CN102049321B - Molecular sieve ion exchange method and method for preparing rare earth Y-type molecular sieve - Google Patents
Molecular sieve ion exchange method and method for preparing rare earth Y-type molecular sieve Download PDFInfo
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- CN102049321B CN102049321B CN2009102366191A CN200910236619A CN102049321B CN 102049321 B CN102049321 B CN 102049321B CN 2009102366191 A CN2009102366191 A CN 2009102366191A CN 200910236619 A CN200910236619 A CN 200910236619A CN 102049321 B CN102049321 B CN 102049321B
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Abstract
The invention discloses a molecular sieve ion exchange method. In the molecular sieve ion exchange, ion exchange reaction equipment is adopted; the equipment comprises an exchange device which comprises a container and a partition plate, wherein the container is divided into a first space and a second space by the partition plate; the volume of the first space is greater than the volume of the second space; a gap is formed between the lower end of the partition plate and the bottom of the container; the first space is communicated with the second space through the gap; the side wall of the container is provided with an opening which is communicated with the second space; and the lower edge of the opening is higher than the lower end of the partition plate and lower than the upper end of the partition plate. The invention also provides a method for preparing a rare earth Y-type molecular sieve by using the equipment. Since the ion exchange reaction equipment can continuously perform ion exchange, the molecular sieve ion exchange method and the method for preparing the rare earth Y-type molecular sieve can be continuously performed to greatly reduce labor intensity during production.
Description
Technical field
The present invention relates to a kind of method of molecular sieve ion-exchange and the preparation method of rare earth Y type molecular sieve.
Background technology
The method of existing molecular sieve ion-exchange mainly contains two kinds, and a kind of is to adopt pot type batch exchange technique, and another kind is the continuous exchange process that carries out at the continuous band filter.When adopting the continuous band filter to carry out molecular sieve ion-exchange, because complicated operation, production process parameters control is strict, and equipment cost is high, therefore, has limited the promotion and application of continuous band filter in the molecular sieve ion exchange process.Therefore, the method of existing molecular sieve ion-exchange is mainly carried out in retort, yet step course of reaction is usually adopted in the ion-exchange of carrying out in retort, the normally in certain sequence batch charging in stirred autoclave of this technique, carries out stage by stage.Production automation degree is low, and labour intensity is large, and production can't be continuous, exchanges each working procedure parameter control and relies on artificial monitoring and control fully, and control deviation is larger.On the other hand, the batch exchange reaction is because unit volume reactor disposal ability is little, want to improve production capacity, only have the volume that strengthens reactor or increase the reactor number, so not only increased the power of motor of reactor, cause energy consumption to increase, restricted by production site.Simultaneously the further lifting of Quality and yield there is larger restriction.
Summary of the invention
The objective of the invention is in order to overcome the defects of existing molecular sieve ion-exchange process, a kind of method of new molecular sieve ion-exchange is provided, adopt the method can realize at an easy rate carrying out continuously the molecular sieve ion-exchange reactions.
Another object of the present invention provides a kind of new method for preparing rare earth Y type molecular sieve.
The invention provides a kind of method of molecular sieve ion-exchange, wherein, a kind of ion-exchange reactions equipment is adopted in molecular sieve ion-exchange, this equipment comprises switch, described switch comprises container and dividing plate, described dividing plate is divided into the first space and second space with described container, and the volume in described the first space is greater than the volume of described second space; The lower end of described dividing plate and the bottom of described container have the space, and described the first space and described second space are communicated with by described space; Be provided with opening on the sidewall of described container, described opening is communicated with described second space, and the lower edge of described opening is higher than the lower end of described dividing plate and is lower than the upper end of described dividing plate; The method comprises a kind of slurries are joined in described the first space continuously mixes contact, described slurries contain molecular sieve and exchange liquid, perhaps molecular sieve and exchange liquid are joined respectively in described the first space continuously, molecular sieve is mixed with exchange liquid contact, the slurries that mix after contacting are flowed out continuously by opening.
The present invention also provides a kind of preparation method of rare earth Y type molecular sieve, the method comprises makes non-rare earth Y type molecular sieve contact with exchange liquid, carry out ion-exchange, wherein, a kind of ion-exchange reactions equipment is adopted in described ion-exchange, and this equipment comprises switch, and described switch comprises container and dividing plate, described dividing plate is divided into the first space and second space with described container, and the volume in described the first space is greater than the volume of described second space; The lower end of described dividing plate and the bottom of described container have the space, and described the first space and described second space are communicated with by described space; Be provided with opening on the sidewall of described container, described opening is communicated with described second space, and the lower edge of described opening is higher than the lower end of described dividing plate and is lower than the upper end of described dividing plate; Described non-rare earth Y type molecular sieve and described exchange liquid are added to mix in described the first space to contact, the slurries that mix after the contact are flowed out continuously by opening.
The present inventor finds by research, by dividing plate is set in switch, and the sidewall at described switch arranges opening, form the polyrrhea groove that volume is less, thereby not only can realize continuous feeding and discharging, and can prolong the time of staying of reactant feed in switch, and then guarantee that reactant feed is by can fully reacting in the process of described switch.Therefore, the method for described molecular sieve ion-exchange provided by the invention can realize continous way production, is specially adapted to the ion-exchange reactions process of Y zeolite.
