CONTINUOUS CRYSTAL TRANSFORMATION AND ION EXCHANGE DEVICE AND PROCESS

Abstract

Provided are a continuous crystal transformation and ion exchange device and process, belonging to the technical field of molecular sieve manufacturing. The continuous crystal transformation and ion exchange device comprises M+N reaction tanks which are in serial connection, wherein a feed opening of a latter reaction tank communicates with a discharge opening of a former reaction tank by means of a reaction solution circulation pipeline, and a discharge opening of an M+Nth reaction tank communicates with a feed opening of a first reaction tank by means of a reaction solution circulation pipeline. No more than M reaction tanks are used for a crystal transformation process, and no more than N reaction tanks are used for an ion exchange process. The method is used for preparing a finished zeolite molecular sieve product, and has the advantages of high exchange capacity, simple process, low cost and the like.

Claims

1. A continuous crystal transformation and ion exchange device, characterized by comprising: M+N reaction tanks which are in serial connection, wherein a feed opening of a latter reaction tank communicates with a discharge opening of a former reaction tank by means of a reaction solution circulation pipeline, and a discharge opening of an M+Nth reaction tank communicates with a feed opening of a first reaction tank by means of a reaction solution circulation pipeline; wherein no more than M reaction tanks are used for a crystal transformation process, and no more than N reaction tanks are used for an ion exchange process; all reaction tanks are each provided with four solution inlet pipelines, three solution outlet pipelines and one reaction solution circulation pipeline, wherein the four solution inlet pipelines are a deionized water inlet pipeline, a new alkali solution inlet pipeline, a new ion exchange solution inlet pipeline and a pH adjusting solution inlet pipeline, respectively, and the three solution outlet pipelines are a waste water outlet pipeline, a waste alkali solution outlet pipeline and a waste ion exchange solution outlet pipeline, respectively; and pipelines communicating with reaction tanks are controlled to be opened and closed by valves.

2. The continuous crystal transformation and ion exchange device according to claim 1, characterized in that, m reaction tanks are crystal transformation process reaction tanks for loading molecular sieve raw materials for crystal transformation; M-m reaction tanks are ion exchange process transition reaction tanks for loading intermediate products to be subjected to ion exchange after crystal transformation; n reaction tanks are ion exchange process reaction tanks for loading intermediate products for ion exchange; and N-n reaction tanks are crystal transformation process transition reaction tanks for loading molecular sieve raw materials to be subjected to crystal transformation.

3. A continuous crystal transformation and ion exchange process, characterized by comprising the following processes based on the continuous crystal transformation and ion exchange device of claim 2: in one cycle, introducing a new alkali solution into a first crystal transformation process reaction tank of the m crystal transformation process reaction tanks, introducing a reaction solution flowing out of the first crystal transformation process reaction tank into a second crystal transformation process reaction tank as a primary alkali solution, and introducing a reaction solution flowing out of the second crystal transformation process reaction tank into a third crystal transformation process reaction tank as a secondary alkali solution, and so on until a reaction solution flowing out of an mth crystal transformation process reaction tank is discharged as a waste alkali solution; after a period of time, first completing molecular sieve crystal transformation in the first crystal transformation process reaction tank, and closing a new alkali solution inlet pipeline and a reaction solution circulation pipeline of the first crystal transformation process reaction tank to convert the first crystal transformation process reaction tank into an ion exchange process transition reaction tank; before a next cycle starts, connecting at least one of the remaining cleaned ion exchange process transition reaction tanks to a tail of an ion exchange process cycle in sequence, using one of the connected ion exchange process transition reaction tanks as a last ion exchange process reaction tank, using the second crystal transformation process reaction tank in this cycle as a first crystal transformation process reaction tank in a next cycle, and then starting a new cycle; and before the new cycle starts, guaranteeing at least one of the ion exchange process transition reaction tanks to complete a cleaning operation for being connected to the tail of the ion exchange process cycle; while introducing the new alkali solution into the first crystal transformation process reaction tank of the m crystal transformation process reaction tanks, introducing a new ion exchange solution into a first ion exchange process reaction tank of the n ion exchange process reaction tanks, introducing a reaction solution flowing out of the first ion exchange process reaction tank into a second ion exchange process reaction tank as a primary ion exchange solution, and introducing a reaction solution flowing out of the second ion exchange process reaction tank into a third ion exchange process reaction tank as a secondary ion exchange solution, and so on until a reaction solution flowing out of an nth ion exchange process reaction tank is discharged as a waste ion exchange solution; after a period of time, first completing molecular sieve ion exchange in the first ion exchange process reaction tank, and closing a new ion exchange solution inlet pipeline and a reaction solution circulation pipeline of the first ion exchange process reaction tank to convert the first ion exchange process reaction tank into a crystal transformation process transition reaction tank; before a next cycle starts, connecting at least one of crystal transformation process transition reaction tanks with molecular sieve raw materials replaced to a tail of a crystal transformation process cycle in sequence, using one of the connected crystal transformation process transition reaction tanks as a last crystal transformation process reaction tank, using the second ion exchange process reaction tank in this cycle as a first ion exchange process reaction tank in a next cycle, and then starting a new cycle; and before the new cycle starts, guaranteeing at least one of the crystal transformation process transition reaction tanks to complete an operation of replacing molecular sieve raw materials for being connected to the tail of the crystal transformation process cycle; and achieving continuous crystal transformation and ion exchange through cycles.

