CN212669467U - Catalytic cracking wet flue gas desulfurization waste water cyclic utilization system - Google Patents
Catalytic cracking wet flue gas desulfurization waste water cyclic utilization system Download PDFInfo
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Abstract
The utility model discloses a catalytic cracking wet flue gas desulfurization waste water cyclic utilization system, the water outlet of an ultrafiltration device is connected with the water inlet of a primary ion exchange device, the water outlet of the primary ion exchange device is connected with the water inlet of an electrodialysis concentration device, the concentrated water outlet of the electrodialysis concentration device is connected with the water inlet of a secondary ion exchange device, the water outlet of the secondary ion exchange device is connected with the water inlet of a bipolar membrane electrodialysis device, and the prepared sulfuric acid and sodium hydroxide; a fresh water outlet of the electrodialysis concentration device is connected with a water inlet of the reverse osmosis device, and a reverse osmosis desalination fresh water outlet of the reverse osmosis device is used for producing domestic water in a plant area; and a concentrated water outlet of the reverse osmosis device and the bipolar membrane dilute brine of the bipolar membrane electrodialysis device are connected to a water inlet of the electrodialysis concentration device again. The utility model provides a catalytic cracking wet flue gas desulfurization waste water cyclic utilization system can continue comprehensive treatment to waste water, realizes desulfurization waste water's resourceful cyclic utilization.
Description
Technical Field
The utility model relates to a waste water treatment equipment technical field, more specifically says so and relates to a catalytic cracking wet flue gas desulfurization waste water cyclic utilization system.
Background
The catalytic device in the petrochemical industry is a core device in the oil refining link, and the treatment of the catalytic device regeneration flue gas device adopts the sodium-alkali desulphurization technology at present, namely sodium hydroxide is adopted as an absorbent, and the absorbent reacts with sulfur dioxide in flue gas in a separation device to generate sodium sulfate.
At present, the desulfurization technology has high treatment efficiency, stable effect, low operation cost and simple operation, but the generated desulfurization wastewater can be directly discharged only after simple coagulating sedimentation. The discharged wastewater contains a large amount of salt, the main component of the discharged wastewater is sodium sulfate, the recycling value is not high, and no effective treatment means of zero discharge or recycling exists at present.
Therefore, how to provide a catalytic cracking wet desulphurization wastewater recycling system is a problem that needs to be solved urgently by the technical personnel in the field.
SUMMERY OF THE UTILITY MODEL
In view of this, the utility model provides a catalytic cracking wet flue gas desulfurization waste water cyclic utilization system can continue to carry out comprehensive treatment to waste water, realizes desulfurization waste water's resourceful cyclic utilization.
In order to achieve the above purpose, the utility model adopts the following technical scheme:
a catalytic cracking wet desulphurization waste water recycling system comprises an ultrafiltration device, a primary ion exchange device, an electrodialysis concentration device, a reverse osmosis device, a secondary ion exchange device and a bipolar membrane electrodialysis device; the water outlet of the ultrafiltration device is connected with the water inlet of the primary ion exchange device, the water outlet of the primary ion exchange device is connected with the water inlet of the electrodialysis concentration device, the concentrated water outlet of the electrodialysis concentration device is connected with the water inlet of the secondary ion exchange device, the water outlet of the secondary ion exchange device is connected with the water inlet of the bipolar membrane electrodialysis device, the bipolar membrane electrodialysis device is connected with a pure water replenishing pipeline, and the prepared sulfuric acid and sodium hydroxide are collected; a fresh water outlet of the electrodialysis concentration device is connected with a water inlet of the reverse osmosis device, and a reverse osmosis desalination fresh water outlet of the reverse osmosis device is used for producing domestic water in a factory; and a concentrated water outlet of the reverse osmosis device and the bipolar membrane dilute brine of the bipolar membrane electrodialysis device are connected to a water inlet of the electrodialysis concentration device again.
The utility model pretreats the waste water through the ultrafiltration device and the primary ion exchange device, and then concentrates the waste water through the electrodialysis concentration device, the electrodialysis fresh water enters the reverse osmosis device, the reverse osmosis fresh water can be directly used for producing and living water in a plant area, and the reverse osmosis concentrated water returns to the electrodialysis device for water intake; and after the electrodialysis concentrated water is treated again by the secondary ion exchange device, the electrodialysis concentrated water enters the bipolar membrane electrodialysis device to generate electrochemical reaction to generate sulfuric acid and sodium hydroxide, and finally the resource recycling of the desulfurization wastewater is realized.
