CN1115298C - Y-type molecular sieve and its prepn. - Google Patents
Y-type molecular sieve and its prepn. Download PDFInfo
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- CN1115298C CN1115298C CN 00107414 CN00107414A CN1115298C CN 1115298 C CN1115298 C CN 1115298C CN 00107414 CN00107414 CN 00107414 CN 00107414 A CN00107414 A CN 00107414A CN 1115298 C CN1115298 C CN 1115298C
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Abstract
The present invention relates to a Y-shaped molecular sieve and a preparation method thereof. The Y-shaped molecular sieve is obtained through at least one step that the molecular sieve is treated for 0.5 to 4 hours in the ammonia gas atmosphere at a temperature between the room temperature and 650 DEG C, preferably a step that the molecular sieve is treated for 1 to 3 hours at 150 to 600 DEG C. The Y-shaped molecular sieve of the present invention is used during the ethylenzene preparation through transalkylation from benzene and polyethylene benzene, and has high transalkylation activity and high activity stability.
Description
The present invention relates to a kind of Y zeolite and preparation method thereof.
Y zeolite has the 3 D pore canal that the aperture is 7.3 , help macromole in molecular sieve pore passage diffusion and on acid sites, react, therefore be widely used in the reactions such as transalkylation of alkylation, benzene and the polyalkylbenzene of catalytic cracking, hydrocracking, hydrotreatment, benzene and alkene.The synthetic NaY molecular sieve SiO that obtains of hydro-thermal
2/ Al
2O
3Be generally about 4.5～5.5.The NaY molecular sieve does not have acidity, does not therefore have catalytic perfomance, and simultaneously because its framework silicon-aluminum is lower, so acid stable is very poor.Can not be directly with acid (H
+) exchange Na wherein
+Ion.Even with NaY type molecular sieve process NH
4 +Direct roasting preparation again after the salt exchange
HYMolecular sieve, its stability is also very poor, and this mainly causes owing to the framework of molecular sieve dealuminzation.Use NH
4 +Salt exchange NaY type molecular sieve, and then the method for roasting prepares HY type molecular sieve, NH
4 +Exchange degree generally can not surpass about 75%, otherwise can be because the roasting deamination causes the crystalline structure of molecular sieve to destroy.NH
4Y molecular sieve obtains the USY molecular sieve after handling through super stabilizing, and its thermostability significantly improves.The super stabilizing method of reporting in the document comprises the deep layer roasting method, methods such as high-temperature vapor processing.The super stabilizing process makes the framework dealumination of Y zeolite, and silicon is mended in the hole that dealuminzation is formed, and the framework si-al ratio of molecular sieve is improved, and the stability of molecular sieve comprises that therefore thermostability, hydrothermal stability, acid acceptance etc. improve.The framework dealumination of Y zeolite is mended the also available gas phase of silicon or liquid phase dealumination complement silicon method, i.e. silicon tetrachloride (SiCl
4) method, or the ammonium silicofluoride method.Because the silica bond distance is less than the alumina bond distance, therefore, when the skeleton of molecular sieve carried out dealumination complement silicon, the lattice constant of Y zeolite can dwindle.Therefore the variation of the lattice constant of Y zeolite can be used for describing the degree that its framework dealumination is mended silicon.
U.S. Pat P3,293,192; 3,354,077; 3,449,070; 3,493,519; Reported in 3,641,177 and 3,929,672 and adopted methods such as high-temperature roasting, water vapour pyroprocessing to prepare the USY molecular sieve of good thermal stability.
At USP3, in 929,672, the process of preparation USY molecular sieve is that the NaY molecular sieve is obtained NH through the ammonium exchange
4NaY is again with this NH of steam-treated
4NaY obtains USY, again through NH
4 +Exchange reduces its Na
2O content obtains the USY zeolite product, and this method for preparing the USY molecular sieve is exactly traditional hydrothermal calcine method.
The purpose of this invention is to provide a kind of Y molecular sieve and preparation method thereof, this Y molecular sieve has better activity and activity stability when the transalkylation reaction that is used for some specific reaction such as benzene and polyalkylbenzene, hydrocracking reaction etc.
