CN116855965B - PTA alkali recovery furnace molten salt separation and purification device - Google Patents
PTA alkali recovery furnace molten salt separation and purification device Download PDFInfo
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- CN116855965B CN116855965B CN202311127332.1A CN202311127332A CN116855965B CN 116855965 B CN116855965 B CN 116855965B CN 202311127332 A CN202311127332 A CN 202311127332A CN 116855965 B CN116855965 B CN 116855965B
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- 150000003839 salts Chemical class 0.000 title claims abstract description 65
- 238000000926 separation method Methods 0.000 title claims abstract description 34
- 238000011084 recovery Methods 0.000 title claims abstract description 28
- 239000003513 alkali Substances 0.000 title claims abstract description 24
- 238000000746 purification Methods 0.000 title claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 238000003723 Smelting Methods 0.000 claims abstract description 24
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 24
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002351 wastewater Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 238000005192 partition Methods 0.000 claims description 14
- 230000001502 supplementing effect Effects 0.000 claims description 14
- 239000000498 cooling water Substances 0.000 claims description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003546 flue gas Substances 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 159000000000 sodium salts Chemical class 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 2
- 239000000155 melt Substances 0.000 abstract description 2
- 230000009466 transformation Effects 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 38
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 30
- 229910000029 sodium carbonate Inorganic materials 0.000 description 19
- 239000012071 phase Substances 0.000 description 17
- 239000011734 sodium Substances 0.000 description 8
- 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 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
Abstract
The application relates to the technical field of separation and purification of sodium salt, in particular to a molten salt separation and purification device of a PTA alkali recovery furnace, which is divided into four compartments of a smelting chamber, an electrolysis chamber, a balance chamber and a liquid outlet chamber, wherein the smelting chamber is communicated with a furnace chamber of an incinerator, molten salt generated by burning PTA wastewater falls down and sequentially enters the four compartments of the smelting chamber and the like, gas generated by electrolysis in the electrolysis chamber is discharged and cooled and condensed to recover bromine simple substance, and the rest gas is returned to the electrolysis chamber. The method has high recovery rate of separated salt, wherein the bromine recovery rate can reach more than 95 percent, and the concentration of bromine in the melt does not influence the separation and extraction efficiency and the purity of the product. The device can be coupled with the existing equipment, has low transformation cost and operation cost, and can reduce carbon emission.
Description
Technical Field
The application relates to the technical field of separation and purification of sodium salt, in particular to a separation and purification device for molten salt of a PTA alkali recovery furnace.
Background
The chemical PTA multi-source waste heat conversion recycling energy-saving device is mainly used for recycling the chemical PTA multi-source waste, and adopts a mode of combining evaporation concentration, an alkali incinerator, flue gas energy-saving purification and salt separation purification. The waste water of the PTA device is subjected to an evaporation concentration process to form high-concentration waste water with the concentration of 50% -60%, and then the high-concentration waste water is conveyed into an alkali incinerator through a liquid phase for resource incineration. The top of the alkali incinerator is provided with a waste liquid spray gun, the concentrated PTA waste water is sprayed into a hearth through the waste liquid spray gun to be incinerated, high-temperature flue gas with the temperature of more than 1100 ℃ generated by incineration is firstly recycled by a waste heat recycling system to produce steam, and then the steam enters a flue gas purification system to be treated and then is discharged after reaching standards.
The ash produced by the PTA incinerator is a mixture of sodium carbonate and sodium bromide, in order to improve the utilization value of the ash, the sodium carbonate and the sodium bromide in the ash are required to be separated respectively, the molten slag produced by common incineration enters a salt separation system for sodium salt recovery after cooling and compatibility, and the salt separation usually adopts processes of evaporation crystallization, cooling crystallization, membrane separation and the like, for example, publication numbers CN112811444B, CN114380441A and CN113461199A. In either of the above separation methods, a large additional energy consumption is required, and the separation effect is general. In addition, the value of sodium bromide in ash slag produced by the PTA incinerator is far higher than that of sodium carbonate, but the sodium bromide is difficult to separate and low in recovery rate due to low content of the sodium bromide, and when the sodium bromide accounts for a low proportion to the lower limit of salt separation, the sodium bromide cannot be separated, so that the purity of the sodium carbonate is further influenced.
Disclosure of Invention
Aiming at the technical problems in the prior art, the application provides a separation and purification device for molten salt of a PTA alkali recovery furnace, which is mainly applicable to the situation that the PTA device by-product waste liquid and molten slag generated after solid waste is incinerated are used for separating and purifying sodium carbonate and sodium bromide.