Description of drawings
Fig. 1 represents the structural representation of ion-exchange reactions equipment of the present invention;
Fig. 2 represents the structural representation of the preferred embodiment of ion-exchange reactions equipment of the present invention;
Fig. 3 represents the structural representation of the preferred embodiment of ion-exchange reactions equipment of the present invention;
Fig. 4 represents the structural formula intention of the further preferred embodiment of ion-exchange reactions equipment of the present invention;
Fig. 5 represents the structural representation of the most preferred embodiment of ion-exchange reactions equipment of the present invention.
The specific embodiment
The present invention also provides a kind of method of molecular sieve ion-exchange, wherein, ion-exchange reactions equipment is as shown in Figure 1 adopted in molecular sieve ion-exchange, this equipment comprises switch, described switch comprises container 1 and dividing plate 11, described dividing plate 11 is divided into the first space 12 and second space 13 with described container 1, and the volume in described the first space 12 is greater than the volume of described second space 13; The bottom of the lower end of described dividing plate 11 and described container 1 has the space, and described the first space 12 and described second space 13 are communicated with by described space; Be provided with opening 14 on the sidewall of described container 1, described opening 14 is communicated with described second space 13, and the lower edge of described opening 14 is higher than the lower end of described dividing plate 11 and is lower than the upper end of described dividing plate 11; The method comprises a kind of slurries are joined in described the first space 12 continuously mixes contact, described slurries contain molecular sieve and exchange liquid, perhaps molecular sieve and exchange liquid are joined respectively in described the first space 12 continuously, molecular sieve is mixed with exchange liquid contact, the slurries that mix after contacting are flowed out continuously by opening 14.
In described ion-exchange reactions equipment, described switch can for the conventional various reactors that use in this area, be preferably retort.In described switch, there is no particular limitation for the set-up mode of described dividing plate 11, for example, can make the side of described dividing plate 11 and sidewall contact or the close contact of described container 1, is preferably close contact.
As shown in Figure 2, in the equipment of described ion-exchange reactions, described switch can also comprise agitator 15, contacts thereby described molecular sieve is mixed under the stirring of described agitator 15 with described exchange liquid, and the stirring of described stirring makes the bottom of described container 1 not have the sediment deposition.There is no particular limitation for the speed that described agitator stirs, and do not have the sediment deposition as long as can guarantee the bottom of described switch, and under the preferable case, the speed of described stirring is 10-1000 rev/min, more preferably 20-200 rev/min.
As shown in Figure 2, in the equipment of described ion-exchange reactions, described switch can also comprise heater 16, mixed liquor by 16 pairs of described molecular sieves of described heater and described exchange liquid heats, thereby the mixed liquor of described molecular sieve and described exchange liquid is in the suitable temperature environment.Described temperature can change with the different of the product that finally will make according to raw material.Generally, in described molecular sieve ion exchange process, described temperature can suitably be selected in 20-100 ℃ scope, is preferably in 40-90 ℃ scope.The various heaters that described heater 16 can use for this area is conventional for example can be heating jacket, heating rod, and when described heater was heating jacket, described heating jacket was coated on the outer surface of bottom of described container 1; When described heater was heating rod, described heating rod directly inserted in the described container 1.
As shown in Figure 2, the equipment of described ion-exchange reactions can also be provided with the first feeding device 2, described molecular sieve and described exchange liquid, perhaps the mixed liquor of described molecular sieve and described exchange liquid supplies to the first space 12 of described container by described the first feeding device 2.Under the preferable case, described the first feeding device 2 can for example can be 1-10 for a plurality of, and described molecular sieve and described exchange liquid supply to respectively the first space 12 of described container by feeding device.Described the first feeding device 2 can for the conventional various feeding devices that use of those skilled in the art, for example can be charging pump, cloth bucket.
As shown in Figure 3, described ion-exchange reactions equipment preferably also comprises filter 3, and described filter 3 receives from the slurries after the described mixing contact of described container 1, and described slurries are filtered.In the present invention, described filter 3 can be the conventional various filters that use in this area, for example can be continuous band filter or flame filter press, be preferably the continuous band filter that to realize continuous filtration, thereby make the slurries after the described mixing contact on described continuous band filter, filter continuously and wash.
As shown in Figure 4, in the equipment of described ion-exchange reactions, can also be provided with Buffer Pool 4 between described switch and described filter 3, the slurries after the described mixing contact enter described Buffer Pool 4 by described opening 14, and are supplied to described filter 3 by described Buffer Pool 4.The existence of described Buffer Pool can pass through to regulate the discharging flow of Buffer Pool, thereby the slurries that obtain in the described container 1 after described mixing contacts are entered in the follow-up filter 3 with suitable flow.And, occurring in the process of of short duration fault at described switch, described Buffer Pool 4 can store a certain amount of for feed, thereby realizes continous way production.
In the equipment of described ion-exchange reactions, the bottom of described container 1 can also be provided with discharge port 17, and described discharge port 17 is communicated with described Buffer Pool 4 by pipeline 18, is provided with valve 19 on the described pipeline 18.In the situation that the normal operation of described ion-exchange reactions equipment, described valve is in closed condition usually.When described switch breaks down, by opening valve 19, make the mixing material in the described container 1 enter described Buffer Pool 4 by described discharge port 17.Described fault refers to affect the various accidents of the normal operation of described reaction unit, generally includes that described dividing plate 11 damages, described agitator 15 damages and at least a in damaging of described heater 16.In the situation that the normal operation of described ion-exchange reactions equipment, described valve 19 is in closed condition usually.
