System for removing caking of ion exchange resin for water treatment in sec-butyl alcohol production
By using sec-butanol soaking in sec-butanol production, the ion exchange capacity of the resin is restored, the resin agglomeration problem is solved, the production cost is reduced and operation is simplified.
Patent Information
- Application Number
- CN202422392898.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-30
- Publication Date
- 2025-08-12
- Estimated Expiration
- 2034-09-30
AI Technical Summary
In the production process of sec-butanol, ion exchange resins are prone to agglomeration of self-polymers generated by butene hydration reaction, resulting in resin failure and increased production costs.
By introducing the sec-butanol feed pipeline at the bottom of the debutylene tower of the hydration reaction device, sec-butanol flows into the cation exchanger and anion exchanger, soaking with sec-butanol and circulating to remove the agglomeration resin, restoring the ion exchange capability of the resin.
Rapidly dissolve the autopolymer, restore the ion exchange capacity of the resin, reduce the frequency of resin replacement, reduce production costs, and reduce the organic content in the wastewater through sec-butanol recovery, which is simple to operate and low cost.
Smart Images
Figure CN223209486U_ABST
Abstract
Description
Technical Field
[0001] The utility model relates to the technical field of secondary butanol production, in particular to a system for removing ion exchange resin agglomerates for water treatment in secondary butanol production. Background Art
[0002] The butene hydration reaction uses high-purity butene and process water as raw materials. Under specific temperature and pressure conditions, the butene partially reacts with water to produce sec-butanol in an adiabatic reactor equipped with a heat-resistant, strongly acidic cation exchange resin hydration catalyst. The resulting water enters a circulating water azeotropic column to recover the sec-butanol. The bottom water enters the water treatment process, where it first passes through a fixed-bed cation exchanger to remove cations and adsorb suspended solids. It then passes through a fixed-bed anion exchanger to remove anions, ensuring that the process water returned to the unit meets standards.
[0003] During normal operation, the anion content in the process circulating water is high, requiring continuous treatment through an anion exchanger. Therefore, two anion exchangers are typically installed, one in operation and one in standby. However, the cation content in the process circulating water rises more slowly, so a single cation exchanger is sufficient. The cation exchanger is filled with the strong-acid macroporous resin D-001Z, while the anion exchanger is filled with the acrylic gel resin IRA67RF. Both resins are designed for use below 100°C.
[0004] During the hydration reaction, because the butene raw material contains a small amount of butadiene and isobutylene components, some self-polymers that are prone to coking will be produced. These self-polymers flow with the process water at high temperatures, but when they reach the cation exchanger and anion exchanger, due to the drop in temperature, they are likely to agglomerate with the resin in the cation exchanger and anion exchanger, causing the pressure difference between the cation exchanger and the anion exchanger to increase, making it difficult to transfer the resin during regeneration and often clogging the resin transfer pipeline. In addition, agglomeration will also cause the resin to fail, and new resin can only be replaced, which increases production costs. Utility Model Content
[0005] The technical problem to be solved by the utility model is: to overcome the shortcomings of the existing technology and provide a system for removing ion exchange resin agglomerates for water treatment in the production of sec-butanol, which can realize that when the resin agglomerates, the autopolymers generated in the butene hydration reaction process are quickly dissolved by soaking and circulating the sec-butanol, and the ion exchange capacity of the resin is restored by resin regeneration.
[0006] The technical solution of the utility model is:
[0007] The system for removing ion exchange resin agglomerates used for water treatment in the production of sec-butyl alcohol comprises a cation regeneration tower, a cation exchanger, a first anion exchanger, a second anion exchanger, a circulating water azeotropic tower and a debutenizer. The cation regeneration tower is connected to the cation exchanger via a pipeline, the cation exchanger is connected to the first anion exchanger and the second anion exchanger via pipelines, the bottom of the circulating water azeotropic tower is connected to the water inlet of the cation exchanger via a water inlet pipeline, and the bottom of the debutenizer is connected to a bottom extraction pipeline; , anion exchanger 1 and anion exchanger 2 are respectively connected to the upper water inlet pipeline and the nitrogen pipeline; the bottom of the debutenizer tower is respectively connected to the sec-butanol feed ports of the cation exchanger, anion exchanger 1 and anion exchanger 2 through the sec-butanol feed pipeline; the cation exchanger, anion exchanger 1 and anion exchanger 2 are respectively connected to the sec-butanol storage tank through the sec-butanol return pipeline 1; the cation exchanger, anion exchanger 1 and anion exchanger 2 are respectively connected to the circulating water azeotropic tower through the sec-butanol return pipeline 2.
