CN100593436C - Multi-stage series-connection fluidization-bed alternative changing-over molecular-sieve ion exchanging process - Google Patents
Multi-stage series-connection fluidization-bed alternative changing-over molecular-sieve ion exchanging process Download PDFInfo
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- CN100593436C CN100593436C CN200610011875A CN200610011875A CN100593436C CN 100593436 C CN100593436 C CN 100593436C CN 200610011875 A CN200610011875 A CN 200610011875A CN 200610011875 A CN200610011875 A CN 200610011875A CN 100593436 C CN100593436 C CN 100593436C
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Abstract
The present invention discloses a molecular sieve ion exchange new process. It is characterized by that after N fluidized-bed exchange columns are series-connected, they can be alternatively worked, the exchange solution can be sequentially flowed through every exchange column, and the flow rate of said solution can be controlled to make the molecular sieve in every exchange column be suspended and fluidized and can not be carried into the next exchange column, so that the alternative sequential change-over of all the exchange columns can implement continuous production of exchange ion high utilization rate.
Description
Technical field
The present invention relates to a kind of technology that various molecular sieve ion-exchanges are produced that is widely used in, belong to chemical field.
Background technology
The method of still formula exchange is generally adopted in the ion-exchange of molecular sieve, be about to molecular sieve to be exchanged and contain finite concentration and treat that the exchange solution making beating of exchange ion mixes, in reactor, stir certain hour at a certain temperature and reach exchange equilibrium, can obtain the zeolite product of certain exchange degree.Often to pass through multistage exchange in order to reach higher exchange degree, still have more exchangeable ion, consumption indicators height and contaminated environment in complex operation and the mother liquor waste liquid after exchange.Molecular sieve molded granulation is exchanged by fixed bed, though can reduce the loss of exchange ion like this, but molecular sieve must can reach the mechanical strength that the fixed bed exchange requires through shaping and roasting, and the resistance to mass tranfer of particle inside is bigger after the moulding, influences exchange efficiency.On the molecular sieve thin layer that forms on the filter cloth of band filter, filter press or centrifuge, also can exchange, especially in large-scale production, use band filter production efficiency than higher, but because the bed of material approaches and wear the relation of filter, the loss of exchange ion is still bigger in the effluent discharge.Thanked in 1994 in the celebrating magnificent disclosed patent (CN:1108586A) " method and the switch thereof of sodium-ion type molecular sieve exchange ", in the exchange still, place a large amount of tubular filter screen, make molecular sieve on the filter membrane that screen surface forms, carry out the ammonium exchange of NaY by vacuum filtration, can improve the utilization rate of ammonium with plural serial stage, reduce the discharging of ammonium in the waste liquid.But this method equipment complexity and filter screen are cumbersome in the cleaning of exchange surface molecular screen membrane, are difficult to use in large-scale production.
Summary of the invention
The object of the present invention is to provide and a kind ofly can carry out quantity-produced high-effect ionic exchange process.Technical scheme of the present invention is as follows:
A kind of molecular sieve ion-exchange process, use N (N 〉=3, N is an integer) exchange column of individual series connection, each exchange column is equipped with molecular sieve to be exchanged, switch in turn in order, each exchange column all experiences the cycling process that changes to afterbody from the first order successively, contain and remain the exchange solution of exchange ion and flow through each exchange column successively, solution flow rate is controlled at the molecular sieve suspension fluidisation that makes in the exchange column and don't as for taking next exchange column out of, thereby realizes the production continuously of exchange ion high usage ground.