As shown in Figure 5, in the situation that described ion-exchange reactions equipment is provided with described Buffer Pool 4, described equipment preferably also comprises the second feeding device 5, and described the second device 5 is directly to described Buffer Pool 4 feed.In the present invention, can add additive in described Buffer Pool 4 by described the second feeding device 5, described additive can be for impelling the material that forms deposition from the slurries after the mixing contact of described container 1.The kind of described additive can be according to the difference of the reactant in the ion-exchange reactions process and difference.Described the second feeding device 5 can be one, also can be for a plurality of simultaneously to described Buffer Pool 4 feed, and generally, the number that described the second feeding device 5 arranges can be 1-5.Described the second feeding device 5 also can for the conventional various feeding devices that use of those skilled in the art, for example can be charging pump, cloth bucket.
In order to guarantee that described molecular sieve and exchange liquid stop the sufficiently long time in described switch, thereby make described molecular sieve and described exchange liquid that sufficient ion-exchange reactions occur, can recently realize with the volume of second space 13 with the relative position of described dividing plate 11 and the first space 12 in the described container 1 by regulating described opening 14.Particularly, when the vertical range of the lower edge of described opening 14 and the lower end of described dividing plate 11 reduced, in the situation that other condition is identical, described molecular sieve and the time of staying of exchange liquid in described container 1 shortened, otherwise then elongated; When the volumetric ratio of described the first space 12 and described second space 13 reduced, in the situation that other condition is identical, described molecular sieve and the time of staying of exchange liquid in described container 1 shortened, otherwise then elongated.In described method provided by the invention, the lower edge of described opening 14 can for the 20-95% of described dividing plate total height, be preferably 40-85% with the vertical range of the lower end of described dividing plate 11; Described the first space 12 can be 2-500 with the volumetric ratio condition of described second space 13: 1, be preferably 10-200: 1.Thereby so that described molecular sieve and the time of staying of described exchange liquid in described container 1 may be controlled to 0.1-3 hour, be preferably 0.5-2 hour.In the present invention, the method of described molecular sieve ion-exchange is applicable in the ion exchange process of molecular sieve of various routines, therefore, be added to described molecular sieve and described exchange liquid in the first space 12 of described container 1, can select the then conventional various molecular sieves that use of those skilled in the art and exchange liquid in the molecular sieve ion exchange process, for example, the molecular sieve that adopts can be the modified molecular screen of NaY molecular sieve and/or NaY molecular sieve, the modified molecular screen of described NaY molecular sieve for example can be the HY molecular sieve, the USY molecular sieve, the DOSY molecular sieve, the REY molecular sieve, at least a in the REUSY molecular sieve, described exchange liquid can comprise rare earths salt and/or ammonium salt solution.
The present invention also provides a kind of preparation method of rare earth Y type molecular sieve, the method comprises makes Y zeolite contact with exchange liquid, carry out ion-exchange, wherein, ion-exchange reactions equipment is as shown in Figure 1 adopted in described ion-exchange, and this equipment comprises switch, and described switch comprises container 1 and dividing plate 11, described dividing plate 11 is divided into the first space 12 and second space 13 with described container 1, and the volume in described the first space 12 is greater than the volume of described second space 13; The bottom of the lower end of described dividing plate 11 and described container 1 has the space, and described the first space 12 and described second space 13 are communicated with by described space; Be provided with opening 14 on the sidewall of described container 1, described opening 14 is communicated with described second space 13, and the lower edge of described opening 14 is higher than the lower end of described dividing plate 11 and is lower than the upper end of described dividing plate 11; Described Y zeolite and described exchange liquid are added to mix in described the first space 12 to contact, the slurries that mix after the contact are flowed out continuously by opening 14.
In described ion-exchange reactions equipment, described switch can for the conventional various reactors that use in this area, be preferably retort.In described switch, there is no particular limitation for the set-up mode of described dividing plate 11, for example, can make the side of described dividing plate 11 and sidewall contact or the close contact of described container 1, is preferably close contact.
As shown in Figure 2, in the equipment of described ion-exchange reactions, described switch can also comprise agitator 15, contact thereby described Y zeolite is mixed under the stirring of described agitator 15 with described exchange liquid, the stirring of described stirring makes the bottom of described container 1 not have the sediment deposition.There is no particular limitation for the speed that described agitator stirs, and do not have the sediment deposition as long as can guarantee the bottom of described switch, and under the preferable case, the speed of described stirring is 10-1000 rev/min, more preferably 20-200 rev/min.
As shown in Figure 2, in the equipment of described ion-exchange reactions, described switch can also comprise heater 16, mixed liquor by 16 pairs of described Y zeolites of described heater and described exchange liquid heats, thereby the mixed liquor of described Y zeolite and described exchange liquid is in the suitable temperature environment.Described temperature can change with the different of the product that finally will make according to raw material.Generally, in described Y zeolite ion exchange process, described temperature can suitably be selected in 20-100 ℃ scope, is preferably in 40-90 ℃ scope.The various heaters that described heater 16 can use for this area is conventional for example can be heating jacket, heating rod, and when described heater was heating jacket, described heating jacket was coated on the outer surface of bottom of described container 1; When described heater was heating rod, described heating rod directly inserted in the described container 1.