[0008] Preferably, a control valve is provided on the tower bottom production pipeline.
[0009] Preferably, a flow meter is provided on the sec-butanol return pipeline 1.
[0010] Preferably, a heat exchanger 1 is connected to the water inlet pipeline.
[0011] Preferably, the sec-butanol feed pipeline is connected to a second heat exchanger.
[0012] Preferably, the anion exchanger 1 and the anion exchanger 2 are respectively connected to a circulating water inlet jumper.
[0013] Preferably, a tower bottom production pump is connected to the water inlet pipeline.
[0014] Preferably, the circulating water azeotropic column is connected to a reboiler 1.
[0015] Preferably, the debutenizer is connected to a second reboiler.
[0016] Compared with the prior art, the present invention has the following beneficial effects:
[0017] 1. The utility model relates to a system for removing agglomerated ion exchange resin for water treatment in the production of sec-butanol. A sec-butanol feed line is drawn out from the bottom of a dealkenizer in a hydration reaction unit to allow the sec-butanol to flow into a cation exchanger, a first anion exchanger, and a second anion exchanger. The sec-butanol is then soaked and circulated to remove agglomerated resin, thereby rapidly dissolving autopolymers generated during the butene hydration reaction. The ion exchange capacity of the resin is restored by resin regeneration, effectively preventing the influence of the butene hydration reaction autopolymers on the water treatment ion exchange resin and resolving the problem of ion exchange resin agglomeration without replacing the resin.
[0018] 2. In the utility model, sec-butanol and water are miscible. The water after washing the resin enters the circulating water azeotropic tower, is concentrated in the sec-butanol refining process, and is added to the sec-butanol product. The sec-butanol is recovered, and the wastewater discharged at the bottom of the tower has a low sec-butanol content, has no impact on the environment and wastewater, and has the advantages of simple operation and low recovery cost.
[0019] 3. The utility model uses nitrogen to pressurize high-purity sec-butanol into the sec-butanol storage tank, ensuring that there is no large amount of water in the sec-butanol, ensuring that the sec-butanol refining process operates stably without causing production fluctuations. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] Figure 1 The utility model is a schematic structural diagram of a system for removing ion exchange resin agglomerates for water treatment in the production of sec-butanol.
[0021] In the figure, 1. Cation regeneration tower; 2. Cation exchanger; 3. Anion exchanger 1; 4. Anion exchanger 2; 5. Circulating water azeotropic tower; 501. Reboiler 1; 6. Decabutene tower; 601. Reboiler 2; 602. Bottom extraction pipeline; 7. Water inlet pipeline; 8. Upper water inlet pipeline; 9. Nitrogen pipeline; 10. Sec-butanol feed pipeline; 11. Sec-butanol return pipeline 1; 12. Sec-butanol return pipeline 2; 13. Control valve; 14. Heat exchanger 1; 15. Heat exchanger 2; 16. Bottom extraction pump; 17. Process water discharge pipeline; 18. Circulating water inlet crossover line. DETAILED DESCRIPTION
[0022] In order to enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.