When reaching steady state operation, all exchange the molecular sieve of solution and the different exchange degrees that suspending in each pillar abrim, wherein as the exchange column of afterbody dress be fresh molecular sieve pulp to be exchanged, it is to pack into after pulling an oar with fresh molecular sieve powder.Fresh exchange solution flows into from first order exchange column, and sequential flow is crossed the exchange columns at different levels of series connection, the control solution flow rate make molecular sieve powder can be in post fluidisation, but be unlikely to be taken out of outside the post, so just at exchange column top formation supernatant layer.Supernatant liquor flows out the pillar top, enters the next stage exchange column.Exchange solution is discharged as waste liquid from afterbody after the plural serial stage exchange.Molecular sieve in the first order exchange column reaches the zeolite product that must exchange by Separation of Solid and Liquid behind certain exchange degree through fresh exchange solution exchange, isolated solution also can be used as fresh solution and utilizes, the pillar that is available new the waiting of packing into exchanges molecular sieve pulp and uses as afterbody, and second level exchange column originally becomes the first order to be used.N exchange column switches the steady and continuous production that the formation operation cycle can realize molecular sieve ion-exchange in proper order.
Above-mentioned exchange solution is the salting liquid that comprises the ion that will exchange molecular sieve, and exchange ion can be ammonium ion, alkali metal ion, alkaline-earth metal ions, rare earth ion, transition metal ions, Actinium series elements ion etc.
Molecular sieve above-mentioned to be exchanged can be any molecular sieve, as y-type zeolite molecular sieve, X type zeolite molecular sieve, A type zeolite molecular sieve, ZSM-5 zeolite molecular sieve, mordenite molecular sieve, beta-zeolite molecular sieve or clinoptilolite molecular sieve etc.
Above-mentioned ion exchange column can be made with any material that is suitable for loading the exchange salting liquid, as iron and steel, plastics, glass, fiberglass, rubber etc.
Multi-stage series-connection fluidization-bed alternative changing-over molecular-sieve ion-exchange process of the present invention, because molecular sieve powder is in fluidized state, the big resistance of bed voidage is little, and solution is few by the external energy that molecular sieve needs, and is easy to realize continuous-flow production, and equipment is simple.By plural serial stage, make the utilization rate of exchange ion greatly improve, the content of exchange ion correspondingly also significantly reduces in the waste liquid that afterbody flows out.
Description of drawings
Fig. 1 is that the fluidized bed plant schematic diagram is switched in the Pyatyi series connection in turn.
Fig. 2 is five exchange column circulation handover operation sequential schematic.
Wherein:
The import of 1～5---exchange column 11---raw molecule screening the pulp liquid
12---fresh exchange solution inlet port 13---waste liquid outlet
14---the outlet of products molecule screening the pulp liquid
The specific embodiment
When switching fluid bed in turn and reach steady state operation with Pyatyi (N=5) series connection below is example, specifies the method for operating (referring to accompanying drawing) of this technology, but does not limit the present invention in any way:
As illustrated in fig. 1 and 2, at first the 5# post is as the afterbody fresh molecular sieve pulp to be exchanged of packing into, and fresh exchange solution flows into from the 1# post as the first order, and supernatant liquor flows out the pillar top, enters the next stage exchange column.Exchange solution flows out as waste liquid from final stage 5# column top after Pyatyi series connection exchange.Treat molecular sieve in the first order 1# pillar reach exchange degree qualified after, molecular sieve and solution in the pillar shift out system, carry out Separation of Solid and Liquid, the zeolite product that obtains exchanging, isolated solution also can be used as fresh solution and re-uses, and the 1# pillar that the is available new molecular sieve pulp to be exchanged of packing into becomes the final stage post and uses.At this moment, the 2# post becomes first order pillar, and 3#, 4#, 5# pillar and then become the 2nd, 3,4 grade of pillar, promptly.So order is switched, and 1 to 5 grade of pairing pillar number becomes 2-3-4-5-1 by 1-2-3-4-5.Transfer sequence becomes successively, and 3-4-5-1-2,4-5-1-2-3,5-1-2-3-4,1-2-3-4-5 constitute operation cycle, can realize the steady and continuous production of molecular sieve.
Steady state operation needs a transitional period from going into operation to realizing, can make just that solid and solution compolision reach stable in the exchange columns at different levels.