Preferably, the ultrafiltration device is made of hollow fibers made of high polymer materials, and the filter membrane is made of one or more of PP, PVDF, PVC and PES.
The beneficial effects of adopting above-mentioned technical scheme are that, filtration membrane surface activation layer is fine and close, and the supporting layer is spongy network structure, so withstand voltage, antipollution, long service life, and can guarantee to produce water quality for a long time, have good separation ability to colloid, suspended particles, colourity, turbidity, bacterium, macromolecular organic matter, guarantee electrodialysis device and bipolar membrane electrodialysis device's normal operating.
Preferably, the electrodialysis concentration device adopts a flat plate type structure, and the membrane material of the electrodialysis membrane stack is one or more of PES, PVC, PE, PS and PP.
The technical scheme has the beneficial effects that the electrodialysis is an electrochemical separation process utilizing the migration effect of ions in a direct current electric field, and is widely applied to the separation of charged media and uncharged media. Electrodialysis is a physical and chemical process for separating ionic solutes from solvents in a solution by utilizing the selective permeability of an anion exchange membrane (A) and a cation exchange membrane (C) to anions and cations in the solution under the action of a direct current electric field. When the sodium sulfate solution passes through the electrodialysis device, ion selective exchange is carried out under the action of the diaphragm and the direct current power plant, concentrated sodium sulfate concentrated water is output, and meanwhile, part of sodium sulfate in the feed liquid does not enter the concentrated water chamber and is output from a feed liquid port in the form of sodium sulfate-containing light salt water.
Preferably, the bipolar membrane electrodialysis device adopts a flat plate type structure, and the membrane material of the electrodialysis membrane stack is one or more of PES, PVC, PE, PS and PP.
The bipolar membrane adopting the technical scheme has the beneficial effect that the bipolar membrane generally consists of an anion exchange resin layer (A), a cation exchange membrane (C) and an intermediate catalyst layer (BP). Under the action of the direct current electric field, water between the cathode film and the anode film composite layer is dissociated into H + and OH-and respectively passes through the anode film and the cathode film to be used as H + and OH-ion sources. When passing through the bipolar membrane electrodialysis device, the concentrated sodium sulfate solution is subjected to ion selective exchange under the action of the diaphragm and the direct current electric field, sulfuric acid and sodium hydroxide are respectively output, and meanwhile, part of sodium sulfate in the feed liquid still enters the acid liquid chamber and the alkali liquid chamber and is output from the feed liquid port in the form of light salt water containing sodium sulfate.
Can know via foretell technical scheme, compare with prior art, the utility model discloses a catalytic cracking wet flue gas desulfurization waste water cyclic utilization device adopts electrodialysis-reverse osmosis-bipolar membrane electrodialysis combined technology to the treatment of sodium-alkali method desulfurization waste water can produce sodium hydroxide and sulfuric acid solution, but sodium hydroxide direct retrieval and utilization is as the desulfurization absorbent, and sulfuric acid solution can directly be used for other with the acid departments in factory. The utility model provides a desulfurization waste water treatment technique has realized waste water zero release and cyclic utilization, when improving the utilization ratio of resource, has reduced the desulfurization absorbent cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a flow chart of the catalytic cracking wet desulphurization wastewater recycling system provided by the utility model.
Fig. 2 is the schematic diagram of the electrodialysis principle in the catalytic cracking wet desulphurization waste water recycling system provided by the utility model.
Fig. 3 is the schematic diagram of the bipolar membrane electrodialysis principle in the catalytic cracking wet desulphurization wastewater recycling system provided by the utility model.
Wherein the reference symbols are:
1-ultrafiltration device, 2-first-stage ion exchange device, 3-electrodialysis concentration device, 4-reverse osmosis device, 5-second-stage ion exchange device and 6-bipolar membrane electrodialysis device.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments in the present invention, all other embodiments obtained by a person skilled in the art without creative work belong to the protection scope of the present invention.