As shown in Figure 2, the equipment of described ion-exchange reactions can also be provided with the first feeding device 2, described Y zeolite and described exchange liquid, perhaps the mixed liquor of described Y zeolite and described exchange liquid supplies to the first space 12 of described container by described the first feeding device 2.Under the preferable case, described the first feeding device 2 can for example can be 1-10 for a plurality of, and described Y zeolite and described exchange liquid supply to respectively the first space 12 of described container by feeding device.Described the first feeding device 2 can for the conventional various feeding devices that use of those skilled in the art, for example can be charging pump, cloth bucket.
As shown in Figure 3, described ion-exchange reactions equipment preferably also comprises filter 3, and described filter 3 receives from the slurries after the described mixing contact of described container 1, and described slurries are filtered.In the present invention, described filter 3 can be the conventional various filters that use in this area, for example can be continuous band filter or flame filter press, be preferably the continuous band filter that to realize continuous filtration, thereby make the slurries after the described mixing contact on described continuous band filter, filter continuously and wash.
As shown in Figure 4, in the equipment of described ion-exchange reactions, can also be provided with Buffer Pool 4 between described switch and described filter 3, the slurries after the described mixing contact enter described Buffer Pool 4 by described opening 14, and are supplied to described filter 3 by described Buffer Pool 4.The existence of described Buffer Pool can pass through to regulate the discharging flow of Buffer Pool, thereby the slurries that obtain in the described container 1 after described mixing contacts are entered in the follow-up filter 3 with suitable flow.And, occurring in the process of of short duration fault at described switch, described Buffer Pool 4 can store a certain amount of for feed, thereby realizes continous way production.
In the equipment of described ion-exchange reactions, the bottom of described container 1 can also be provided with discharge port 17, and described discharge port 17 is communicated with described Buffer Pool 4 by pipeline 18, is provided with valve 19 on the described pipeline 18.In the situation that the normal operation of described ion-exchange reactions equipment, described valve is in closed condition usually.When described switch breaks down, by opening valve 19, make the mixing material in the described container 1 enter described Buffer Pool 4 by described discharge port 17.Described fault refers to affect the various accidents of the normal operation of described reaction unit, generally includes that described dividing plate 11 damages, described agitator 15 damages and at least a in damaging of described heater 16.In the situation that the normal operation of described ion-exchange reactions equipment, described valve 19 is in closed condition usually.
As shown in Figure 5, in the situation that described ion-exchange reactions equipment is provided with described Buffer Pool 4, described equipment preferably also comprises the second feeding device 5, and described the second device 5 is directly to described Buffer Pool 4 feed.In the present invention, can in described Buffer Pool 4, add additive by described the second feeding device 5, described additive can be for can impelling the material that forms deposition from the slurries after the described mixing contact of described container 1, and what described additive for example can be in ammoniacal liquor, sodium hydroxide solution, water glass solution, flocculant and the ammonium phosphate is at least a.Described the second feeding device 5 can be one, also can be for a plurality of simultaneously to described Buffer Pool 4 feed, and generally, the number that described the second feeding device 5 arranges can be 1-5.Described the second feeding device 5 also can for the conventional various feeding devices that use of those skilled in the art, for example can be charging pump, cloth bucket.
In order to guarantee that described Y zeolite and described exchange liquid stop the sufficiently long time in described switch, thereby make described Y zeolite and described exchange liquid that sufficient ion-exchange reactions occur, can recently realize with the volume of second space 13 with the relative position of described dividing plate 11 and the first space 12 in the described container 1 by regulating described opening 14.Particularly, when the vertical range of the lower edge of described opening 14 and the lower end of described dividing plate 11 reduced, in the situation that other condition is identical, described molecular sieve and the time of staying of exchange liquid in described container 1 shortened, otherwise then elongated; When the volumetric ratio of described the first space 12 and described second space 13 reduced, in the situation that other condition is identical, described molecular sieve and the time of staying of exchange liquid in described container 1 shortened, otherwise then elongated.In described method provided by the invention, the lower edge of described opening 14 can for the 20-95% of described dividing plate total height, be preferably 40-85% with the vertical range of the lower end of described dividing plate 11; Described the first space 12 can be 2-500 with the volumetric ratio condition of described second space 13: 1, be preferably 10-200: 1.Thereby so that described Y zeolite and the time of staying of described exchange liquid in described container 1 may be controlled to 0.1-3 hour, be preferably 0.5-2 hour.
In the preparation method of described rare earth Y type molecular sieve provided by the invention, described Y zeolite and exchange liquid can select the then conventional various Y zeolites that use in this area and exchange liquid in the preparation process of rare earth Y type molecular sieve.
Described Y zeolite can be the modified molecular screen of NaY molecular sieve and/or NaY molecular sieve, described NaY molecular sieve can in the sodium content of sodium oxide molybdena for being not less than 1 % by weight, be preferably the NaY molecular sieve of 1-15 % by weight; The modified molecular screen of described NaY molecular sieve for example can be in HY molecular sieve, USY molecular sieve, DOSY molecular sieve, REY molecular sieve, the REUSY molecular sieve at least a.
Described exchange liquid can comprise rare earths salt and ammonium salt solution.Described ammonium salt can be preferably ammonium chloride and/or ammonium sulfate for being selected from least a in ammonium chloride, ammonium sulfate, ammonium acetate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), the ammonium nitrate, most preferably is ammonium chloride.Described rare earth compound can be rare earth-iron-boron and/or rare earth nitrades, and described rare earth element can be selected from least a in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, the neptunium.Under the preferable case, described rare earth compound is rare earth-iron-boron, and described rare earth element is preferably lanthanum and/or cerium.