In order to achieve the above purpose, the present application is realized by the following technical scheme:
the application provides a molten salt separation and purification device of a PTA alkali recovery furnace, wherein the molten salt separation and purification device 1 is arranged at the bottom of an incinerator 29 and is separated by a first transverse plate 26, and the molten salt separation and purification device 1 is transversely divided into four compartments, namely a smelting chamber 2, an electrolysis chamber 3, a balance chamber 4 and a liquid outlet chamber 5; the smelting chamber 2 is communicated with the incinerator 29, molten salt generated by burning PTA wastewater falls down and is converged into the smelting chamber 2 by the first transverse plate 26, a first vertical plate 27 is arranged between the smelting chamber 2 and the electrolysis chamber 3, the upper end of the first vertical plate 27 is connected with the first transverse plate 26, and a channel 15 from the smelting chamber to the lower part of the electrolysis chamber is formed by the lower end of the first vertical plate 27 and the bottom of the molten salt separation and purification device 1 at intervals; the electrolysis chamber 3 is divided into an anode chamber 31 and a cathode chamber 32 from left to right by a second vertical plate 28, the top end of the second vertical plate 28 is connected with the first transverse plate 26, the lower parts of the anode chamber 31 and the cathode chamber 32 are communicated, the anode chamber 31 and the cathode chamber 32 are respectively provided with a corresponding discharge electrode 6 for electrolyzing molten salt, the upper parts of the anode chamber 31 and the cathode chamber 32 are respectively provided with an anode cavity 24 and a cathode cavity 25, the anode cavity 24 is provided with a first electrolysis chamber gas-phase circulation pipe 7 for discharging electrolysis gas, the electrolysis gas is cooled and condensed to recover bromine simple substance, and the rest gas is returned to the space between the discharge electrodes 6 of the electrolysis chamber 3; a first partition wall 19 is arranged between the electrolytic chamber 3 and the balance chamber 4, a channel 16 from the electrolytic chamber to the middle of the balance chamber is arranged in the middle of the first partition wall 19, and a gas supplementing pipe 21 for supplementing carbon dioxide is arranged at the bottom of the balance chamber 4.
Specifically, the electrolytic cell 3 is an anode cell 31 on the side of the melting cell 2, and a cathode cell 32 on the side of the electrolytic cell 3 near the balance cell 4.
Specifically, the first electrolytic chamber gas-phase circulation pipe 7 is connected with the heat exchanger 8 and the gas-liquid separator 9 in sequence, the heat exchanger 8 and the gas-liquid separator 9 are respectively connected with the bromine storage tank 10, and the gas-liquid separator 9 returns the separated gas to the space between the discharge electrodes 6 of the electrolytic chamber 3 through the second electrolytic chamber gas-phase circulation pipe 30.
In particular, the heat exchanger 8 is provided with a circulating cooling water inlet 12 and a circulating cooling water outlet 11 for cooling water to enter and exit, and a circulating fan 13 for providing circulating power is arranged in the gas-phase circulating pipe of the electrolytic chamber.
In particular, the cathode cavity 25 is provided with a cathode cavity balance tube 23 for communicating with the furnace chamber of the incinerator 29.
In particular, a second partition wall 14 is arranged between the balancing chamber 4 and the liquid outlet chamber 5, and a channel 17 from the balancing chamber to the liquid outlet chamber is arranged in the middle of the second partition wall 14.
In particular, the upper cavity of the balancing chamber 4 is provided with a balancing chamber gas-phase balancing pipe 22 for communication with the furnace chamber of the incinerator 29.
In particular, the air supplementing pipe 21 draws the clean flue gas generated by burning in the incinerator 29 and processed through the air supplementing fan 20, and the clean flue gas is led into the balance chamber 4.
In particular, the first cross plate 26 is inclined by 5-10 degrees.
In particular, the side wall of the liquid outlet chamber 5 is provided with a liquid outlet chute 18.