The exchange of embodiment 1:NaY molecular sieve ammonium
The Pyatyi series connection as shown in Figure 1.Exchange column is a glass tube, and long 24cm, volume are 60mL.The bottom is that taper is so that cause the solution high flow velocities to make the molecular sieve fluidisation.Each pillar pack into 6 the gram NaY; At 90 ℃ is the NH of 20g/L with concentration down
4Cl exchange solution carries out tandem ion-exchange.Solution flow rate is 50ml/h.Liquid waste concentration is about 0.6g/L after reaching stable state, and remaining ammonium only is 3% of an original ammonium concentration, and the utilization rate of ammonium reaches 97%.Only have an appointment 57% with still formula exchange utilization rate.
The exchange of embodiment 2:NaY molecular sieve ammonium
Temperature is 80 ℃, and other conditions are with embodiment one.Obtaining the ammonium utilization rate is 95%.With contrast, only have an appointment 50% with still formula exchange utilization rate.
The exchange of embodiment 3:NaY molecular sieve ammonium
Temperature is 85 ℃, and exchange solution is (NH
4)
2S0
4, concentration is 30g/L, other conditions are with embodiment one.Obtaining the ammonium utilization rate is 95%.With contrast, have only 52% with still formula exchange utilization rate.
The exchange of embodiment 4:NaY molecular sieve ammonium
The Pyatyi series connection as shown in Figure 1.Exchange column is a plastic tube, and long 200cm, volume are 5000mL.The bottom is that taper is so that cause the solution high flow velocities to make the molecular sieve fluidisation.Each pillar pack into 400 the gram NaY; At 90 ℃ is the NH of 40g/L with concentration down
4Cl exchange solution carries out tandem ion-exchange.Solution flow rate is 2000ml/h.Liquid waste concentration is about 0.8g/L after reaching stable state, and remaining ammonium only is 2% of an original ammonium concentration, and the utilization rate of ammonium reaches 98%.With contrast, have only 57% with still formula exchange utilization rate.
The exchange of embodiment 5:13X molecular sieve calcium
Temperature is 70 ℃, and exchange solution is CaCl
2, concentration is 30g/L, other conditions are with embodiment one.Obtaining the Ca utilization rate is 98%.With contrast, only have an appointment 80% with still formula exchange Ca utilization rate.
The exchange of embodiment 6:4A molecular sieve calcium
Temperature is 60 ℃, and exchange solution is CaCl
2, concentration is 30g/L, other conditions are with embodiment one.Obtaining the Ca utilization rate is 97%.With contrast, only have an appointment 80% with still formula exchange Ca utilization rate.
The exchange of embodiment 7:4A molecular sieve potassium
Temperature is 80 ℃, and exchange solution is KCl, and concentration is 30g/L, and other conditions are with embodiment one.Obtaining the potassium utilization rate is 97%.With contrast, exchange sharp potassium with the still formula and only have an appointment 70% with rate.
The exchange of embodiment 8:4A molecular sieve potassium
The Pyatyi series connection as shown in Figure 1.Exchange column is a steel pipe, and long 300cm, volume are 30L.The bottom is that taper is so that cause the solution high flow velocities to make the molecular sieve fluidisation.Each pillar 4A molecular sieve 2000 gram of packing into; At 80 ℃ is that the KCl of 40g/L exchanges solution and carries out tandem ion-exchange with concentration down.Solution flow rate is 15L/h.Liquid waste concentration is about 0.8g/L after reaching stable state, and remaining ammonium only is 2% of an original ammonium concentration, and the utilization rate of potassium reaches 98%.With contrast, only have an appointment 70% with still formula exchange potassium utilization rate.