Y zeolite provided by the invention is characterized in that said Y zeolite handled 0.5～4 hour in room temperature～650 ℃ under ammonia atmosphere by at least one step, handles 1～3 hour step and obtains for preferred 150～600 ℃.
Y zeolite provided by the invention, its feature is that also a desorption peaks only appears in said Y zeolite in its temperature programmed desorption(TPD) curve after ammonia atmosphere is handled about 110 ℃, and conventional Y zeolite occurs NH also occurring the desorption peaks after 150 ℃ after ammonium ion exchange except that about 110 ℃ in the prior art
3Desorption peaks.
Its relative crystallinity of Y zeolite provided by the invention is more than 70%, and is preferred more than 75% (with respect to NaY molecular sieve raw material); Its Na
2O content is generally less than 1.0%, preferably less than 0.5%, is more preferably less than 0.3%; The lattice constant of molecular sieve is 2.465～2.435 nanometers, is preferably 2.460～2.445 nanometers; The specific surface area that records with the BET method is generally greater than 500M
2/ g.
Said ammonia atmosphere is meant that the percent by volume of ammonia is at least 1% in the atmosphere in the Y zeolite provided by the invention, preferably be at least 5%, more preferably be at least 10% atmosphere, this atmosphere can be pure ammonia atmosphere, also can be the atmosphere that contains air, nitrogen and/or water vapour or other gas, wherein preferably contain the atmosphere of the ammonia of water vapour and/or air and at least 1 volume %.Said ammonia atmosphere can be the atmosphere that mobile contains ammonia, also can be the atmosphere that contains ammonia of static sealing, the wherein preferably static atmosphere that contains ammonia of sealing.
The method that another kind of ammonia atmosphere is handled among the present invention is that molecular sieve is soaked with ammonia soln earlier, the pH value general requirement of soaking is greater than 9.0, be preferably more than 9.5, filtering drying then, also can be without filtering directly oven dry, then the molecular sieve that obtains is carried out above-mentioned ammonia atmosphere and handle, the effect that is obtained is better.
The step acquisition that Y zeolite provided by the invention is handled by containing said ammonia atmosphere of acid treatment and at least one step; Said acid-treated method is the conventional method that adopts in the prior art, the present invention has no particular limits it, for example, used acid can be mineral acids such as sulfuric acid, hydrochloric acid, nitric acid, silicofluoric acid, organic acids such as also available acetic acid, citric acid, acid-treated pH value is generally between 1.5～4.5, and is preferred 2.0～4.0, and more preferably 2.0～3.5; The used temperature of acid treatment is a room temperature to 100 ℃, and preferred 50～98 ℃, more preferably 60～95 ℃, the acid-treated time is 0.5～4 hour, generally filters after the acid treatment, washes to remove remaining acid and acid ion.
In implementation process of the present invention, when the preparation Y zeolite, except can carrying out ammonium exchange and acid treatment respectively, also can be with NH
4 +Ion-exchange and said acid treatment are carried out together.Be about to Y zeolite and use NH simultaneously
4 +Salt and acid are handled.Described ammonium is exchanged for the conventional steps that this area prepares Y zeolite, and the present invention has no particular limits it; The NH that uses of clearing house for example
4 +Salt can be ammonium sulfate, ammonium nitrate or ammonium chloride and ammonium acetate etc., and give-and-take conditions are room temperature～100 ℃ processing 0.5～4 hour, and described exchange generally also comprises filtration, washes and remove remaining salt or anionic step.