The technical scheme has the following advantages or beneficial effects: the method has high recovery rate of separated salt, wherein the bromine recovery rate can reach more than 95 percent, and the concentration of bromine in the melt does not influence the separation and extraction efficiency and the purity of the product. The device can be coupled with the existing equipment, has low reconstruction cost, and has short process flow, low investment and low operation cost. The method can reduce carbon emission of corresponding volume while recovering bromine. The device directly separates and purifies molten sodium bromide and sodium carbonate, reduces the subsequent steps, solves the energy loss caused by salt separation by cooling, dissolving and crystallizing molten salt, and can reduce the consumption of 4 tons of fresh steam and 200 tons of circulating cooling water per ton of molten salt. Compared with the traditional salt separation process, the steam consumption can be reduced by 100%, the electricity consumption can be reduced by more than 90%, and the circulating cooling water can be reduced by more than 70%. Of course, not all of the advantages described above are necessarily achieved at the same time by any one of the solutions of the application.
Drawings
Fig. 1 is a schematic structural view of a molten salt separation and purification apparatus of a PTA alkali recovery furnace and an incinerator 29 according to an embodiment of the present application.
Fig. 2 is a schematic structural view of a molten salt separation and purification apparatus of a PTA alkali recovery furnace according to an embodiment of the present application.
Wherein, 1-molten salt separating and purifying device; 2-a smelting chamber; 3-an electrolysis chamber; a 4-balancing chamber; 5-a liquid outlet chamber; 6-discharging electrode; 7-a first electrolysis chamber gas circulation tube; 8-a heat exchanger; 9-a gas-liquid separator; 10-bromine storage tank; 11-a circulating cooling water outlet; 12-a circulating cooling water inlet; 13-a circulating fan; 14-a second partition; 15-a lower passage from the smelting chamber to the electrolysis chamber; 16-a middle channel from the electrolysis chamber to the balance chamber; 17-a middle channel from the balance chamber to the liquid outlet chamber; 18-a liquid outlet chute; 19-a first partition; 20-an air supplementing fan; 21-an air supplementing pipe; 22-balancing chamber gas phase balancing pipe; 23-cathode cavity balance tube; 24-anode cavity; 25-cathode cavity; 26-a first cross plate; 27-a first riser; 28-a second riser; 29-an incinerator; 30-a second electrolysis chamber gas circulation tube; 31-an anode chamber; 32-cathode chamber.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below with reference to the accompanying drawings. It is obvious that the described embodiments are only some of the embodiments of the present application and are intended to explain the inventive concept. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.
The terms "center," "longitudinal," "transverse," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "axial," "radial," "circumferential," and the like as used in the description are based on the orientation or positional relationship shown in the drawings and are merely for simplicity of description and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operate in a particular orientation.
The terms "first," "second," and the like, as used in the description, are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. The term "plurality" means two or more, unless specifically defined otherwise.
The terms "coupled," "connected," and the like as used in the description herein are to be construed broadly and may be, for example, fixedly coupled, detachably coupled, or integrally formed, unless otherwise specifically defined and limited; may be a mechanical connection, an electrical connection; can be directly connected and indirectly connected through an intermediate medium; may be a communication between two elements or an interaction between two elements. The specific meaning of the terms in the embodiments can be understood by those of ordinary skill in the art according to the specific circumstances.
Unless expressly stated or limited otherwise, a first feature "above," "below," or "above" a second feature may be either the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" or "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. A first feature "under", "beneath" or "under" a second feature may be either the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "under", "beneath" or "under" a second feature may be a first feature being directly under or diagonally under the second feature, or simply indicating that the first feature is less level than the second feature.
The terms "one particular embodiment" and "one particular embodiment" as used in this description mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Referring to fig. 1 and 2, a specific embodiment of the present application proposes a molten salt separation and purification apparatus of a PTA alkali recovery furnace, the molten salt separation and purification apparatus 1 is designed based on an existing PTA wastewater incinerator, such as an incinerator previously disclosed by the applicant, publication No.: CN115371061B, name: an incineration device for high-concentration salt-containing organic waste liquid and an incineration melting slag separation and recovery process. The molten salt separation and purification device 1 is arranged at the bottom of the incinerator 29, and is spaced from the incinerator 29 by a first transverse plate 26, and preferably, the first transverse plate 26 is inclined by 5-10 degrees.