In the described method for preparing rare earth Y type molecular sieve provided by the invention, the weight ratio that described Y zeolite, described rare-earth salts and described ammonium salt add can be 1: 0.01-0.6: 0.01-2 is preferably 1: 0.05-0.5: 0.05-0.6.
In the described method for preparing rare earth Y type molecular sieve, there is no particular limitation for the adding mode of described Y zeolite, described rare-earth salts and described ammonium salt, be added to again in the first space 12 of described container 1 after described Y zeolite, described rare earths salt and described ammonium salt solution can being mixed, described Y zeolite, described rare earths salt and described ammonium salt solution are added to respectively in the first space 12 of described container 1.For convenient control ingredient proportion and feed rate, described Y zeolite, described rare earths salt and described ammonium salt solution are added to respectively in the first space 12 of described container 1.
In the situation in the first space 12 that described Y zeolite, described rare earths salt and described ammonium salt solution is added to respectively described container 1, described Y zeolite can add with the form of slurries, and the content of Y zeolite is the 5-60 % by weight in described slurries; The concentration of described rare earths salt can be the 50-400 grams per liter; The concentration of described ammonium salt solution can be the 50-400 grams per liter.
In the preferred case, can also comprise acid solution or aqueous slkali in the described exchange liquid, the adding of described acid solution or described aqueous slkali is so that the pH value of mixing the slurries that obtain after the contact in described container 1 for 3-9, is preferably 3-6.Described acid can be selected from least a in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, the oxalic acid, is preferably hydrochloric acid; Described alkali can be selected from least a in ammoniacal liquor, NaOH, potassium hydroxide, sodium carbonate, the sodium acid carbonate, is preferably NaOH.The concentration of described acid solution can be the 0.5-10 % by weight, and the concentration of described aqueous slkali can be the 0.1-40 % by weight.
In the preparation method with described rare earth Y type molecular sieve provided by the invention, described method can also comprise that the filter cake that makes through obtaining after ion-exchange and the filtration carries out roasting, thereby is met the rare earth Y type molecular sieve of production requirement.There is no particular limitation in the present invention for the method for described roasting, can adopt the conventional method of using of those skilled in the art to implement.
The present invention is further detailed explanation by the following examples.
The present embodiment is used for illustrating the method for molecular sieve ion-exchange provided by the invention and the preparation method of rare earth Y type molecular sieve.
Adopt ion-exchange reactions equipment as shown in Figure 5 to prepare rare earth Y type molecular sieve, described system comprises the first feeding device 2, the second feeding device 5, switch, Buffer Pool 4 and filter 3, described the first feeding device 2 and the second feeding device 5 are charging pump, and described the first feeding device 2 is to described switch feed, and described the second feeding device 5 is directly to described Buffer Pool 4 feed; Described switch is that volume is 5m
3Retort, described retort comprises container 1 and dividing plate 11, agitator 15, heater 16, and be provided with opening 14 on the sidewall of described retort, the bottom is provided with discharge port 17, two sides of described dividing plate 11 and the sidewall close contact of described retort, and described retort is divided into the first space 12 and the second space 13 that is interconnected, described the first space 12 is 50: 1 with the volumetric ratio of described second space 13, and the lower edge of described opening 14 is 80% of described dividing plate total height with the vertical range of the lower end of described dividing plate 11; Described Buffer Pool 4 is 15m for volume
3Container, described Buffer Pool 4 is communicated with described second space 13 by described opening 14, and the discharge port 17 of described retort bottom is communicated with described Buffer Pool by pipeline 18, and the middle valve 19 that is provided with of described pipeline is to control discharging; In addition, the opening that described Buffer Pool arranges by the bottom is to described filter 3 feed, and described filter 3 be continuous band filter (by Yueyang Hengzhong Mechanical Engineering Technology Co., Ltd.'s production, model is DI36/2500).
To contain the NaY molecular sieve of 25 % by weight (in described NaY molecular sieve by a charging pump respectively, in sodium oxide molybdena, the content of sodium is 14.5 % by weight, lattice constant is 24.70 dusts, produced by catalyst Chang Ling branch company of China Petrochemical Industry) molecular sieve pulp, concentration is the ammonium chloride solution of 100 grams per liters, concentration is the solution of the lanthanum chloride of 120 grams per liters, concentration is the first space that the hydrochloric acid solution of 1 % by weight is added to described retort, thereby mix by agitator and to obtain mixed serum, and described container bottom does not have the sediment deposition, in described mixed serum, the NaY molecular sieve, the weight ratio of lanthanum chloride and ammonium chloride is 1: 0.2: 0.4, the addition of described hydrochloric acid is so that the pH value of described mixed serum is 5, by heater 16 mixed serum in the described retort is heated to 60 ℃, and makes the time of staying of above-mentioned reactant feed in described retort be controlled to be 1 hour.Mixed serum in the described retort enters described Buffer Pool 4 by described opening 14, described Buffer Pool with described mixed serum with 6m
3/ hour flow supply on the described band filter, described mixed liquor filters continuously and washs on described band filter, then (Ruide Dry Technology Co., Ltd., Lanzhou City produces the final filter cake that forms on the described band filter to be transferred to roaster, model is φ 1200 * 25400) in carry out roasting, the temperature of described roasting is 600 ℃, time is 3.5 hours, thereby obtains rare earth Y type molecular sieve A1.