4. The continuous crystal transformation and ion exchange process according to claim 3, characterized in that, after a first cycle is finished, a flow direction of liquid is switched by a valve, a second crystal transformation process reaction tank is used as a first crystal transformation process reaction tank in a next cycle, and a second ion exchange process reaction tank is used as a first ion exchange process reaction tank in the next cycle to start a second cycle; after the second cycle is finished, a third crystal transformation process reaction tank is used as a first crystal transformation process reaction tank in a next cycle, and a third ion exchange process reaction tank is used as a first ion exchange process reaction tank in the next cycle to start a third cycle; and so on, and in all previous cycles, continuous dynamic switching is carried out to keep the number of the crystal transformation process reaction tanks and the number of the ion exchange process reaction tanks unchanged.

5. The continuous crystal transformation and ion exchange process according to claim 3, characterized in that, the new alkali solution comprises at least one of lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide and magnesium hydroxide.

6. The continuous crystal transformation and ion exchange process according to claim 3, characterized in that, the new ion exchange solution is a solution corresponding to target ions in a finished molecular sieve product obtained by an ion exchange process.

7. The continuous crystal transformation and ion exchange process according to claim 3, characterized in that, in a crystal transformation and ion exchange reaction, a corresponding amount of pH adjusting solution is introduced into a corresponding reaction tank to stabilize a pH value of each reaction tank according to a process flow.

8. The continuous crystal transformation and ion exchange process according to claim 7, characterized in that, the pH adjusting solution comprises at least one of lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide and magnesium hydroxide.

9. The continuous crystal transformation and ion exchange process according to claim 3, characterized in that, all reaction tanks are arranged in a space with constant temperature control.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0030] FIG. 1 is a flow chart of a cycle process of Example 1.

DETAILED DESCRIPTION

[0031] The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments. The experimental methods without specific conditions in the Examples are carried out according to conventional methods and conditions.

Example 1

[0032] As shown in FIG. 1, this example includes: M+N reaction tanks which are in serial connection, wherein a feed opening of a latter reaction tank communicates with a discharge opening of a former reaction tank by means of a reaction solution circulation pipeline, and a discharge opening of an M+Nth reaction tank communicates with a feed opening of a first reaction tank by means of a reaction solution circulation pipeline.

[0033] All reaction tanks are each provided with four solution inlet pipelines, three solution outlet pipelines and one reaction solution circulation pipeline, wherein the four solution inlet pipelines are a deionized water inlet pipeline, a new alkali solution inlet pipeline, a new lithium solution inlet pipeline and a pH adjusting solution inlet pipeline, respectively, and the three solution outlet pipelines are a waste water outlet pipeline, a waste alkali solution outlet pipeline and a waste lithium solution outlet pipeline, respectively.

[0034] All reaction tanks are arranged in a space with constant temperature control.

[0035] This example is illustrated by taking FIG. 1 as an example, wherein reaction tanks numbered Z.sub.1 to Z.sub.m are crystal transformation process reaction tanks, and reaction tanks numbered Z.sub.m+1 to Z.sub.m are crystal transformation process transition reaction tanks; reaction tanks numbered L.sub.1 to L.sub.n are lithium-ion exchange process reaction tanks, and reaction tanks numbered L.sub.n+1 to L.sub.N are lithium-ion exchange process transition reaction tanks; and this example is used for the preparation of a lithium-type molecular sieve.