The embodiment of the utility model discloses a catalytic cracking wet flue gas desulfurization waste water recycling device, which comprises an ultrafiltration device 1, a primary ion exchange device 2, an electrodialysis concentration device 3, a reverse osmosis device 4, a secondary ion exchange device 5 and a bipolar membrane electrodialysis device 6; the water outlet of the ultrafiltration device 1 is connected with the water inlet of the primary ion exchange device 2, the water outlet of the primary ion exchange device 2 is connected with the water inlet of the electrodialysis concentration device 3, the concentrated water outlet of the electrodialysis concentration device 3 is connected with the water inlet of the secondary ion exchange device 5, the water outlet of the secondary ion exchange device 5 is connected with the water inlet of the bipolar membrane electrodialysis device 6, the bipolar membrane electrodialysis device 6 is communicated with a pure water replenishing pipeline, and the prepared sulfuric acid and sodium hydroxide are collected; a fresh water outlet of the electrodialysis concentration device 3 is connected with a water inlet of the reverse osmosis device 4, and a reverse osmosis desalination fresh water outlet of the reverse osmosis device 4 is used for producing domestic water in a factory; the concentrated water outlet of the reverse osmosis device 4 and the bipolar membrane dilute brine of the bipolar membrane electrodialysis device 6 are connected to the water inlet of the electrodialysis concentration device 3 again.
The utility model discloses a raw water is sodium alkali method desulfurization waste water, the principal ingredients is sodium sulfate solution (1-10% wt), but contain certain suspended solid and other impurity, and certain hardness has, for guaranteeing the concentrated stability of electrodialysis, at first adopt ultrafiltration device 1 to detach the suspended solid in the raw water, impurity such as colloid, then rethread one-level ion exchange device 2 gets rid of the hardness, the raw water rethread electrodialysis device 3 through refined is concentrated, the concentrated water of electrodialysis gets into the subsequent handling, the weak brine of electrodialysis gets into reverse osmosis degree of depth device 4. The reverse osmosis fresh water can be directly used for producing domestic water in a factory, and the reverse osmosis concentrated water returns to the electrodialysis inflow water. And (3) enabling the electrodialysis concentrated water to pass through a secondary ion exchange system again, further refining the concentrated water, enabling the refined concentrated water to enter a bipolar membrane electrodialysis device to produce sulfuric acid (5-20 wt%) and sodium hydroxide (4-16 wt%), and enabling the bipolar membrane dilute brine to return to electrodialysis inlet water.
Wherein, the ultrafiltration device 1 adopts hollow fiber made of high polymer material, and the filtration membrane is made of one or more of PP, PVDF, PVC and PES. The surface activation layer is compact, the supporting layer is of a spongy network structure, so that the pressure resistance, pollution resistance and long service life are realized, the water quality of produced water can be ensured for a long time, the good separation capability is realized on colloid, suspended particles, chroma, turbidity, bacteria and macromolecular organic matters, and the normal operation of the electrodialysis device and the bipolar membrane electrodialysis device is ensured.
The electrodialysis concentration device 3 or the bipolar membrane electrodialysis device 6 both adopt a flat plate type structure, and the membrane material of the electrodialysis membrane stack is one or more of PES, PVC, PE, PS and PP. Electrodialysis is an electrochemical separation process that utilizes the migration of ions in a direct current electric field, and is widely applied to the separation of charged media and uncharged media. Electrodialysis is a physical and chemical process for separating ionic solutes from solvents in a solution by utilizing the selective permeability of an anion exchange membrane (A) and a cation exchange membrane (C) to anions and cations in the solution under the action of a direct current electric field.
The electrodialysis concentration device 3 adopts a flat plate type structure, and the equipment comprises a membrane, a partition plate, a locking device and a power supply and distribution device; the film base material is selected from one or more of PES, PVC, PE, PS and PP.
The operation principle of the electrodialysis device for wastewater containing sodium sulfate salt is shown in figure 2.
When passing through the electrodialysis concentration device 3, the sodium sulfate solution is subjected to ion selective exchange under the action of the diaphragm and the direct current electric field, concentrated sodium sulfate concentrated water is output, and meanwhile, part of sodium sulfate in the feed liquid does not enter the concentrated water chamber and is output from a feed liquid port in the form of sodium sulfate-containing light salt water.
The bipolar membrane is generally composed of an anion exchange resin layer (a), a cation exchange membrane (C) and an intermediate catalytic layer (BP). Under the action of the direct current electric field, water between the cathode film and the anode film composite layer is dissociated into H + and OH-and respectively passes through the anode film and the cathode film to be used as H + and OH-ion sources.
