DAY) and (consults US3,442,795; NPRA Annual Meeting 1986, AM-86-30 etc.); Also can adopt chemical dealuminization to combine and be used alternatingly and prepare high-silicon Y-Zeolite (consulting Chinese patent CN1065253A) with hydrothermal treatment consists.
Chemical dealuminization prepares high silicon Y and boils sometimes, for example adopts EDTA, when the dealuminzation degree surpass framework aluminum content 30% the time, zeolite crystallinity begins to descend, and surpasses at 50% o'clock, it is more serious to descend, the acidity owing to EDTA is stronger simultaneously, the solubleness in water is little, with Al
3+Complex ability a little less than, therefore when dealumination reaction, be the degree of crystallinity that keeps zeolite, must add reaction system with extremely slow speed with very rare solution, in addition, EDTA costs an arm and a leg, the organic acid discharging can produce environmental pollution, thereby this method inconvenience is adopted in industrial production.Adopt SiCl
4The shortcoming of isomorphous substitution method is that corrodibility is strong, and reaction is difficult for evenly carrying out, and the non-framework aluminum of generation is difficult to wash-out, and the duct that reduces zeolite is unobstructed, in addition, and SiCl
4The secondary pore that isomorphous substitution method produces does not seldom even produce secondary pore.Utilize (NH
4)
2SiF
6Carry out isomorphous substitution, though reaction conditions gentleness, non-framework aluminum content is low in the dealuminated zeolite of preparation, rejected region is few in the crystalline structure, but when zeolite framework aluminium removes 50-60% when above, zeolite crystal structure still is seriously damaged, and the indissoluble fluorochemical that reaction process is mingled in the zeolite is difficult for washing to the greatest extent, and residual fluorochemical high temperature can destroy the crystalline structure of zeolite down.In addition, the discharging of fluorochemical can cause the serious environmental pollution.
Chinese patent CN1065253A discloses a kind of preparation method of high-silicon Y-Zeolite, the method that wherein adopts chemical dealuminization-hydrothermal treatment consists to be used alternatingly, and the loss of gained molecular sieve crystallinity is bigger.
Comprehensive prior art is at the very little (a for example of preparation lattice constant
0Less than 2.440 nanometers) y-type zeolite the time because dealumination depth is too dark, zeolite framework destroys serious, is difficult to obtain degree of crystallinity and keeps good zeolite product.
The purpose of this invention is to provide a kind of deep sealumination modified method for preparing small cell Y-zeolite of y-type zeolite that makes, adopt the high-silicon Y-Zeolite of this method preparation, its degree of crystallinity height, secondary pore is more.
The invention provides a kind of method that lattice constant is the high-silicon Y-Zeolite of 2.420-2.440 nanometer for preparing, this method comprises that the y-type zeolite with NaY zeolite or process super stabilizing processing carries out the exchange of one or many ammonium, hydrothermal treatment consists and/or chemical dealuminization; It is characterized in that in the exchange of said ammonium the ammonium exchange first time before hydrothermal treatment consists and/or chemical dealuminization at least be adopt temperature be room temperature to the cryogenic selective ammonium exchange that is lower than 60 ℃, remaining ammonium exchange or for room temperature to being lower than 60 ℃ cryogenic selective ammonium exchange or being 60-90 ℃ conventional ammonium exchange.
Said hydrothermal treatment consists and/or chemical dealuminization can carry out one or many in the method provided by the invention; When being raw material,, generally need carry out secondary or secondary above hydrothermal treatment consists and/or chemical dealuminization in order to obtain needed lattice constant with the NaY zeolite; When being raw material with the y-type zeolite of handling through super stabilizing, because the structure cell of zeolite has had contraction to a certain degree, can only carry out hydrothermal treatment consists and/or chemical dealuminization this moment as required, perhaps carries out secondary or secondary above hydrothermal treatment consists and/or chemical dealuminization.In the process of carrying out said hydrothermal treatment consists and/or chemical dealuminization, preferably both carry out hydrothermal treatment consists and also carried out chemical dealuminization, more preferably carry out hydrothermal treatment consists earlier and carry out chemical dealuminization again.After each hydrothermal treatment consists and/or chemical dealuminization step, perhaps between hydrothermal treatment consists and/or chemical dealuminization step, the step that the ammonium exchange can be arranged, perhaps when carrying out said chemical dealuminization, carry out the ammonium exchange, the ammonium exchange of this moment both can be said cryogenic selective ammonium exchange, also can be conventional ammonium exchange.