[0023] Example 1
[0024] like Figure 1As shown, this embodiment provides a system for removing ion exchange resin agglomerates for water treatment in the production of secondary butanol, comprising a cation regeneration tower 1, a cation exchanger 2, an anion exchanger 1 3, an anion exchanger 2 4, a circulating water azeotropic tower 5 and a debutene tower 6, wherein the cation regeneration tower 1 is connected to the cation exchanger 2 via a pipeline, the cation exchanger 2 is connected to the anion exchanger 1 3 and the anion exchanger 2 4 via pipelines, and the anion exchanger 1 3 and the anion exchanger 2 4 are connected to a process water discharge pipe. Line 17, of which two anion exchangers 3 are in use and one is in standby; the bottom of the circulating water azeotropic tower 5 is connected to the water inlet of the cation exchanger 2 through the water inlet pipeline 7, and the water inlet pipeline 7 is connected to the bottom extraction pump 16 and the heat exchanger 14; the bottom of the debutenizer 6 is connected to the bottom extraction pipeline 602, which is used to transport the sec-butanol extracted from the bottom of the tower to the sec-butanol storage tank, and the bottom extraction pipeline 602 is provided with a control valve 13; the circulating water azeotropic tower 5 and the debutenizer 6 are respectively connected to the reboiler 1 501 and the reboiler 2 601.
[0025] The cation exchanger 2, the anion exchanger 1 3 and the anion exchanger 2 4 are respectively connected to the upper water inlet pipeline 8 and the nitrogen pipeline 9; the bottom of the debutenizer 6 is respectively connected to the sec-butanol feed ports of the cation exchanger 2, the anion exchanger 1 3 and the anion exchanger 2 4 via the sec-butanol feed pipeline 10, and the sec-butanol feed pipeline 10 is connected to the heat exchanger 2 15; the cation exchanger 2, the anion exchanger 1 3 and the anion exchanger 2 4 are respectively connected to the sec-butanol storage tank via the sec-butanol return pipeline 11, and the sec-butanol return pipeline 11 is provided with a flow meter; the cation exchanger 2, the anion exchanger 1 3 and the anion exchanger 2 4 are respectively connected to the circulating water azeotropic tower 5 via the sec-butanol return pipeline 2 12.
[0026] Working principle:
[0027] First, the cation exchanger 2, anion exchanger 1 3 or anion exchanger 2 4 is cut out and emptied (i.e., the process circulating water therein is drained), and nitrogen is introduced through the nitrogen pipeline 9 to blow out the remaining water therein, and the valves on the water inlet pipeline 7 of the cation exchanger 2, anion exchanger 1 3 or anion exchanger 2 4 and the sec-butanol return pipeline 1 11 and the sec-butanol return pipeline 2 12 are closed, and the vent valve of the cation exchanger 2, anion exchanger 1 3 or anion exchanger 2 4 is opened. At this time, the sec-butanol product at the bottom of the debutenizer 6 is cooled by the heat exchanger 2 15. Next, the sec-butanol flows through sec-butanol feed line 10 into cation exchanger 2, anion exchanger 3, or anion exchanger 4. After contacting and fully soaking the resin for 8 hours, the sec-butanol gradually dissolves the aggregates in the resin. The valve on sec-butanol return line 11 is then opened, and control valve 13 on bottom extraction line 602 of debutenizer 6 is appropriately closed to control the flow rate of sec-butanol flowing through cation exchanger 2, anion exchanger 3, or anion exchanger 4 to 3 t / h. After the circulation time reaches 8 hours, the valve on sec-butanol feed line 10 is closed. Subsequently, nitrogen line 9 is opened to pressurize cation exchanger 2, anion exchanger 3, or anion exchanger 4 to 0.4 MPa. The remaining high-purity sec-butanol is then pumped into the sec-butanol storage tank via sec-butanol return line 11. After the nitrogen is compressed, the valve on the nitrogen connection is closed to relieve the pressure of the cation exchanger 2, the anion exchanger 1 3 or the anion exchanger 2 4. Then, the upper water inlet line 8 of the cation exchanger 2, the anion exchanger 1 3 or the anion exchanger 2 4 is opened and filled with water. The vent valve is closed and the residual sec-butanol in the cation exchanger 2, the anion exchanger 1 3 or the anion exchanger 2 4 is washed with purified water. The sec-butanol is returned to the circulating water azeotropic column 5 through the sec-butanol return line 2 12, concentrated in the sec-butanol refining step, and added to the sec-butanol product. The sec-butanol is recovered. The content of sec-butanol in the bottom water of the circulating water azeotropic column 5 is less than 0.01 wt.%, which has no impact on the environment and sewage. The operation is simple and the recovery cost is low. At the same time, anion exchanger 1 3 and anion exchanger 2 4 are respectively connected to a circulating water inlet jumper 18. When the cation exchanger needs to be cut out for regeneration or soaked in sec-butanol and circulated, the circulating water inlet jumper 18 can be opened to allow the process circulating water to pass through the circulating water inlet jumper 18 and directly enter the anion exchanger 1 3 or the anion exchanger 2 4, remove the anions in the process circulating water, and then return to the process circulating water tank.