Claims (4)
1. molecular sieve ion-exchange process, use the exchange column of N series connection, the bottom of described exchange column is taper, contain and remain the fresh exchange solution of exchange ion and flow into from first order exchange column, sequential flow is crossed the exchange columns of waiting to exchange molecular sieve that are equipped with at different levels of series connection, the control solution flow rate makes that molecular sieve powder can be in post inner suspension fluidisation, but be unlikely to be taken out of outside the post, the clear liquid that forms at the exchange column top flows out the pillar top, enter the next stage exchange column, exchange solution is after the plural serial stage exchange, discharge as waste liquid from afterbody, molecular sieve in the first order exchange column reaches the zeolite product that must exchange by Separation of Solid and Liquid behind the regulation exchange degree through fresh exchange solution exchange, new waiting exchanges molecular sieve pulp and uses as afterbody and the pillar that is available is packed into, at this moment, second level exchange column originally becomes first order exchange column, so each exchange column switches in order in turn, constitute operation cycle, each exchange column all experiences the cycling process that changes to afterbody from the first order successively, realize the steady and continuous production of molecular sieve ion-exchange, wherein: N is an integer, N 〉=3.
2. the method for claim 1 is characterized in that, described exchange solution is the salting liquid that comprises the ion that will exchange molecular sieve.
3. method as claimed in claim 2 is characterized in that, described ion is ammonium radical ion, alkali metal ion, alkaline-earth metal ions, rare earth ion, transition metal ions He/Huo Actinium series elements ion.
4. the method for claim 1, it is characterized in that molecular sieve described to be exchanged is y-type zeolite molecular sieve, X type zeolite molecular sieve, A type zeolite molecular sieve, ZSM-5 zeolite molecular sieve, mordenite molecular sieve, beta-zeolite molecular sieve or clinoptilolite molecular sieve.
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| CN100593436C true CN100593436C (en) | 2010-03-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103769249B (en) * | 2012-10-25 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of ion-exchange process |
| CN103769250B (en) * | 2012-10-25 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of ion-exchange process |
| CN108187766B (en) * | 2018-03-02 | 2023-11-03 | 中触媒新材料股份有限公司 | Multi-column serial connection self-control ion exchange device and method |
| CN113120916B (en) * | 2019-12-31 | 2022-10-11 | 中国石油化工股份有限公司 | Method for modifying molecular sieve by using multivalent noble metal |
| CN115121213B (en) * | 2022-07-06 | 2023-11-10 | 江苏洁欧康科技有限公司 | Rotary tandem circulation calcium exchange reaction device and method |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1382450A (en) * | 1971-12-28 | 1975-01-29 | Rossing Uranium Ltd | Continuous ion exchange process and apparatus |
| US4048284A (en) * | 1976-03-08 | 1977-09-13 | Engelhard Minerals & Chemicals Corporation | Method and system for ion-exchanging particles |
| CN1108586A (en) * | 1994-10-07 | 1995-09-20 | 谢庆华 | Method for exchanging sodium-ion type molecular sieve and its exchanging apparatus |
| EP0863109A1 (en) * | 1997-03-03 | 1998-09-09 | Bayer Ag | Process and device for ion exchange in zeolites |
| CN1417118A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Molecular sieve ammonium ion exchange process |
| CN1485137A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Exchange method of ammonium and rare earth ion for molecular sieve |
-
2006
- 2006-05-11 CN CN200610011875A patent/CN100593436C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1382450A (en) * | 1971-12-28 | 1975-01-29 | Rossing Uranium Ltd | Continuous ion exchange process and apparatus |
| US4048284A (en) * | 1976-03-08 | 1977-09-13 | Engelhard Minerals & Chemicals Corporation | Method and system for ion-exchanging particles |
| CN1108586A (en) * | 1994-10-07 | 1995-09-20 | 谢庆华 | Method for exchanging sodium-ion type molecular sieve and its exchanging apparatus |
| EP0863109A1 (en) * | 1997-03-03 | 1998-09-09 | Bayer Ag | Process and device for ion exchange in zeolites |
| CN1417118A (en) * | 2001-10-30 | 2003-05-14 | 中国石油化工股份有限公司 | Molecular sieve ammonium ion exchange process |
| CN1485137A (en) * | 2002-09-28 | 2004-03-31 | 中国石油化工股份有限公司 | Exchange method of ammonium and rare earth ion for molecular sieve |
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