The condition of said hydrothermal treatment consists is well known to those of ordinary skill in the art in the method provided by the invention, and there is no particular limitation to it in the present invention; General condition is under 400-700 ℃ temperature and 20-100% water vapour atmosphere roasting 1-4 hour, preferably under 500-650 ℃ temperature and 40-100% water vapour atmosphere roasting 1-3 hour.
The condition of said chemical dealuminization is well known to those of ordinary skill in the art in the method provided by the invention, and there is no particular limitation to it in the present invention; Chemical dealuminization among the present invention both can be to adopt for example the liquid phase aluminium extracting and silicon supplementing method or the employing SiCl of silicofluoric acid, ammonium silicofluoride etc.
4The gas phase aluminium extracting and silicon supplementing method, also can be to adopt acid or complexing agent chemical dealuminization method, or the combination of these methods as dealumination agent.Metallization processes, the environmental friendliness of conforming to the principle of simplicity and the consideration that reduces cost, the simplest method be adopt mineral acid for example hydrochloric acid, sulfuric acid and nitric acid etc. as the chemical dealuminization method of dealumination agent.
Said aluminium extracting and silicon supplementing method carries out according to existing aluminium-eliminating and silicon-replenishing reaction conditions in the method provided by the invention, as according to USP4,503,023, the method and the reaction conditions of the relevant aluminium-eliminating and silicon-replenishing that proposes among CN1048835A, CN1088247A, CN1121484A, CN1127161A, the CN1205915A etc. carry out.
Said employing acid or complexing agent are meant with compounds such as Neutral ammonium fluoride, oxalic acid, citric acid, EDTA, hydrochloric acid, sulfuric acid, nitric acid as the chemical dealuminization method of dealumination agent and take out reactive aluminum in the method provided by the invention.This condition of taking out reactive aluminum is (for example can referring to CN1065253A, CN1058358A) well known to those skilled in the art, generally is in ℃ down reaction 0.5～5 hour of room temperature to 100.When adopting mineral acid as dealumination agent, the concentration of aqueous acid is generally 0.1-5N, preferred 0.5-2N; When adopting complexing agent as dealumination agent, the concentration of complexing agent aqueous solution is generally 1-20 weight %, preferred 5-15 weight %.
In the method provided by the invention the condition of said cryogenic selective ammonium exchange be in room temperature to being lower than under 60 ℃ the temperature exchange 5 minutes to 1 hour, preferably exchange 10-50 minute under 0-50 ℃ temperature.The effect of selectivity ammonium exchange is the positively charged ion (Na that removes specific position
+), for example remove in the Y zeolite positively charged ion in the big cage and do not remove positively charged ion in the little cage substantially, like this; The structure of Y zeolite is difficult for destroyed in hydrothermal treatment consists of carrying out subsequently and/or chemical dealuminization process, thereby can improve the degree of crystallinity of zeolite product, and hydro-thermal and/or the chemical treating process of the positively charged ion that is not removed of beginning by subsequently further removes its migration and conventional ammonium exchange or the exchange of cryogenic selective ammonium by the back.
No matter be said cryogenic selective ammonium exchange or said conventional ammonium exchange, the time of the raw material that the ammonium clearing house is used, the consumption of ammonium salt and exchange is well known to those of ordinary skill in the art; For example the raw material used of clearing house is generally ammonium sulfate, ammonium chloride, ammonium nitrate, ammonium phosphate etc.; The consumption of ammonium salt is generally ammonium salt: molecular sieve=(0.1-2): 1 (weight ratio); The time of conventional ammonium exchange was generally 0.1-3 hour, and preferred 0.5-2 hour, the time of said selectivity ammonium exchange can be shorter.