Claims
1. A system for removing ion exchange resin agglomerates for water treatment in the production of secondary butanol, comprising a cation regeneration tower (1), a cation exchanger (2), a first anion exchanger (3), a second anion exchanger (4), a circulating water azeotropic tower (5) and a debutenizer (6), wherein the cation regeneration tower (1) is connected to the cation exchanger (2) via a pipeline, the cation exchanger (2) is connected to the first anion exchanger (3) and the second anion exchanger (4) via pipelines, the bottom of the circulating water azeotropic tower (5) is connected to the water inlet of the cation exchanger (2) via a water inlet pipeline (7), and the bottom of the debutenizer (6) is connected to a bottom extraction pipeline (602); characterized in that The cation exchanger (2), the anion exchanger (1) (3) and the anion exchanger (2) (4) are respectively connected to an upper water inlet pipeline (8) and a nitrogen pipeline (9); the bottom of the debutanol tower (6) is respectively connected to the sec-butanol feed ports of the cation exchanger (2), the anion exchanger (1) (3) and the anion exchanger (2) (4) via a sec-butanol feed pipeline (10); the cation exchanger (2), the anion exchanger (1) (3) and the anion exchanger (2) (4) are respectively connected to a sec-butanol storage tank via a sec-butanol return pipeline (11); and the cation exchanger (2), the anion exchanger (1) (3) and the anion exchanger (2) (4) are respectively connected to a circulating water azeotropic tower (5) via a sec-butanol return pipeline (12).
2. The system for removing ion exchange resin agglomerates for water treatment in the production of sec-butyl alcohol according to claim 1, wherein: The tower bottom extraction pipeline (602) is provided with a control valve (13).
3. The system for removing ion exchange resin agglomerates for water treatment in the production of sec-butyl alcohol according to claim 1, wherein: The sec-butyl alcohol return pipeline 1 (11) is provided with a flow meter.
4. The system for removing ion exchange resin agglomerates for water treatment in the production of sec-butyl alcohol according to claim 1, wherein: The water inlet pipeline (7) is connected to a heat exchanger (14).
5. The system for removing ion exchange resin agglomerates for water treatment in the production of sec-butyl alcohol according to claim 1, wherein: The sec-butyl alcohol feed pipeline (10) is connected to a second heat exchanger (15).
6. The system for removing ion exchange resin agglomerates for water treatment in the production of sec-butyl alcohol according to claim 1, wherein: The anion exchanger 1 (3) and the anion exchanger 2 (4) are respectively connected to a circulating water inlet crossover line (18).
7. The system for removing ion exchange resin agglomerates for water treatment in the production of sec-butyl alcohol according to claim 1, characterized in that: The water inlet pipeline (7) is connected to a tower bottom extraction pump (16).
8. The system for removing ion exchange resin agglomerates for water treatment in the production of sec-butyl alcohol according to claim 1, wherein: The circulating water azeotropic column (5) is connected to a reboiler 1 (501).
9. The system for removing ion exchange resin agglomerates for water treatment in the production of sec-butyl alcohol according to claim 1, wherein: The debutene tower (6) is connected to a second reboiler (601).