The bipolar membrane electrodialysis device 6 adopts a flat plate type structure, and the equipment comprises a membrane, a partition plate, a locking device and a power supply and distribution device; the film base material is selected from one or more of PES, PVC, PE, PS and PP.
The operation principle of the bipolar membrane electrodialysis device 6 for the sodium sulfate-containing wastewater is shown in the attached figure 3.
When passing through the bipolar membrane electrodialysis device 6, the concentrated sodium sulfate solution is subjected to ion selective exchange under the action of the diaphragm and the direct current electric field, sulfuric acid and sodium hydroxide are respectively output, and meanwhile, part of sodium sulfate in the feed liquid still enters the acid liquid chamber and the alkali liquid chamber and is output from the feed liquid port in the form of light salt water containing sodium sulfate.
The utility model discloses a catalytic cracking wet flue gas desulfurization waste water cyclic utilization system is that the working process includes following step:
s1, removing impurities such as suspended matters, colloids and the like in the raw water by using an ultrafiltration device to obtain primary raw water;
s2, removing hardness of the primary raw water obtained in the step S1 through a primary ion exchange device to obtain refined raw water;
s3, concentrating the refined raw water obtained in the step S2 through an electrodialysis concentration device, enabling electrodialysis concentrated water to enter a secondary ion exchange device in an amount of 5-25 wt%, and enabling electrodialysis light salt water to enter a reverse osmosis device in an amount of 0.5-5 wt% for deep desalination;
s4, directly using the reverse osmosis fresh water for producing domestic water in a factory, and returning the reverse osmosis concentrated water to the electrodialysis concentration device;
and S5, enabling the electrodialysis concentrated water to pass through a secondary ion exchange device, further refining the concentrated water, enabling the refined concentrated water to enter a bipolar membrane electrodialysis device to produce sulfuric acid and sodium hydroxide, and returning the bipolar membrane dilute brine to the electrodialysis concentration device.
The utility model discloses an embodiment 1:
referring to the attached figure 1, the raw water of 25L/h sodium alkali desulphurization waste water in the embodiment contains 5.4% of sodium sulfate, 25Mg/L of Ca2+, 10Mg/L of Mg2+ and 50Mg/L of SS;
performing primary pretreatment on raw water by using an ultrafiltration device to remove most of SS in the raw water, wherein the SS content in the treated primary raw water is less than 0.5 mg/L;
removing Ca2+ and Mg2+ in the raw water by using a primary ion exchange device to obtain refined raw water, wherein the total amount of Ca2+ and Mg2+ in the refined raw water is less than 0.5 Mg/L;
concentrating the refined raw water by using an electrodialysis device, wherein electrodialysis concentrated water (containing 15% of sodium sulfate) is produced by electrodialysis;
further removing impurities from the electrodialysis concentrated water by a secondary ion exchange device to obtain refined concentrated water, and feeding dilute brine produced by electrodialysis into a reverse osmosis system for further treatment;
the electrodialysis dilute brine is used for producing fresh water through a reverse osmosis system, and the produced reverse osmosis concentrated water (containing 5.4% of sodium sulfate) is returned to the electrodialysis device for secondary concentration;
feeding the refined concentrated water into a bipolar membrane electrodialysis device to obtain a sulfuric acid solution (9.8 wt%) and a sodium hydroxide solution (8 wt%);
the bipolar membrane electrodialysis device needs to be supplemented with pure water at the same time, bipolar membrane dilute brine (containing 5.4% of sodium sulfate) is generated, and the bipolar membrane dilute brine is returned to the electrodialysis device for concentration.
Embodiment 1 adopts electrodialysis-reverse osmosis-bipolar membrane electrodialysis combined technology to treat sodium-alkali desulfurization wastewater, can produce sodium hydroxide and sulfuric acid solution, and sodium hydroxide can be directly recycled as desulfurization absorbent, and sulfuric acid solution can be directly used in other acid places in the plant, so that zero discharge and cyclic utilization of wastewater are realized, and the cost of the desulfurization absorbent is reduced while the utilization rate of resources is improved.