The preparation method of described Y zeolite provided by the invention can contain the following step:
(1) the NaY molecular sieve is exchanged with ammonium salt, make the ammonium ion exchange degree reach 50～85%, then with its water vapour or contain water vapour and/or the atmosphere of ammonia under carry out roasting, maturing temperature is 450～700 ℃, the lattice constant of molecular sieve is 2.445～2.465 nanometers after the roasting;
(2) with ammonium salt exchange, acid treatment or the two bonded method the molecular sieve that step (1) obtains is handled, made the Na of molecular sieve
2O content is reduced to less than 1.0 weight %, preferably less than 0.5 weight %, is more preferably less than 0.3 weight %; This ammonium exchange, acid treatment or the two bonded step can be carried out one or many;
(3) under the described in front ammonia atmosphere condition step (2) gained molecular sieve is handled, the temperature of processing is a room temperature to 650 ℃, and preferred temperature is 150～600 ℃, and the time of processing is 0.5～4 hour, preferred 1～3 hour;
The USY molecular sieve of steam treatment or deep layer roasting method preparation in the prior art, its preparation method is through NH with NaY
4 +Exchanging to exchange degree is 50～98%, and in the presence of still air or water vapour, through 550 ℃～850 ℃ roastings 2～4 hours, the lattice constant of the USY molecular sieve that obtains was about 2.435～2.460 nanometers then; The inventor thinks, if when roasting NH
4The deamination speed of Y molecular sieve is too fast, can cause the destruction in various degree of molecular sieve structure, and its degree of crystallinity is descended.And characteristics of the present invention are, in order to obtain the USY molecular sieve of higher crystallinity, keep ammonia atmosphere more than the 1.0 volume % at least from being warmed up to constant temperature system.Under condition of the present invention, the degree of crystallinity of gained USY molecular sieve is generally at (with respect to the NaY molecular sieve) more than 75%.The roasting of this ammonia atmosphere has not only improved the stability of molecular sieve, also makes the Na in the hexagonal prism cage and β cage in the molecular sieve simultaneously
+Ion moves in supercage, and this helps remaining Na in the molecular sieve
+The ionic exchange is removed.
Another characteristics of the present invention are with the USY molecular sieve NH through handling under water vapour and the ammonia condition
4 +Salt brine solution continues exchange and/or handles with acid solution, and acid-treated condition is relatively gentleer, generally controls it and can remove the aluminium on the non-skeleton of molecular sieve and do not remove aluminium on the skeleton, be i.e. the structure of saboteur's sieve not; Through after this a series of processing, the degree of crystallinity of molecular sieve generally remains on (with respect to the NaY molecular sieve) more than 75%; Its Na
2O content is generally less than 0.5%, preferably less than 0.3%, is more preferably less than 0.2%; The lattice constant of molecular sieve is 2.465～2.435 nanometers, is preferably 2.450～2.445 nanometers; The specific surface area that records with the BET method is generally greater than 500M
2/ g.
Through after the above-mentioned acid and ammonia treatment, obvious variation has taken place in the physico-chemical property of molecular sieve of the present invention.Wherein, the TG curve that records with thermogravimetric method (temperature programmed desorption(TPD) method) shows that before acid treatment and ammonia atmosphere processing, the temperature programmed desorption(TPD) curve of ammonium exchange molecular sieve occurs two owing to NH
3The weightless peak of desorption.After peracid treatment and ammonia atmosphere processing, a desorption peaks only appears in the temperature programmed desorption(TPD) curve, and 200～300 ℃ former weightless peak disappears.This explanation ammonia atmosphere is handled and is made acid sites that noticeable change take place.
The most outstanding advantage of Y zeolite provided by the invention is that reactive behavior improves when carrying out the activity of such catalysts constituent element of transalkylation reaction as benzene and many ethylbenzene, and activity stability obviously improves (seeing embodiment 7,8,9).But its range of application is not limited to the catalyzer of benzene and many ethylbenzene transalkylation reaction, also can be used for the alkylation of catalytic cracking, hydrocracking, hydrotreatment, benzene and alkene and the reaction process such as transalkylation of benzene and polyalkylbenzene.
Fig. 1 is the temperature programmed desorption(TPD) curve of embodiment 4 gained sieve sample USY-E, and Fig. 2 is the temperature programmed desorption(TPD) curve of Comparative Examples 1 gained sieve sample USY-C, and the temperature rise rate of its temperature programmed desorption(TPD) is 10 ℃/minute (still air atmosphere).
The following examples are used to illustrate in greater detail the present invention, but scope of the present invention is not only limited to these
The scope of embodiment.