The high-silicon Y-Zeolite that method provided by the invention makes is compared with the Y zeolite that existing method makes, and it still has higher crystallization reservation degree when less lattice constant (＜2.440 nanometer), have more secondary pore simultaneously.
The following examples will be further described the specific embodiment of the present invention, but can not be interpreted as the qualification to protection domain of the present invention.
In each embodiment and Comparative Examples, the secondary pore pore volume of zeolite is measured with low-temperature nitrogen adsorption method; The lattice constant a of zeolite
0Measure (referring to " petrochemical complex analytical procedure (RIPP test method) " with conventional X-ray diffraction method with the crystallization reservation degree (with respect to initial NaY zeolite) of zeolite, Yang Cui waits volume surely, Science Press, nineteen ninety version, the 412-415 page or leaf), the sodium content x-ray fluorescence spectrometry of zeolite.
Embodiment 1
Ammonium sulfate 50 grams are dissolved in 1500 ml waters, (Qilu Petrochemical company catalyst plant is produced to get 100 gram (butt) NaY zeolites, down together), join in the above-mentioned solution for preparing, stirred 30 minutes down in 20 ℃, filter, with deionized water making beating washing, refilter, obtain the Y zeolite of selectivity ammonium exchange.
Then the gained zeolite is put into temperature and is 650 ℃ tube furnace hydrothermal calcine 2 hours under 50% water vapour atmosphere.
Getting zeolite 20 grams after the above-mentioned roasting and ammonium sulfate 20 restrains to join together in 300 ml distilled waters and stirs, under agitation in 60 minutes time, add 30 milliliters of the hydrochloric acid of 0.1N then, filter water making beating washing, refilter, in 105 ℃ of dryings 3 hours.
Carry out hydrothermal calcine and salt acid treatment again according to above-mentioned steps, obtain high-Si Y-type molecular sieve of the present invention, be designated as A, its physico-chemical property is listed in table 1 and the table 2.
Embodiment 2
Ammonium sulfate 50 grams are dissolved in 1500 ml waters, get 100 gram (butt) NaY zeolites, join in the above-mentioned solution for preparing, stirred 30 minutes down, filter,, refilter with deionized water making beating washing in 50 ℃.
The gained zeolite being added water then is 55 weight % to water content, puts into crucible, adds a cover to cover completely, puts into temperature and be 600 ℃ retort furnace hydrothermal calcine 3 hours.
Getting zeolite 20 grams after the above-mentioned roasting and ammonium sulfate 20 restrains to join together in 300 ml distilled waters and stirs, under agitation in 40 minutes time, add 20 milliliters of the hydrochloric acid of 0.2N then, filter water making beating washing, refilter, in 105 ℃ of dryings 3 hours.
The gained zeolite being added water again is 55 weight % to water content, puts into crucible, adds a cover to cover completely, puts into temperature and be 600 ℃ retort furnace hydrothermal calcine 3 hours.
Again the zeolite behind the above-mentioned re-baking 20 gram and ammonium sulfate 20 are restrained to join together in 300 ml distilled waters and stir, 10 milliliters of hydrochloric acid that under agitation in 30 minutes time, add 0.5N then, filter, water making beating washing, refilter,, obtain high-Si Y-type molecular sieve of the present invention in 105 ℃ of dryings 3 hours, be designated as B, its physico-chemical property is listed in table 1 and the table 2.
Embodiment 3
Ammonium sulfate 50 grams are dissolved in 1500 ml waters, get 100 gram (butt) NaY zeolites, join in the above-mentioned solution for preparing, stirred 30 minutes down, filter,, refilter with deionized water making beating washing in 20 ℃.
Then the gained zeolite is put into temperature and is 650 ℃ tube furnace hydrothermal calcine 2 hours under 100% water vapour atmosphere.
Get zeolite 40 grams after the above-mentioned roasting and ammonium sulfate 40 grams and join together in 600 ml distilled waters and stir, under agitation, filter and wash with water, then by exchanging three times with the quadrat method ammonium in 95 ℃ of ammoniums exchanges 2 hours.
Then the gained zeolite is put into temperature and is 650 ℃ tube furnace hydrothermal calcine 2 hours under 100% water vapour atmosphere.