Example 2:
referring to the attached figure 1, the 50L/h sodium alkali desulphurization wastewater raw water in the embodiment contains 2.5% of sodium sulfate, 35Mg/L of Ca2+, 15Mg/L of Mg2+ and 40Mg/L of SS;
performing primary pretreatment on raw water by using an ultrafiltration device to remove most of SS in the raw water, wherein the SS content in the treated primary raw water is less than 0.5 mg/L;
removing Ca2+ and Mg2+ in the raw water by using a primary ion exchange resin system to obtain refined raw water, wherein the total amount of Ca2+ and Mg2+ in the refined raw water is less than 0.5 Mg/L;
concentrating the refined raw water by using an electrodialysis device, wherein electrodialysis concentrated water (containing 10% of sodium sulfate) is produced by electrodialysis;
further removing impurities from the electrodialysis concentrated water by a secondary ion exchange device to obtain refined concentrated water, and feeding dilute brine produced by electrodialysis into a reverse osmosis system for further treatment;
the electrodialysis dilute brine is used for producing fresh water through a reverse osmosis system, and the produced reverse osmosis concentrated water (containing 2.5 percent of sodium sulfate) is returned to the electrodialysis device for secondary concentration;
feeding the refined concentrated water into a bipolar membrane electrodialysis device to obtain a sulfuric acid solution (7.35 wt%) and a sodium hydroxide solution (6 wt%);
the bipolar membrane electrodialysis device needs to be supplemented with pure water at the same time, bipolar membrane dilute brine (containing 2.5% of sodium sulfate) is generated, and the bipolar membrane dilute brine is returned to the electrodialysis device for concentration.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. A catalytic cracking wet desulphurization wastewater recycling system is characterized by comprising an ultrafiltration device (1), a primary ion exchange device (2), an electrodialysis concentration device (3), a reverse osmosis device (4), a secondary ion exchange device (5) and a bipolar membrane electrodialysis device (6);
the water outlet of the ultrafiltration device (1) is connected with the water inlet of the primary ion exchange device (2), the water outlet of the primary ion exchange device (2) is connected with the water inlet of the electrodialysis concentration device (3), the concentrated water outlet of the electrodialysis concentration device (3) is connected with the water inlet of the secondary ion exchange device (5), the water outlet of the secondary ion exchange device (5) is connected with the water inlet of the bipolar membrane electrodialysis device (6), the bipolar membrane electrodialysis device (6) is communicated with a pure water replenishing pipeline, and the prepared sulfuric acid and sodium hydroxide are collected; a fresh salt water outlet of the electrodialysis concentration device (3) is connected with a water inlet of the reverse osmosis device (4), and a reverse osmosis desalination fresh water outlet of the reverse osmosis device (4) is used for producing domestic water in a plant area; and a concentrated water outlet of the reverse osmosis device (4) and the bipolar membrane dilute brine of the bipolar membrane electrodialysis device (6) are connected to the water inlet of the electrodialysis concentration device (3) again.
2. The system for recycling the catalytic cracking wet desulphurization wastewater as recited in claim 1, wherein the ultrafiltration device (1) is made of hollow fiber made of high polymer material, and the filtration membrane is made of one of PP, PVDF, PVC and PES.
3. The system for recycling the catalytic cracking wet desulphurization wastewater according to claim 1, wherein the electrodialysis concentration device (3) is of a flat plate type structure, and the membrane material of the electrodialysis membrane stack is one of PES, PVC, PE, PS and PP.
4. The system for recycling the catalytic cracking wet desulphurization wastewater according to claim 1, wherein the bipolar membrane electrodialysis device (6) adopts a flat plate structure, and the membrane material of the electrodialysis membrane stack is one of PES, PVC, PE, PS and PP.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716095A (en) * | 2022-03-25 | 2022-07-08 | 浙江彤然技术有限公司 | Organic silicon wastewater treatment system and treatment method thereof |
| CN114873814A (en) * | 2022-04-08 | 2022-08-09 | 中国石油化工股份有限公司 | Resourceful treatment method and device for catalytic cracking flue gas desulfurization wastewater |
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2020
- 2020-08-04 CN CN202021595070.3U patent/CN212669467U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716095A (en) * | 2022-03-25 | 2022-07-08 | 浙江彤然技术有限公司 | Organic silicon wastewater treatment system and treatment method thereof |
| CN114873814A (en) * | 2022-04-08 | 2022-08-09 | 中国石油化工股份有限公司 | Resourceful treatment method and device for catalytic cracking flue gas desulfurization wastewater |
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