The molten salt separation and purification device 1 is transversely divided into four compartments, comprising a smelting chamber 2, an electrolysis chamber 3, a balance chamber 4 and a liquid outlet chamber 5, wherein the smelting chamber 2 is communicated with an incinerator 29, the first transverse plate 26 isolates the electrolysis chamber 3, the balance chamber 4 and the liquid outlet chamber 5 from the incinerator 29, and molten salt generated by burning PTA wastewater falls down and is converged into the smelting chamber 2 by the first transverse plate 26. A first vertical plate 27 is arranged between the smelting chamber 2 and the electrolysis chamber 3, the upper end of the first vertical plate 27 is connected with a first transverse plate 26, and the lower end of the first vertical plate 27 and the bottom of the molten salt separating and purifying device 1 are separated to form a smelting chamber to electrolysis chamber lower passage 15 for molten salt to flow. A first partition wall 19 is arranged between the electrolytic chamber 3 and the balance chamber 4, and a channel 16 from the electrolytic chamber for flowing molten salt to the middle part of the balance chamber is arranged in the middle of the first partition wall 19. A second partition wall 14 is arranged between the balance chamber 4 and the liquid outlet chamber 5, and a channel 17 from the balance chamber for flowing molten salt to the middle part of the liquid outlet chamber is arranged in the middle of the second partition wall 14. The side wall of the liquid outlet chamber 5 is provided with a liquid outlet chute 18.
The electrolytic chamber 3 is divided into an anode chamber 31 and a cathode chamber 32 by a second vertical plate 28, the top end of the second vertical plate 28 is connected with the first transverse plate 26, the lower parts of the anode chamber 31 and the cathode chamber 32 are communicated, the anode chamber 31 and the cathode chamber 32 are respectively provided with a corresponding discharge electrode 6 for electrolyzing molten salt, the upper parts of the anode chamber 31 and the cathode chamber 32 are respectively provided with an anode cavity 24 and a cathode cavity 25, and the anode cavity 24 is provided with a first electrolytic chamber gas-phase circulating pipe 7 for discharging gases such as electrolytic bromine. The first electrolytic chamber gas-phase circulating pipe 7 is connected with a heat exchanger 8 and a gas-liquid separator 9 in sequence, and the heat exchanger 8 is provided with a circulating cooling water inlet 12 and a circulating cooling water outlet 11 for cooling water to enter and exit. The heat exchanger 8 and the gas-liquid separator 9 are respectively connected with the bromine storage tank 10, the separated gas is sent back to the space between the discharge electrodes 6 of the electrolysis chamber 3 through the second electrolysis chamber gas-phase circulating pipe 30 after the gas-liquid separator 9, and the first electrolysis chamber gas-phase circulating pipe 7 and/or the second electrolysis chamber gas-phase circulating pipe 30 are provided with a circulating fan 13 for providing circulating power. The cathode cavity 25 is provided with a cathode cavity balance tube 23 for communicating with the furnace chamber of the incinerator 29.
The cavity at the upper part of the balance chamber 4 is provided with a balance chamber gas-phase balance pipe 22 for communicating with the furnace chamber of the incinerator 29, the bottom of the balance chamber 4 is provided with a gas supplementing pipe 21, the clean flue gas generated by the incineration of the incinerator 29 and treated by the gas supplementing fan 20 is pumped into the balance chamber 4, the cations in the molten salt after electrolysis are balanced by the carbon dioxide in the clean flue gas, and the clean flue gas passes through the molten salt to float upwards and returns to the furnace chamber of the incinerator 29 through the balance chamber gas-phase balance pipe 22.
The process of the application is as follows: the molten salt by-produced in the incinerator 29 automatically flows into the smelting chamber 2, and then enters the electrolysis chamber 3 through the lower passage 15 of the electrolysis chamber. The left side of the electrolytic chamber 3 is a positive electrode, the right side is a negative electrode, discharge is carried out between the positive electrode and the negative electrode, the electrolytic sodium bromide and the electrolytic sodium carbonate react, and the total electrolytic reaction of the sodium bromide is 2 NaBr-2Na+Br 2 E, -; the total electrolytic reaction of sodium carbonate is Na 2 CO 3 →2Na+CO 2 ↑+1/2O 2 And ≡. Sodium bromide and sodium carbonate molar Gibbs free energy in a bath environment at 1000 ℃ below: naBr- > 1/2Na ++1/2 Br 2 ↑，△Gθ(kJ/mol)=331；Na 2 CO 3 →2Na↑+CO 2 ↑+1/2O 2 It is known that electrolysis of NaBr preferentially occurs in a bath environment at 1000 c, and that some