Embodiment 1
(Ba Ling petro-chemical corporation Chang Ling catalyst plant is produced, SiO to take by weighing 100g NaY molecular sieve
2/ Al
2O
3Mol ratio is 5.0), add 1500g deionized water and 100g ammonium nitrate,, filter after 1 hour 95 ℃ of exchanges; Repeated exchanged once after, filter washing, and 110 ℃ of oven dry down.With the NH that obtains thus
4NaY molecular sieve compressing tablet is broken for 10～20 purpose particles, gets the part particle and packs in the stainless steel reaction pipe of Φ 50mm, be warming up to 350 ℃ after, feed water vapour, the weight space velocity of water vapour is 3 hours
-1, continue to be warming up to 560 ℃ after constant temperature 3 hours.Stop into water steam then, cooling.
Gained USY molecular sieve is analyzed through X-ray diffraction (XRD) and X fluorescence spectrum (XRF), and recording its lattice constant is 2.457 nanometers, and relative crystallinity (is benchmark with the NaY raw material) is 79%, Na
2O content is 2.8%.
Take by weighing above-mentioned USY molecular sieve 50g, add deionized water 750g, add ammonium nitrate 50g, stir exchange 2 hours down, filter at 95 ℃; Exchange again once with same condition, filter.Filter cake is added the 600g deionized water, and making beating stirs evenly, and adds aqueous nitric acid, makes the pH value of slurries transfer to 2.5, temperature is risen to 70 ℃ then, and constant temperature stirred 1 hour; Repeat the acid treatment condition, up to the Na that makes molecular sieve
2O content is less than 0.2%, filters, and is washed to neutrality, with filter cake 120 ℃ of oven dry.
With above-mentioned sieve sample compression molding and be broken for 20～40 purpose particles, take by weighing the 30g sample and pack in the stainless steel reactor of Φ 25mm, put into alumina ball below the sample, and separate with stainless (steel) wire and sieve particle.Under the ammonia flow that feeds the 150ml/ branch, heat temperature raising, heat-up rate is 120 ℃/hour, rises to 540 ℃, and constant temperature is after 1 hour, close the ammonia inlet valve and stop air inlet, close outlet valve simultaneously, constant temperature was cooled to room temperature after 1 hour again, took out molecular sieve, the gained molecular sieve is designated as USY-A, and recording its lattice constant is 2.456 nanometers.
Embodiment 2
Take by weighing the USY-A molecular sieve 21g (dry basis) of embodiment 1 preparation, add pseudo-boehmite (production of Chang Ling catalyst plant) 9g (dry basis), mix the back and add an amount of aqueous nitric acid kneading and compacting, trifolium orifice plate extruded moulding with Φ 1.5 is a catalyzer again, with this catalyzer 120 ℃ of oven dry, after 4 hours, be cooled to room temperature through 550 ℃ of roastings.The catalyzer that obtains is designated as Cat-1.
Embodiment 3
Get the USY molecular sieve of 50g embodiment 1 preparation, add the 750g deionized water, add ammonium nitrate 50g again, under 95 ℃ of conditions, stir exchange 2 hours, filter; With filter cake repeated exchanged under same condition, until Na
2O content＜0.2%.Filter washing, 120 ℃ of oven dry.
The molecular sieve that obtains is carried out ammonia atmosphere according to the condition of embodiment 1 handle, but treatment condition are 500 ℃ of constant temperature 1 hour.The molecular sieve that obtains after the cooling is designated as USY-B, and recording its lattice constant is 2.455 nanometers.
Take by weighing USY-B molecular sieve 21g (dry basis), add pseudo-boehmite 9g (dry basis), according to the method extruded moulding of embodiment 2, oven dry, roasting, the catalyzer of making is designated as Cat-2.
Comparative Examples 1
Get the USY molecular sieve of 50g embodiment 1 preparation, add the 750g deionized water, add ammonium nitrate 50g again, under 95 ℃ of conditions, stir exchange 2 hours, filter; With filter cake repeated exchanged under same condition, until Na
2O content＜0.2%.After molecular sieve filtration, washing, oven dry, be designated as USY-C, recording its lattice constant is 2.457 nanometers.
With the method for USY-C according to embodiment 2, extruded moulding is prepared into catalyzer, and note is made Cat-3.
