CN111825266A - Catalytic cracking wet desulphurization waste water recycling system and method - Google Patents
Catalytic cracking wet desulphurization waste water recycling system and method Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 43
- 238000004064 recycling Methods 0.000 title claims abstract description 28
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 149
- 238000000909 electrodialysis Methods 0.000 claims abstract description 122
- 239000012528 membrane Substances 0.000 claims abstract description 67
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 41
- 238000005342 ion exchange Methods 0.000 claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012267 brine Substances 0.000 claims abstract description 18
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 18
- 239000013505 freshwater Substances 0.000 claims abstract description 14
- 238000010612 desalination reaction Methods 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 7
- 239000000084 colloidal system Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000012510 hollow fiber Substances 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- -1 suspended matters Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 27
- 229910052938 sodium sulfate Inorganic materials 0.000 description 26
- 235000011152 sodium sulphate Nutrition 0.000 description 26
- 239000000243 solution Substances 0.000 description 21
- 238000006477 desulfuration reaction Methods 0.000 description 13
- 230000023556 desulfurization Effects 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000003513 alkali Substances 0.000 description 9
- 230000005684 electric field Effects 0.000 description 9
- 230000002745 absorbent Effects 0.000 description 8
- 239000002250 absorbent Substances 0.000 description 8
- 230000009471 action Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005341 cation exchange Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003011 anion exchange membrane Substances 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
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- 230000000750 progressive effect Effects 0.000 description 1
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- 238000004062 sedimentation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a catalytic cracking wet desulphurization wastewater recycling system, wherein a water outlet of an ultrafiltration device is connected with a water inlet of a primary ion exchange device, a water outlet of the primary ion exchange device is connected with a water inlet of an electrodialysis concentration device, a concentrated water outlet of the electrodialysis concentration device is connected with a water inlet of a secondary ion exchange device, a water outlet of the secondary ion exchange device is connected with a water inlet of a bipolar membrane electrodialysis device, and 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 invention provides a catalytic cracking wet desulphurization waste water recycling system and method, which can continuously carry out comprehensive treatment on waste water and realize resource recycling of desulphurization waste water.
Description
Technical Field
The invention relates to the technical field of wastewater treatment equipment, in particular to a catalytic cracking wet desulphurization wastewater recycling system and a catalytic cracking wet desulphurization wastewater recycling method.
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 system and a method for recycling catalytic cracking wet desulphurization waste water is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a system and a method for recycling catalytic cracking wet desulphurization wastewater, which can continuously perform comprehensive treatment on the wastewater and realize resource recycling of the desulphurization wastewater.
In order to achieve the purpose, the invention 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.
According to the invention, wastewater is pretreated by an ultrafiltration device and a primary ion exchange device, and then is concentrated by an electrodialysis concentration device, electrodialysis light salt water enters a reverse osmosis device, reverse osmosis fresh water can be directly used for producing and living water in a plant area, and reverse osmosis concentrated water returns to the electrodialysis device for water inlet; 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 or 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 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.
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. 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.
Wherein, the electrodialysis concentrated water accounts for 5-25 wt% by weight, and the electrodialysis weak brine accounts for 0.5-5 wt% by weight.
The invention also provides a recycling method of the catalytic cracking wet desulphurization waste water, which adopts the catalytic cracking wet desulphurization waste water recycling device of the claim and comprises the following steps:
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 by an electrodialysis concentration device, feeding electrodialysis concentrated water with the weight percentage of 5-25 wt% into a secondary ion exchange device, and feeding electrodialysis fresh salt water with the weight percentage of 0.5-5 wt% into a reverse osmosis device 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.
According to the technical scheme, compared with the prior art, the invention discloses and provides the device and the method for recycling the catalytic cracking wet desulphurization wastewater, the electrodialysis-reverse osmosis-bipolar membrane electrodialysis combined technology is adopted to treat the sodium-alkali desulphurization wastewater to produce sodium hydroxide and sulfuric acid solution, the sodium hydroxide can be directly recycled as a desulphurization absorbent, and the sulfuric acid solution can be directly used for other acid sites in a plant area. The desulfurization wastewater treatment technology provided by the invention realizes zero discharge and cyclic utilization of wastewater, improves the utilization rate of resources and reduces the cost of the desulfurization absorbent.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings 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 process flow diagram of a catalytic cracking wet desulfurization waste water recycling system provided by the invention.
FIG. 2 is a schematic diagram of the electrodialysis principle in the catalytic cracking wet desulphurization wastewater recycling system provided by the invention.
FIG. 3 is a schematic diagram of the bipolar membrane electrodialysis principle in the catalytic cracking wet desulphurization wastewater recycling system provided by the invention.
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 clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a catalytic cracking wet desulphurization 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 raw water is sodium-alkali desulfurization wastewater, the main component of the raw water is sodium sulfate solution (1-10 wt%), but the raw water contains certain suspended matters and other impurities and has certain hardness, in order to ensure the stability of electrodialysis concentration, firstly, an ultrafiltration device 1 is adopted to remove the suspended matters, colloid and other impurities in the raw water, then, a primary ion exchange device 2 is adopted to remove the hardness, the refined raw water is concentrated by an electrodialysis device 3, electrodialysis concentrated water enters a subsequent process, and electrodialysis dilute brine enters a reverse osmosis 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 invention also discloses a recycling method of the catalytic cracking wet desulphurization waste water, and the device for recycling the catalytic cracking wet desulphurization waste water comprises the following steps:
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.
Example 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 claimed 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 or more 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) or the bipolar membrane electrodialysis device (6) both adopt a flat plate structure, and the membrane material of the electrodialysis membrane stack is one or more of PES, PVC, PE, PS and PP.
4. A catalytic cracking wet desulphurization waste water recycling method is characterized in that the catalytic cracking wet desulphurization waste water recycling device of any one of claims 1 to 3 is adopted, and the method comprises the following steps:
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 with the weight percentage of 5-25% to enter a secondary ion exchange device, and enabling electrodialysis light salt water with the weight percentage of 0.5-5% to enter a reverse osmosis device 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.
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| 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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