sodium carbonate is inevitably electrolyzed. Electrolytically generated Br 2 ↑、CO 2 ↑、O 2 The mixed gas of ∈ is introduced into a heat exchanger 8 from an anode cavity 24 at the upper part of an anode at the left side of an electrolytic chamber 3 through a gas-phase circulating pipe 7 of the first electrolytic chamber for cooling and condensing, bromine is recovered by condensing, part of bromine solution is introduced into a bromine storage tank 10 from a bottom self-flowing pipe, the rest gas-liquid mixture is introduced into a gas-liquid separator 9 for further separation, bromine is introduced into the bromine storage tank 10 from the bottom of the gas-liquid separator 9, and the rest CO is introduced into a gas-liquid separator 9 2 And O 2 The gas is discharged from the top of the gas-liquid separator 9 and then is introduced into the bottom of the electrolysis chamber 3 to inhibit the electrolysis of sodium carbonate, so that the sodium carbonate reaches an equilibrium point; in addition, the residual gas led back to the bottom of the electrolysis chamber 3 plays a role in isolation and protection, and for the sodium simple substance generated on the right side of the electrolysis chamber 3, most of the volatilized sodium simple substance enters a cathode cavity 25 on the right side of the electrolysis chamber 3 through ascending air flow, so that sodium simple substance generated by cathode electrolysis is prevented from entering a left anode cavity 24, and sodium simple substance generated by a molten pool cathode chamber 32 and introduced CO are prevented from entering a left anode cavity 24 2 Reacting to form Na 2 CO 3 Returning to the electrolysis chamber 3. Electrolytically generated CO 2 And O 2 The gas is always half-circulated in the electrolytic chamber 3, and the amount of carbon dioxide electrolyzed in the molten salt is equal to the amount of carbon dioxide absorbed by the molten salt when the gas-phase carbon dioxide concentration reaches a set saturation partial pressure.
The electrolyzed molten salt enters the balance chamber 4 from the electrolysis chamber to the middle channel 16 of the balance chamber, at the moment, part of sodium ions are brought into the balance chamber 4, the bottom of the balance chamber 4 is provided with a gas supplementing pipe 21, the tail clean flue gas extracted by the gas supplementing pipe 21 is introduced for aeration, and CO in the flue gas is utilized for the aeration 2 Balance sodium ions in the molten salt, balance negative ions and positive ions, reduce carbon emission, return redundant flue gas to an incinerator 29 through a balance chamber gas-phase balance pipe 22, enter the liquid outlet chamber 5 through a channel 17 from the balance chamber to the middle part of the liquid outlet chamber, finally discharge sodium carbonate melt through a liquid outlet chute 18 at the upper part of the liquid outlet chamber 5, and cool to obtain finished products for packaging.
Example 1
A certain 250 ten thousand tons of PTA wastewater zero-emission recycling project is characterized in that 7.6t/h of PTA wastewater with 50% organic salt content is concentrated, 3.8t/h of dry basis is obtained, and 2.21% wt of bromine and 7.94% wt of sodium are contained in 7.6t/h of concentrated solution. The incineration treatment process comprises the following steps: PTA wastewater concentrate- & gt incinerator 29 hearth. 7.6t/h PTA wastewater concentrate is incinerated by an alkali recovery furnace to generate 1.5t/h molten salt, wherein the molten salt comprises 14.44% sodium bromide and 85.56% sodium carbonate. Molten salt generated by the alkali recovery furnace is collected by an inclined plate at the upper part of a molten salt separating bed and enters the smelting chamber 2, and then enters the electrolysis chamber 3 from a channel 15 from the smelting chamber to the lower part of the electrolysis chamber.
The molten sodium bromide is electrolyzed to generate bromine gas, the bromine gas enters a heat exchanger 8 through a gas-phase circulating pipe 7 of a first electrolysis chamber to be cooled, condensed and recovered to obtain bromine, and 168kg/h bromine is generated in the part. The molten salt with bromine separated enters the balance chamber 4, and redundant sodium ions absorb carbon dioxide in the air supply to form sodium carbonate, and the carbon dioxide emission is reduced by 92kg/h. After the molten salt is balanced, sodium carbonate in a high-purity molten state is produced by a liquid outlet chute 18 of the liquid outlet chamber 5, and the molten sodium carbonate is cooled and packed to obtain sodium carbonate solid powder, wherein 1391kg/h of sodium carbonate is produced.
The foregoing is merely a preferred embodiment of the present application, and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the concept of the present application, and such modifications and adaptations are intended to be comprehended within the scope of the present application.