Comparative Examples 2
With the 30g compression molding is that USY-C molecular sieve behind the particle is put into the stainless steel reaction pipe, divides N at 150ml/
2Be warming up to 550 ℃ under the air-flow, and constant temperature 3 hours, the molecular sieve that obtains note is made USY-D, and recording its lattice constant is 2.456 nanometers.
USY-D is prepared into catalyzer according to the method extruded moulding of embodiment 2, and note is made Cat-4.
Embodiment 4
(Ba Ling petro-chemical corporation Chang Ling catalyst plant is produced, SiO to take by weighing 10g NaY molecular sieve
2/ Al
2O
3Mol ratio is 5.0), add 150g deionized water and 10g ammonium nitrate,, filter after 1 hour 95 ℃ of exchanges; Repeated exchanged once after, filter washing, and 110 ℃ of oven dry down.With the NH that obtains thus
4NaY molecular sieve compressing tablet is broken for 10～20 purpose particles, gets the part particle and packs in the stainless steel reaction pipe of Φ 50mm, be warming up to 350 ℃ after, feed water vapour and ammonia, the weight space velocity of water vapour is 3 hours
-1, the volume fraction of ammonia is 20%, continue to be warming up to 560 ℃ after constant temperature 3 hours.Stop into water steam and ammonia then, cooling.
Gained USY molecular sieve is analyzed through X-ray diffraction (XRD) and X fluorescence spectrum (XRF), and recording its lattice constant is 2.458 nanometers, and relative crystallinity (is benchmark with the NaY raw material) is 81%, Na
2O content is 2.6%.
Take by weighing above-mentioned USY molecular sieve 50g, add deionized water 750g, add ammonium nitrate 50g, stir exchange 2 hours down, filter at 95 ℃; Exchange again once with same condition, filter.Filter cake is added the 600g deionized water, add aqueous nitric acid and make the pH value transfer to 3.After it is warming up to 60 ℃, slowly add silicofluoric acid (20 weight %) aqueous solution 8ml, add back constant temperature and continue to stir 2 hours.Filter, the processing above repeating is until the Na of molecular sieve
2O content＜0.2%.Filter, be washed to no fluorion.Then the gained molecular sieve is carried out ammonia atmosphere according to the condition among the embodiment 1 and handle, treatment condition are room temperature constant temperature 4 hours, take out sieve sample.Gained molecular sieve note is made USY-E, and recording its lattice constant is 2.445 nanometers.
According to the method for embodiment 2 with the molecular sieve extruded moulding, oven dry, roasting is prepared into catalyzer, this catalyzer note is made Cat-5.
Embodiment 5
Take by weighing the USY molecular sieve 50g of embodiment 1 preparation, add deionization 750g, add ammonium nitrate 50g, stir exchange 2 hours down, filter at 95 ℃; Exchange again once with same condition, filter.It is even that filter cake is added the 750g deionized water for stirring, adds aqueous acetic acid and make pH transfer to 3.2, it is warming up to 80 ℃ after, constant temperature continues to stir 2 hours, filters; Ammonium exchange and acid treatment step above repeating are until the Na of molecular sieve
2O content＜0.2%.Filter washing, oven dry.With above-mentioned sieve sample compression molding and be broken for 20～40 purpose particles, take by weighing the 30g sample and pack in the stainless steel reactor of Φ 25mm, put into alumina ball below the sample, and separate with stainless (steel) wire and sieve particle.Under the mixed airflow of nitrogen that feeds the 150ml/ branch and ammonia (wherein the flow velocity of ammonia is about the 30ml/ branch), heat temperature raising, heat-up rate is 120 ℃/hour, rise to 300 ℃ of constant temperature after 1 hour, close the ammonia inlet valve and stop air inlet, close outlet valve simultaneously, constant temperature was cooled to room temperature after 1 hour again, take out molecular sieve, note is made USY-F, and recording its lattice constant is 2.455 nanometers.
According to the method for embodiment 2, with USY-F molecular sieve extruded moulding, oven dry, roasting is prepared into catalyzer, and note is made Cat-6.