Again the zeolite behind the above-mentioned re-baking 20 is restrained in the hydrochloric acid that joins 300 milliliters of 0.2N and stir, being warming up to 90 ℃ stirred 1 hour, filter, water making beating washing, refilter,, obtain high-Si Y-type molecular sieve of the present invention in 110 ℃ of dryings 2 hours, be designated as C, its physico-chemical property is listed in table 1 and the table 2.
Comparative Examples 1
Ammonium sulfate 50 grams are dissolved in 700 ml waters, get 50 gram (butt) NaY zeolites, join in the above-mentioned solution for preparing, under agitation, filter and wash with water, then by exchanging three times with the quadrat method ammonium in 95 ℃ of ammonium exchanges 2 hours.Dry.
Then the gained zeolite is put into temperature and is 650 ℃ tube furnace hydrothermal calcine 2 hours under 100% water vapour atmosphere.
Getting zeolite 40 grams after the above-mentioned roasting and ammonium sulfate 40 restrains to join together in 600 ml distilled waters and stirs, under agitation in 60 minutes time, add 30 milliliters of the hydrochloric acid of 0.1N then, filter water making beating washing, refilter, in 105 ℃ of dryings 3 hours.
Then the gained zeolite is put into temperature and is 650 ℃ tube furnace hydrothermal calcine 2 hours under 100% water vapour atmosphere.
Again the zeolite behind the above-mentioned re-baking 20 gram and ammonium sulfate 20 are restrained to join together in 300 ml distilled waters and stir, 40 milliliters of hydrochloric acid that under agitation in 60 minutes time, add 0.1N then, filter, water making beating washing, refilter, in 105 ℃ of dryings 3 hours, the high-Si Y-type molecular sieve that obtains was designated as D, and its physico-chemical property is listed in table 1 and the table 2.
Comparative Examples 2
With the NaY zeolite is raw material, is placed in the tube furnace, according to the 5 described method SiCl of the example among the Chinese patent CN1194941A
4Vapor phase process is handled molecular sieve, and the gained molecular sieve is designated as E, and its physico-chemical property is listed in table 1 and the table 2.
Embodiment 4
Ammonium sulfate 50 grams are dissolved in 1500 ml waters, get 100 gram (butt) ultrastable Y (Qilu Petrochemical company catalyst plant product, lattice constant a
0Be 24.53 , be designated as Y-A), join in the above-mentioned solution for preparing, stirred 30 minutes down in 20 ℃, filter, with deionized water making beating washing, refilter.
Then the gained zeolite is put into temperature and is 650 ℃ tube furnace hydrothermal calcine 2 hours under 50% water vapour atmosphere.
Again the zeolite after the above-mentioned roasting 20 gram is joined in the hydrochloric acid of 300 milliliters of 0.2N and stir, be warming up to 90 ℃ and stirred 1 hour, filter, water making beating washing refiltered, in 110 ℃ of dryings 2 hours, obtain high-Si Y-type molecular sieve of the present invention, be designated as F, its physico-chemical property is listed in table 1 and the table 2.
Comparative Examples 3
Ammonium sulfate 50 grams are dissolved in 700 ml waters, get 50 gram (butt) ultrastable Y (Qilu Petrochemical company catalyst plant product, lattice constant a
0Be 24.53 , be designated as Y-A), join in the above-mentioned solution for preparing, stir down in 90 ℃ and exchange 2 hours, filter, with deionized water making beating washing, refilter.
Then the gained zeolite is put into temperature and is 650 ℃ tube furnace hydrothermal calcine 2 hours under 50% water vapour atmosphere.
Again the zeolite after the above-mentioned roasting 20 gram is joined in the hydrochloric acid of 300 milliliters of 0.2N and stir, be warming up to 90 ℃ and stirred 1 hour, filter, water making beating washing refiltered, in 110 ℃ of dryings 2 hours, the gained zeolite is designated as G, and its physico-chemical property is listed in table 1 and the table 2.