[0036] In one cycle, a new alkali solution is introduced into the reaction tank numbered Z.sub.1 for a crystal transformation reaction, a reaction solution flowing out of the reaction tank Z.sub.1 is introduced into the reaction tank Z.sub.2 as a primary alkali solution to continue the crystal transformation reaction, and a reaction solution flowing out of the reaction tank Z.sub.2 is introduced into the reaction tank Z.sub.3 as a secondary alkali solution to continue the crystal transformation reaction; and so on until a reaction solution flowing out of the reaction tank Z.sub.m−1 is introduced into the reaction tank Z.sub.m as an m−1th alkali solution to continue the crystal transformation reaction, and a reaction solution flowing out of the reaction tank Z.sub.m is discharged as a waste liquid through a waste alkali solution outlet pipeline; after the crystal transformation reaction in the reaction tank Z.sub.1 is sufficient, the reaction tank Z.sub.1 is cleaned with deionized water and is then used as a new lithium-ion exchange process transition reaction tank; and in a next cycle, the reaction tank Z.sub.m+1 cleaned by deionized water is connected to a tail of a crystal transformation process cycle as a last crystal transformation process reaction tank; while for the lithium-ion exchange process reaction tanks, in this cycle, a new lithium solution is introduced into the reaction tank numbered Li for a lithium-ion exchange reaction, a reaction solution flowing out of the reaction tank Li is introduced into the reaction tank L.sub.2 as a primary lithium solution to continue the lithium-ion exchange reaction, and a reaction solution flowing out of the reaction tank L.sub.2 is introduced into the reaction tank L.sub.3 as a secondary lithium solution to continue the lithium-ion exchange reaction; and so on until a reaction solution flowing out of the reaction tank L.sub.n+1 is introduced into the reaction tank L.sub.n as an n−1th lithium solution to continue the lithium-ion exchange reaction, and a reaction solution flowing out of the reaction tank L.sub.n is discharged as a waste liquid through a waste lithium solution outlet pipeline; after the lithium-ion exchange reaction in the reaction tank Li is sufficient, the reaction tank Li is cleaned with deionized water, discharged and replaced with new molecular sieve raw materials to be used as a new crystal transformation process transition reaction tank; and in a next cycle, the heated reaction tank L.sub.n+1 with molecular sieve raw materials replaced is connected to a tail of a lithium-ion exchange process cycle as a last lithium-ion exchange process reaction tank.

[0037] After a first cycle is finished, a flow direction of liquid is switched by a valve, a second crystal transformation process reaction tank is used as a first crystal transformation process reaction tank in a next cycle, and a second lithium-ion exchange process reaction tank is used as a first lithium-ion exchange process reaction tank in the next cycle to start a second cycle; after the second cycle is finished, a third crystal transformation process reaction tank is used as a first crystal transformation process reaction tank in a next cycle, and a third lithium-ion exchange process reaction tank is used as a first lithium-ion exchange process reaction tank in the next cycle to start a third cycle; and so on, and in all previous cycles, continuous dynamic switching is carried out to keep the number of the crystal transformation process reaction tanks and the number of the lithium exchange process reaction tanks unchanged.

[0038] A first crystal transformation process reaction tank in each cycle is a reaction tank where a new alkali solution is introduced, and a first lithium-ion exchange process reaction tank in each cycle is a reaction tank where a new lithium solution is introduced. The new alkali solution is preferably sodium hydroxide or potassium hydroxide. The new lithium solution is preferably lithium sulfate.

[0039] In the above-mentioned crystal transformation and lithium-ion exchange reaction, according to a process flow, a corresponding amount of pH adjusting solution is introduced into a corresponding reaction tank to stabilize a pH value of each reaction tank. The pH adjusting solution is preferably lithium hydroxide.

[0040] In this example, M=8 and N=9; 5 crystal transformation process reaction tanks, 6 lithium-ion exchange process reaction tanks, 3 crystal transformation process transition reaction tanks and 3 lithium-ion exchange process transition reaction tanks are provided; the molecular sieve raw materials are a low-silica sodium-potassium type molecular sieve NaK-LsX; a flow rate of each reaction tank at the corresponding discharge opening is set to be 9 L/min, the time of one cycle is 8 hours, and the lithium-ion exchange rate is 98%-98.5%.

[0041] It should be emphasized that the above is only a preferred example of the present invention, and is not intended to limit the present invention in any form. Any simple changes, equivalent variations and modifications made to the above example according to the technical substance of the present invention are still within the scope of the technical solution of the present invention.