Preparation example 1
Adopt step method to prepare rare earth Y type molecular sieve, ion-exchange in its preparation process is carried out in retort, wherein, the condition of ion-exchange is identical with embodiment 1, as the NaY molecular sieve of selecting is identical with embodiment 1, the weight ratio of NaY molecular sieve, lanthanum chloride and ammonium chloride addition is identical with embodiment 1, and pH value, the temperature of material are identical with embodiment 1 in the described retort, and the time of carrying out ion-exchange in the retort is identical with the time of staying of reactant in retort among the embodiment 1; And, the mixed serum that obtains in the retort is filtered with the method for filter cake being carried out roasting also adopt the method identical with embodiment 1, thereby obtain rare earth Y type molecular sieve B1.
Embodiment 2
The present embodiment is used for illustrating the preparation method of ion-exchange reactions equipment provided by the invention and rare earth Y type molecular sieve.
The ion-exchange reactions equipment that uses in the present embodiment is identical with embodiment 1.
To contain the NaY molecular sieve of 30 % by weight (in sodium oxide molybdena by a charging pump respectively, the content of sodium is 13.8 % by weight, lattice constant is 24.70 dusts, produced by catalyst Chang Ling branch company of China Petrochemical Industry) molecular sieve pulp, concentration is the ammonium chloride solution of 120 grams per liters, concentration is the solution of the lanthanum chloride of 90 grams per liters, concentration is the first space that the hydrochloric acid solution of 2 % by weight is added to described retort, thereby mix by agitator and to obtain mixed serum, and described container bottom does not have the sediment deposition, in described mixed serum, the NaY molecular sieve, the weight ratio of lanthanum chloride and ammonium chloride is 1: 0.05: 0.45, the addition of described hydrochloric acid is so that the pH value of described mixed serum is 3, by heater 16 mixed serum in the described retort is heated to 90 ℃, and makes the time of staying of above-mentioned reactant feed in described retort be controlled to be 0.5 hour.Mixed serum in the described retort enters described Buffer Pool 4 by described opening 14, described Buffer Pool with described mixed serum with 7m
3/ hour flow be fed on the described band filter, described mixed liquor filters continuously and washs on described band filter, then (Ruide Dry Technology Co., Ltd., Lanzhou City produces the final filter cake that forms on the described band filter to be transferred to roaster, model is φ 1200 * 25400) in carry out roasting, the temperature of described roasting is 550 ℃, time is 4 hours, thereby obtains rare earth Y type molecular sieve A2.
Preparation example 2
Adopt step method to prepare rare earth Y type molecular sieve, ion-exchange in its preparation process is carried out in retort, wherein, the condition of ion-exchange is identical with embodiment 2, as the NaY molecular sieve of selecting is identical with embodiment 2, the weight ratio of NaY molecular sieve, lanthanum chloride and ammonium chloride addition is identical with embodiment 2, and pH value, the temperature of material are identical with embodiment 2 in the described retort, and the time of carrying out ion-exchange in the retort is identical with the time of staying of reactant in retort among the embodiment 2; And, the mixed serum that obtains in the retort is filtered with the method for filter cake being carried out roasting also adopt the method identical with embodiment 2, thereby obtain rare earth Y type molecular sieve B2.
The present embodiment is used for illustrating the preparation method of ion-exchange reactions equipment provided by the invention and rare earth Y type molecular sieve.
The ion-exchange reactions equipment that uses in the present embodiment is identical with embodiment 1.
To contain the NaY molecular sieve of 30 % by weight (in sodium oxide molybdena by a charging pump respectively, the content of sodium is 13.8 % by weight, lattice constant is 24.70 dusts, produced by catalyst Chang Ling branch company of China Petrochemical Industry) molecular sieve pulp, concentration is the ammonium chloride solution of 80 grams per liters, concentration is the solution of the lanthanum chloride of 140 grams per liters, concentration is the first space that the hydrochloric acid solution of 0.5 % by weight is added to described retort, thereby mix by agitator and to obtain mixed serum, and described container bottom does not have the sediment deposition, in described mixed serum, the NaY molecular sieve, the weight ratio of lanthanum chloride and ammonium chloride is 1: 0.4: 0.1, the addition of described hydrochloric acid is so that the pH value of described mixed serum is 6, by heater 16 mixed serum in the described retort is heated to 75 ℃, and makes the time of staying of above-mentioned reactant feed in described retort be controlled to be 1.8 hours.Mixed serum in the described retort enters described Buffer Pool 4 by described opening 14, described Buffer Pool with described mixed serum with 7m
3/ hour flow be fed on the described band filter, described mixed liquor filters continuously and washs on described band filter, then (Ruide Dry Technology Co., Ltd., Lanzhou City produces the final filter cake that forms on the described band filter to be transferred to roaster, model is φ 1200 * 25400) in carry out roasting, the temperature of described roasting is 700 ℃, time is 3 hours, thereby obtains rare earth Y type molecular sieve A3.