Embodiment 5,
Ammonium sulfate 50 grams are dissolved in 1500 ml waters, get 100 gram (butt) NaY zeolites, join in the above-mentioned solution for preparing, stirred 30 minutes down, filter,, refilter, obtain the Y zeolite of selectivity ammonium exchange with deionized water making beating washing in 20 ℃.
Then the gained zeolite is put into temperature and is 650 ℃ tube furnace hydrothermal calcine 2 hours under 100% water vapour atmosphere.
Molecular sieve 40 gram of above-mentioned roasting and ammonium sulfate 40 restrained to join together in 600 ml distilled waters stir, under agitation in 60 minutes time, add 50 milliliters of the ammonium fluosilicate solutions of 1N then, filter water making beating washing, refilter, in 105 ℃ of dryings 3 hours.
Then the gained zeolite is put into temperature and is 650 ℃ tube furnace hydrothermal calcine 2 hours under 100% water vapour atmosphere.
Molecular sieve 30 gram of above-mentioned roasting is joined in the hydrochloric acid of 300 milliliters of 0.2N and stir, be warming up to 90 ℃ and stirred 1 hour, filter, water making beating washing refilters, and in 110 ℃ of dryings 2 hours, the gained zeolite was designated as H, and its physico-chemical property is listed in table 1 and the table 2.
Embodiment 6,
Ammonium sulfate 50 grams are dissolved in 1500 ml waters, get 100 gram (butt) NaY zeolites, join in the above-mentioned solution for preparing, stirred 30 minutes down, filter,, refilter, obtain the Y zeolite of selectivity ammonium exchange with deionized water making beating washing in 20 ℃.
Then the gained zeolite is put into temperature and is 600 ℃ tube furnace hydrothermal calcine 3 hours under 100% water vapour atmosphere.
Molecular sieve 40 gram of above-mentioned roasting and ammonium sulfate 40 restrained to join together in 600 ml distilled waters stir, 30 milliliters (wherein concentration of hydrochloric acid is 2N under agitation to add the mixing solutions of hydrochloric acid and EDTA then in 60 minutes time, EDTA concentration is 1N), filter, water making beating washing, refilter, in 105 ℃ of dryings 3 hours.
Then the gained zeolite is put into temperature and is 600 ℃ tube furnace hydrothermal calcine 3 hours under 100% water vapour atmosphere.
Molecular sieve 30 gram of above-mentioned roasting added and ammonium sulfate 20 restrains in the hydrochloric acid of 300 milliliters of 0.2N and stirs, be warming up to 90 ℃ and stirred 1 hour, filtration, water making beating washing refiltered, in 110 ℃ of dryings 2 hours, the gained zeolite is designated as I, and its physico-chemical property is listed in table 1 and the table 2.
The character of table 1, molecular sieve
| The molecular sieve numbering | Lattice constant (nanometer) | Degree of crystallinity % | ???Na 2O％ | |
| Embodiment 1 | ????A | ????2.437 | ????87.1 | ????0.094 |
| Embodiment 2 | ????B | ????2.435 | ????87.6 | ????0.033 |
| Embodiment 3 | ????C | ????2.434 | ????85.7 | ????0.032 |
| Comparative Examples 1 | ????D | ????2.433 | ????70.3 | ????0.04 |
| Comparative Examples 2 | ????E | ????2.437 | ????77.8 | ????0.35 |
| ????Y-A | ????2.453 | ????81.8 | ????1.1 | |
| Embodiment 4 | ????F | ????2.432 | ????78.1 | ????0.11 |
| Comparative Examples 3 | ????G | ????2.428 | ????58.4 | ????0.04 |
| Embodiment 5 | ????H | ????2.431 | ????85.1 | ????0.05 |
| Embodiment 6 | ????I | ????2.430 | ????81.4 | ????0.02 |
The pore structure of table 2, molecular sieve
| Molecular sieve | Total surface area SBET (m 2/g) | Micropore area (m 2/g) | Outer surface area (m 2/g) | Micropore pore volume (ml/g) | Total pore volume (ml/g) | Secondary pore pore volume (ml/g) |
| ???A | ?????677 | ????636 | ????41 | ???0.297 | ???0.451 | ????0.154 |
| ???B | ?????675 | ????630 | ????45 | ???0.293 | ???0.456 | ????0.163 |
| ???C | ?????653 | ????601 | ????52 | ???0.280 | ???0.441 | ????0.161 |
| ???D | ?????667 | ????634 | ????33 | ???0.296 | ???0.378 | ????0.082 |
| ???E | ?????598 | ????575 | ????23 | ???0.268 | ???0.307 | ????0.039 |
| ???Y-A | ?????658 | ????617 | ????42 | ???0.287 | ???0.361 | ????0.074 |
| ???F | ?????634 | ????568 | ????66 | ???0.272 | ???0.408 | ????0.136 |
| ???G | ?????566 | ????448 | ????118 | ???0.254 | ???0.389 | ????0.135 |
| ???H | ?????725 | ????649 | ????76 | ???0.303 | ???0.526 | ????0.223 |
| ???I | ?????694 | ????623 | ????71 | ???0.301 | ???0.510 | ????0.209 |
From table 1 and table 2 data as can be seen, at first adopt the exchange of selectivity ammonium to handle according to of the present invention, the further molecular sieve handled of super stabilizing can keep higher degree of crystallinity and specific surface area, and have bigger secondary pore pore volume then.