Claims (10)
1. The utility model provides a PTA alkali recovery furnace molten salt separation purification device which characterized in that: the molten salt separation and purification device (1) is arranged at the bottom of the incinerator (29) and is separated by a first transverse plate (26), and the molten salt separation and purification device (1) is transversely divided into four compartments, namely a smelting chamber (2), an electrolysis chamber (3), a balance chamber (4) and a liquid outlet chamber (5); the smelting chamber (2) is communicated with the incinerator (29), molten salt generated by burning PTA wastewater falls down and is converged into the smelting chamber (2) by the first transverse plate (26), a first vertical plate (27) is arranged between the smelting chamber (2) and the electrolysis chamber (3), the upper end of the first vertical plate (27) is connected with the first transverse plate (26), and a channel (15) from the smelting chamber to the lower part of the electrolysis chamber is formed between the lower end of the first vertical plate (27) and the bottom of the molten salt separation and purification device (1); the electrolysis chamber (3) is divided into an anode chamber (31) and a cathode chamber (32) from left to right by a second vertical plate (28), the top end of the second vertical plate (28) is connected with the first transverse plate (26), the lower parts of the anode chamber (31) and the cathode chamber (32) are communicated, corresponding discharge electrodes (6) are respectively arranged in the anode chamber (31) and the cathode chamber (32) and are used for electrolyzing molten salt, the upper parts of the anode chamber (31) and the cathode chamber (32) are respectively provided with an anode cavity (24) and a cathode cavity (25), the anode cavity (24) is provided with a first electrolysis chamber gas-phase circulation pipe (7) used for discharging electrolysis gas, the electrolysis gas is cooled and condensed to recover bromine simple substances, and the rest gas is returned between the discharge electrodes (6) of the electrolysis chamber (3); a first partition wall (19) is arranged between the electrolysis chamber (3) and the balance chamber (4), a channel (16) from the electrolysis chamber to the middle part of the balance chamber is arranged in the middle of the first partition wall (19), and a gas supplementing pipe (21) for supplementing carbon dioxide is arranged at the bottom of the balance chamber (4).
2. The device for separating and purifying molten salt of PTA alkali recovery furnace according to claim 1, wherein: the side of the electrolysis chamber (3) close to the smelting chamber (2) is an anode chamber (31), and the side of the electrolysis chamber (3) close to the balance chamber (4) is a cathode chamber (32).
3. The device for separating and purifying molten salt of PTA alkali recovery furnace according to claim 1, wherein: the first electrolytic chamber gas-phase circulating pipe (7) is connected with the heat exchanger (8) and the gas-liquid separator (9) in sequence, the heat exchanger (8) and the gas-liquid separator (9) are respectively connected with the bromine storage tank (10), and the separated gas is returned to the space between the discharge electrodes (6) of the electrolytic chamber (3) through the second electrolytic chamber gas-phase circulating pipe (30) after passing through the gas-liquid separator (9).
4. The apparatus for separating and purifying molten salt in a PTA alkali recovery furnace according to claim 3, wherein: the heat exchanger (8) is provided with a circulating cooling water inlet (12) for cooling water to enter and exit and a circulating cooling water outlet (11), and a circulating fan (13) for providing circulating power is arranged in the gas-phase circulating pipe of the electrolysis chamber.
5. The device for separating and purifying molten salt of PTA alkali recovery furnace according to claim 1, wherein: the cathode cavity (25) is provided with a cathode cavity balance pipe (23) which is used for being communicated with a furnace chamber of the incinerator (29).
6. The device for separating and purifying molten salt of PTA alkali recovery furnace according to claim 1, wherein: a second partition wall (14) is arranged between the balance chamber (4) and the liquid outlet chamber (5), and a channel (17) from the balance chamber to the liquid outlet chamber is formed in the middle of the second partition wall (14).
7. The device for separating and purifying molten salt of PTA alkali recovery furnace according to claim 1, wherein: the cavity at the upper part of the balance chamber (4) is provided with a balance chamber gas-phase balance pipe (22) which is used for communicating with the furnace chamber of the incinerator (29).
8. The device for separating and purifying molten salt of PTA alkali recovery furnace according to claim 1, wherein: the air supplementing pipe (21) extracts purified flue gas generated by burning in the incinerator (29) through the air supplementing fan (20) and treated to be introduced into the balance chamber (4).
9. The device for separating and purifying molten salt of PTA alkali recovery furnace according to claim 1, wherein: the first transverse plate (26) is inclined by 5-10 degrees.
10. The device for separating and purifying molten salt of PTA alkali recovery furnace according to claim 1, wherein:
the side wall of the liquid outlet chamber (5) is provided with a liquid outlet chute (18).
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