Embodiment 6
Take by weighing the USY molecular sieve 50g of embodiment 1 preparation, add deionized water 750g, add ammonium nitrate 50g, stir exchange 2 hours down, filter at 95 ℃; Exchange again once with same condition, filter.Filter cake is added the 600g deionized water, and making beating stirs evenly, and adds aqueous nitric acid, and the pH value of slurries is transferred to about 2.5, temperature is risen to 70 ℃ then, and constant temperature stirred 1 hour; Repeat the acid treatment condition, up to the Na that makes molecular sieve
2O content filters less than 0.2%; Filter cake is added the 600g deionized water, add 4.0g La (NO
3)
36H
2O, the exchange temperature is 95 ℃, and constant temperature 2 hours, after the filtration, washing, oven dry.Carry out ammonia atmosphere according to the condition in the example 2 and handle, treatment temp is 500 ℃ of constant temperature 1 hour, reduce to room temperature after, take out sieve sample, note is made USY-G.
Take by weighing USY-G molecular sieve 15g (dry basis), add pseudo-boehmite 15g (dry basis), according to the method extruded moulding of embodiment 2, oven dry, roasting, the catalyzer of making is designated as Cat-7.
Comparative Examples 3
Get beta-molecular sieve 50g, add deionized water 750g, add ammonium nitrate 50g again, stir exchange 1 hour down at 95 ℃, repeated exchanged makes Na
2O content reduces to＜and 0.2%.
According to the method for embodiment 2, with the molecular sieve extruded moulding, oven dry, roasting is prepared into catalyzer, and note is made Cat-8.
Embodiment 7
Present embodiment explanation catalyzer of the present invention and comparative catalyst are used for the initial activity evaluation of benzene and many ethylbenzene liquid phase transalkylation reaction.
The catalyst breakage of above-mentioned preparation is become 16～20 purpose particles, pack in the stainless steel reactor of Φ 12.5mm, it is 7 transalkylation reaction material that analytically pure benzene and many ethylbenzene (containing ethylbenzene 3.0%, diethylbenzene 87.5, triethyl-benzene 7.0%) are mixed with benzene/ethyl branch mol ratio.With catalyzer 120 ℃ with nitrogen purging after, enter the transalkylation reaction material continuously with fresh feed pump.The liquid volume air speed of charging is 3 hours
-1, system rises to 230 ℃ with 50 ℃/hour temperature rise rate.Reaction pressure 3.5MPa, the gained evaluation result is listed in the table 1, and transformation efficiency wherein and selectivity are respectively at go forward side by side average result behind the circumstances in which people get things ready for a trip spectrum analysis of beginning charging play 16 hours, 24 hours, 42 hours time sampling.
Table 1
| Catalyzer | Diethylbenzene transformation efficiency % | Triethyl-benzene transformation efficiency % | Ethylbenzene selectivity % |
| Cat-1 | 84.0 | 59.6 | 99.3 |
| Cat-2 | 82.5 | 60.2 | 99.5 |
| Cat-5 | 85.4 | 61.5 | 99.2 |
| Cat-6 | 79.5 | 58.6 | 98.7 |
| Cat-7 | 78.9 | 57.2 | 99.0 |
| Cat-3 | 73.5 | 52.3 | 98.2 |
| Cat-4 | 72.6 | 50.5 | 98.5 |
| Cat-8 | 45.2 | 30.5 | 98.5 |
By table 1 result as seen, molecular sieve is through after the processing of the present invention, and the transformation efficiency of diethylbenzene and triethyl-benzene obviously improves, and ethylbenzene selectivity also increases to some extent.
Embodiment 8
Present embodiment explanation catalyzer of the present invention and comparative catalyst are used for the activity stability evaluation of benzene and many ethylbenzene liquid phase transalkylation reaction.
The catalyst breakage of above-mentioned preparation is become 8 milliliters of 16～20 purpose particles, pack in the stainless steel reactor of Φ 12.5mm, it is 8 transalkylation reaction material that analytically pure benzene and many ethylbenzene (containing ethylbenzene 3.0%, diethylbenzene 87.5, triethyl-benzene 7.0%) are mixed with benzene/ethyl branch mol ratio.With catalyzer 120 ℃ with nitrogen purging after, enter the transalkylation reaction material with fresh feed pump.The liquid volume air speed of charging is 3 hours
-1, system rises to 190 ℃ with 50 ℃/hour temperature rise rate.Reaction pressure 3.0MPa keeps 75% with the diethylbenzene transformation efficiency, and 1500 hours needed temperature of reaction of catalyst runs compare activity of such catalysts stability, and the gained evaluation result is listed in the table 2.