Preparation example 3
Adopt step method to prepare rare earth Y type molecular sieve, ion-exchange in its preparation process is carried out in retort, wherein, the condition of ion-exchange is identical with embodiment 3, as the NaY molecular sieve of selecting is identical with embodiment 3, the weight ratio of NaY molecular sieve, lanthanum chloride and ammonium chloride addition is identical with embodiment 3, and pH value, the temperature of material are identical with embodiment 3 in the described retort, and the time of carrying out ion-exchange in the retort is identical with the time of staying of reactant in retort among the embodiment 3; And, the mixed serum that obtains in the retort is filtered with the method for filter cake being carried out roasting also adopt the method identical with embodiment 3, thereby obtain rare earth Y type molecular sieve B3.
Test case
Adopt atomic absorption spectrography (AAS) in " Petrochemical Engineering Analysis method (RIPP test method) " measure respectively among rare earth Y type molecular sieve A1-A3 that embodiment 1-3 and preparation example 1-3 make and the B1-B3 in the content of rare earth of rare earth oxide with in the sodium content of sodium oxide molybdena, its result is as shown in table 1 below.
Table 1
| A1 | B1 | A2 | B2 | A3 | B3 | |
| Content of rare earth | 9.8 | 9.5 | 2.4 | 2.2 | 14.1 | 13.6 |
| Sodium content | 1.2 | 1.5 | 2.0 | 2.3 | 1.0 | 1.3 |
As can be seen from Table 1, adopt the prepared rare earth Y type molecular sieve of method provided by the invention and adopt the content of rare earth in the prepared rare earth Y type molecular sieve of step mode very approaching, this shows, adopt the prepared rare earth Y type molecular sieve of method provided by the invention can satisfy production requirement.Simultaneously, the method for described molecular sieve ion-exchange provided by the invention has realized continous way production with the method for preparing rare earth Y type molecular sieve, has greatly alleviated the labour intensity in the production process.
Claims (33)
1. the method for a molecular sieve ion-exchange, it is characterized in that, a kind of ion-exchange reactions equipment is adopted in molecular sieve ion-exchange, this equipment comprises switch, described switch comprises container (1) and dividing plate (11), described dividing plate (11) is divided into the first space (12) and second space (13) with described container (1), the volume in described the first space (12) is greater than the volume of described second space (13), and described the first space (12) is 10-200:1 with the volumetric ratio of described second space (13); The bottom of the lower end of described dividing plate (11) and described container (1) has the space, and described the first space (12) and described second space (13) are communicated with by described space; Be provided with opening (14) on the sidewall of described container (1), described opening (14) is communicated with described second space (13), and the lower edge of described opening (14) is higher than the lower end of described dividing plate (11) and is lower than the upper end of described dividing plate (11), and the lower edge of described opening (14) is the 20-95% of described dividing plate (11) total height with the vertical range of the lower end of described dividing plate (11); The method comprises a kind of slurries are joined in described the first space (12) continuously mixes contact, described slurries contain molecular sieve and exchange liquid, perhaps molecular sieve and exchange liquid are joined respectively in described the first space (12) continuously, molecular sieve is mixed with exchange liquid contact, the slurries that mix after contacting are flowed out continuously by opening (14).
2. method according to claim 1, wherein, the sidewall close contact of the side of described dividing plate (11) and described container (1).
3. method according to claim 1, wherein, described switch also comprises agitator (15), described molecular sieve is mixed under the stirring of described agitator (15) with described exchange liquid contact, and the stirring of described stirring makes the bottom of described container (1) not have the sediment deposition.
4. method according to claim 1, wherein, described switch also comprises heater (16), heats by the mixed liquor of described heater (16) to described molecular sieve and described exchange liquid.
5. method according to claim 1, wherein, described equipment also comprises the first feeding device (2), described molecular sieve and described exchange liquid, and perhaps the mixed liquor of described molecular sieve and described exchange liquid supplies to first space (12) of described container by described the first feeding device (2).
6. method according to claim 5, wherein, described the first feeding device (2) is a plurality of, described molecular sieve and described exchange liquid supply to respectively first space (12) of described container by feeding device.
7. method according to claim 1, wherein, described equipment also comprises filter (3), the slurries after the described mixing contact enter described filter (3) continuously by opening (14).
8. method according to claim 7, wherein, between described switch and described filter (3), also be provided with Buffer Pool (4), slurries after the described mixing contact enter described Buffer Pool (4) by described opening (14), and are supplied to described filter (3) by described Buffer Pool (4).
9. method according to claim 8, wherein, the bottom of described container (1) also is provided with discharge port (17), and described discharge port (17) is communicated with described Buffer Pool (4) by pipeline (18), is provided with valve (19) on the described pipeline (18); When described switch breaks down, by opening valve (19), make the mixing material in the described container (1) enter described Buffer Pool (4) by described discharge port (17).
10. method according to claim 8, wherein, described equipment also comprises the second feeding device (5), add additive by described the second feeding device (5) in described Buffer Pool (4), described additive is for impelling the material that forms deposition from the slurries after the mixing contact of described container (1).
11. the described method of any one according to claim 1-10, wherein, described molecular sieve and the time of staying of described exchange liquid in described container (1) are 0.1-3 hour.
12. method according to claim 1, wherein, it is 20-100 ℃ that described molecular sieve mixes the temperature that contacts with described exchange liquid.
13. method according to claim 1, wherein, described molecular screening is from the modified molecular screen of NaY molecular sieve and/or NaY molecular sieve; Described exchange liquid comprises rare earths salt and/or ammonium salt solution.