Claims (10)
1, a kind ofly prepare the method that lattice constant is the high-silicon Y-Zeolite of 2.420-2.440 nanometer, this method comprises carries out the exchange of one or many ammonium, hydrothermal treatment consists and/or chemical dealuminization with NaY zeolite or the y-type zeolite handled through super stabilizing; It is characterized in that in the exchange of said ammonium the ammonium exchange first time before hydrothermal treatment consists and/or chemical dealuminization at least be adopt temperature be room temperature to the cryogenic selective ammonium exchange that is lower than 60 ℃, remaining ammonium exchange step or for room temperature to being lower than 60 ℃ cryogenic selective ammonium exchange or being 60-90 ℃ conventional ammonium exchange.
2, according to the process of claim 1 wherein when being raw material with the NaY zeolite, said hydrothermal treatment consists and/or chemical dealuminization carry out secondary or more than the secondary; When being raw material with the y-type zeolite of handling through super stabilizing, said hydrothermal treatment consists and/or chemical dealuminization carry out one or many.
3, according to the method for claim 1, the step that the ammonium exchange is wherein optionally arranged after each hydrothermal treatment consists and/or chemical dealuminization step or between hydrothermal treatment consists and/or chemical dealuminization step is perhaps carried out the ammonium exchange when carrying out said chemical dealuminization; The ammonium of this moment exchanges or is said cryogenic selective ammonium exchange, perhaps is said conventional ammonium exchange.
4, according to the process of claim 1 wherein that the condition of said hydrothermal treatment consists is under 400-700 ℃ temperature and 20-100% water vapour atmosphere roasting 1-4 hour.
5, according to the method for claim 4, wherein the condition of said hydrothermal treatment consists is under 500-650 ℃ temperature and 40-100% water vapour atmosphere roasting 1-3 hour.
6, according to the process of claim 1 wherein said chemical dealuminization for adopt contain silicofluoric acid and/or ammonium silicofluoride as the liquid phase aluminium extracting and silicon supplementing method of reactant, adopt SiCl
4As the gas phase aluminium extracting and silicon supplementing method of reactant or adopt acid or complexing agent as the chemical dealuminization method of dealumination agent.
7, according to the method for claim 6, wherein said chemical dealuminization contains silicofluoric acid and/or the ammonium silicofluoride liquid phase aluminium extracting and silicon supplementing method as reactant for adopting.
8, according to the method for claim 6, wherein said chemical dealuminization is for adopting hydrochloric acid, sulfuric acid or the nitric acid chemical dealuminization method as dealumination agent.
9, according to the process of claim 1 wherein that the condition of said cryogenic selective ammonium exchange is to being lower than under 60 ℃ the temperature exchange 5 minutes to 1 hour in room temperature.
10, according to the method for claim 9.The condition of wherein said cryogenic selective ammonium exchange is to exchange 10-50 minute under 0-50 ℃ temperature.
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