Table 2
| Catalyzer | Final reaction temperature ℃ |
| Cat-1 | 215 |
| Cat-2 | 218 |
| Cat-5 | 215 |
| Cat-6 | 218 |
| Cat-7 | 220 |
| Cat-3 | 235 |
| Cat-4 | 238 |
| Cat-8 | 250 |
By table 2 result as seen, after molecular sieve processing of the present invention, activity of such catalysts stability obviously improves.
Embodiment 9
Present embodiment explanation catalyzer of the present invention and comparative catalyst are used for the initial activity evaluation of benzene and diisopropylbenzene(DIPB) liquid phase transalkylation reaction.
The catalyst breakage of above-mentioned preparation is become 16～20 purpose particles, pack in the stainless steel reactor of Φ 12.5mm, analytically pure benzene and diisopropylbenzene(DIPB) (are contained isopropyl benzene 3.0%, diisopropylbenzene(DIPB) 95.5, tri-isopropyl benzene 5.0%) mol ratio that is mixed with benzene/sec.-propyl side chain is 7 transalkylation reaction material.With catalyzer 120 ℃ with nitrogen purging after, enter the transalkylation reaction material with fresh feed pump.The liquid volume air speed of charging is 3 hours
-1, system rises to 200 ℃ with 50 ℃/hour temperature rise rate.Reaction pressure 3.0MPa, the gained evaluation result is listed in the table 3, and transformation efficiency wherein and selectivity are respectively at go forward side by side average result behind the circumstances in which people get things ready for a trip spectrum analysis of beginning charging play 16 hours, 24 hours, 42 hours time sampling.。
Table 3
| Catalyzer | Diisopropylbenzene(DIPB) transformation efficiency % | Isopropyl benzene selectivity % |
| Cat-5 | 79.2 | 99.2 |
| Cat-3 | 70.8 | 99.5 |
By table 3 result as seen, molecular sieve is through after the processing of the present invention, and the transformation efficiency of diisopropylbenzene(DIPB) obviously improves.
Claims (17)
1, a kind of Y zeolite is characterized in that a ℃ step of handling 0.5～4 hour obtains said Y zeolite in room temperature～650 under ammonia atmosphere by at least one step.
2, according to the molecular sieve of claim 1, its feature also is only to occur in the temperature programmed desorption(TPD) curve of said Y zeolite after ammonia atmosphere is handled a NH about 110 ℃
3Desorption peaks.
3, according to the molecular sieve of claim 1, its relative crystallinity with respect to NaY molecular sieve raw material of wherein said Y zeolite is more than 70%; Its Na
2O content is less than 1.0 weight %; Its lattice constant is 2.465～2.435 nanometers.
4, according to the molecular sieve of claim 3, its relative crystallinity with respect to NaY molecular sieve raw material of wherein said Y zeolite is more than 75%; Its Na
2O content is less than 0.5 weight %; Its lattice constant is 2.460～2.445 nanometers.
5, according to the molecular sieve of claim 4, the Na of said Y zeolite wherein
2O content is less than 0.3 weight %.
6,, it is characterized in that said Y zeolite obtained in 150～600 ℃ of steps of handling 1～3 hour under ammonia atmosphere by at least one step according to the molecular sieve of claim 1.
7, according to the molecular sieve of claim 1 or 6, wherein said ammonia atmosphere is pure ammonia atmosphere or the atmosphere that contains air, nitrogen and/or water vapour, and wherein the percent by volume of ammonia is at least 1%.
8, according to the molecular sieve of claim 7, the percent by volume of ammonia is at least 5% in the wherein said ammonia atmosphere.
9, according to the molecular sieve of claim 8, the percent by volume of ammonia is at least 10% in the wherein said ammonia atmosphere.