14. the preparation method of a rare earth Y type molecular sieve, the method comprises makes Y zeolite contact with exchange liquid, carry out ion-exchange, it is characterized in that, a kind of ion-exchange reactions equipment is adopted in described ion-exchange, this equipment comprises switch, described switch comprises container (1) and dividing plate (11), described dividing plate (11) is divided into the first space (12) and second space (13) with described container (1), the volume in described the first space (12) is greater than the volume of described second space (13), and described the first space (12) is 10-200:1 with the volumetric ratio of described second space (13); The bottom of the lower end of described dividing plate (11) and described container (1) has the space, and described the first space (12) and described second space (13) are communicated with by described space; Be provided with opening (14) on the sidewall of described container (1), described opening (14) is communicated with described second space (13), and the lower edge of described opening (14) is higher than the lower end of described dividing plate (11) and is lower than the upper end of described dividing plate (11), and the lower edge of described opening (14) is the 20-95% of described dividing plate (11) total height with the vertical range of the lower end of described dividing plate (11); Described Y zeolite and described exchange liquid are added to mix in described the first space (12) to contact, the slurries that mix after the contact are flowed out continuously by opening (14).
15. method according to claim 14, wherein, the sidewall close contact of the side of described dividing plate (11) and described container (1).
16. method according to claim 14, wherein, described switch also comprises agitator (15), described Y zeolite is mixed under the stirring of described agitator (15) with described exchange liquid contact, the stirring of described stirring makes the bottom of described container (1) not have the sediment deposition.
17. method according to claim 14, wherein, described switch also comprises heater (16), heats by the mixed liquor of described heater (16) to described Y zeolite and described exchange liquid.
18. method according to claim 14, wherein, described equipment also comprises the first feeding device (2), described Y zeolite and described exchange liquid, perhaps the mixed liquor of described Y zeolite and described exchange liquid supplies to first space (12) of described container (1) by described the first feeding device (2).
19. method according to claim 18, wherein, described the first feeding device (2) is a plurality of, and described Y zeolite and described exchange liquid supply to respectively first space (12) of described container (1) by feeding device.
20. method according to claim 14, wherein, described equipment also comprises filter (3), and the slurries after the described mixing contact enter described filter (3) continuously by opening (14).
21. method according to claim 20, wherein, between described switch and described filter (3), also be provided with Buffer Pool (4), slurries after the described mixing contact enter described Buffer Pool (4) by described opening (14), and are supplied to described filter (3) by described Buffer Pool (4).
22. method according to claim 21, wherein, the bottom of described container (1) also is provided with discharge port (17), and described discharge port (17) is communicated with described Buffer Pool (4) by pipeline (18), is provided with valve (19) on the described pipeline (18); When described switch breaks down, by opening valve (19), make the mixing material in the described container (1) enter described Buffer Pool (4) by described discharge port (17).
23. method according to claim 21, wherein, described equipment also comprises the second feeding device (5), add additive by described the second feeding device (5) in described Buffer Pool (4), described additive is for impelling the material that forms deposition from the slurries after the mixing contact of described container (1).
24. method according to claim 23, wherein, described additive is at least a in ammoniacal liquor, sodium hydroxide solution, water glass solution, flocculant and the ammonium phosphate.
25. the described method of any one according to claim 14-24, wherein, described molecular sieve and the time of staying of described exchange liquid in described container (1) are 0.1-3 hour.
26. method according to claim 14, wherein, it is 20-100 ℃ that described molecular sieve mixes the temperature that contacts with described exchange liquid.
27. method according to claim 14, wherein, described Y zeolite is selected from the modified molecular screen of NaY molecular sieve and/or NaY molecular sieve; Described exchange liquid comprises rare earths salt and ammonium salt solution.
28. method according to claim 27, wherein, the weight ratio that described Y zeolite, described rare-earth salts and described ammonium salt add is 1:0.01-0.6:0.01-2.
29. method according to claim 27, wherein, described Y zeolite is the NaY molecular sieve; Described ammonium salt is selected from least a in ammonium chloride, ammonium sulfate, ammonium acetate, ammonium phosphate, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), the ammonium nitrate; Described rare earth compound is rare earth-iron-boron and/or rare earth nitrades, and described rare earth element is selected from least a in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protactinium, uranium, the neptunium.
30. method according to claim 29, wherein, in described NaY molecular sieve, in sodium oxide molybdena, the content of sodium is the 1-15 % by weight; Described ammonium salt be ammonium chloride and/ammonium sulfate, described rare earth compound is the chloride of lanthanum and/or cerium.
31. method according to claim 27, wherein, described exchange liquid also comprises acid solution or aqueous slkali.
32. method according to claim 31, wherein, the addition of described acid solution or aqueous slkali is so that the pH value of the slurries after the described mixing contact is 3-9.
33. method according to claim 32, wherein, described acid is selected from least a in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, the oxalic acid; Described alkali is selected from least a in ammoniacal liquor, NaOH, potassium hydroxide, sodium carbonate, the sodium acid carbonate.
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| CN85200078U (en) * | 1985-04-01 | 1985-09-10 | 甘健秋 | Reverse flow type ion-exchange appatus |
| CN2142834Y (en) * | 1992-10-14 | 1993-09-29 | 甘健秋 | Double-flow ion-exchanger of regenerating on back flow |
| US6527958B1 (en) * | 1997-11-27 | 2003-03-04 | T & P S.P.A. | Device for reducing water hardness (softener) having a resins exhaustion sensor, and washing machine having said device |
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