10, according to the molecular sieve of claim 1, wherein said ammonia atmosphere is the atmosphere that mobile contains ammonia, or the atmosphere that contains ammonia of static sealing.
11, according to the molecular sieve of claim 1, the step acquisition that wherein said Y zeolite is handled by containing said ammonia atmosphere of acid treatment and at least one step; Said acid-treated pH value is 1.5～4.5; Acid-treated temperature is a room temperature to 100 ℃; The acid-treated time is 0.5～4 hour.
12, according to the molecular sieve of claim 11, the used acid of wherein said acid treatment is the mineral acid that is selected from sulfuric acid, hydrochloric acid, nitric acid or silicofluoric acid, perhaps for being selected from the organic acid of acetic acid or citric acid; Said acid-treated pH value is 2.0～4.0; Said acid-treated temperature is 50～98 ℃.
13,, wherein also comprise the step of carrying out the ammonium exchange with ammonium salt solution in the preparation of said Y zeolite according to the molecular sieve of claim 1.
14, according to the molecular sieve of claim 13, wherein said ammonium exchange and said acid treatment are carried out simultaneously.
15, the preparation method of the described molecular sieve of claim 1 is characterized in that this method contains the following step:
(1) the NaY molecular sieve is exchanged with ammonium salt, make the ammonium ion exchange degree reach 50～85%, then with its water vapour or contain water vapour and/or the atmosphere of ammonia under carry out roasting, maturing temperature is 450～700 ℃, the lattice constant of gained molecular sieve is 2.445～2.465 nanometers after the roasting;
(2) with ammonium salt exchange, acid treatment or the two bonded method the molecular sieve that step (1) obtains is handled, made the Na of molecular sieve
2O content is reduced to less than 1.0 weight %;
(3) under the ammonia atmosphere condition step (2) gained molecular sieve is handled, the temperature of processing is a room temperature to 650 ℃, and the time of processing is 0.5～4 hour;
16, according to the method for claim 15, the Na of the described molecular sieve of step (2) wherein
2O content is reduced to less than 0.5 weight %.
17, according to the method for claim 15, wherein the temperature of the described ammonia atmosphere processing of step (3) is 150～600 ℃.
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|---|---|---|---|
| CN 00107414 CN1115298C (en) | 2000-05-12 | 2000-05-12 | Y-type molecular sieve and its prepn. |
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| CN 00107414 CN1115298C (en) | 2000-05-12 | 2000-05-12 | Y-type molecular sieve and its prepn. |
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| Publication Number | Publication Date |
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| CN1323739A CN1323739A (en) | 2001-11-28 |
| CN1115298C true CN1115298C (en) | 2003-07-23 |
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| CN 00107414 Expired - Lifetime CN1115298C (en) | 2000-05-12 | 2000-05-12 | Y-type molecular sieve and its prepn. |
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Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101623649B (en) * | 2008-07-08 | 2011-08-17 | 中国石油化工股份有限公司 | Alkaline molecular sieve catalyst for preparing styrene |
| CN102765732A (en) * | 2011-05-06 | 2012-11-07 | 天津神能科技有限公司 | Preparation method of Y with high silica-alumina ratio |
| CN102557070B (en) * | 2012-03-07 | 2013-08-28 | 华东师范大学 | Method for exchanging to eliminate sodium by using organic carboxylic acid in process of preparing Y type molecular sieve |
| CN103359760A (en) * | 2012-04-06 | 2013-10-23 | 华东理工大学 | Method for removing sodium from sodium zeolite molecular sieve through ion exchange |
| CN107583667B (en) * | 2016-07-08 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket |
| CN107583670B (en) * | 2016-07-08 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking and preparation method thereof improving octane number bucket |
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| CN107970974B (en) * | 2016-10-21 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
| CN107973310B (en) * | 2016-10-21 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of Y molecular sieve and preparation method thereof containing rare earth |
| CN107970972B (en) * | 2016-10-21 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
| CN107970973B (en) * | 2016-10-21 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of catalytic cracking catalyst and preparation method thereof |
| CN106669776A (en) * | 2017-01-05 | 2017-05-17 | 兰州理工大学 | Preparation method of toluene alkylation catalyst prepared from benzene |
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2000
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