CN113041812A - Device and method for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification - Google Patents

Device and method for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification Download PDF

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CN113041812A
CN113041812A CN202110281082.1A CN202110281082A CN113041812A CN 113041812 A CN113041812 A CN 113041812A CN 202110281082 A CN202110281082 A CN 202110281082A CN 113041812 A CN113041812 A CN 113041812A
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flue gas
chamber
bipolar membrane
seawater
ozone
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赵颖颖
金辉
袁俊生
纪志永
刘杰
郭小甫
李非
王士钊
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Hebei University of Technology
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    • B01D2258/0283—Flue gases
    • 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
    • C02F2103/08—Seawater, e.g. for desalination

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Abstract

The invention provides a device and a method for coupling seawater decalcification and flue gas carbon fixation, desulfurization and denitrification, wherein the method comprises the following steps: (1) carrying out oxidation treatment on the flue gas to obtain oxidized flue gas; (2) and (3) carrying out bipolar membrane electrodialysis treatment on the seawater and the oxidized flue gas obtained in the step (1) to respectively obtain the decalcified seawater and the purified flue gas. The device comprises a flue gas input unit, an electrodialysis unit and a tail gas treatment unit; the electrodialysis unit comprises a bipolar membrane electrodialysis device; the bipolar membrane electrodialysis device comprises a bipolar membrane stack, and a polar chamber, an acid chamber, an alkali chamber and a salt chamber which are respectively and independently connected with the bipolar membrane stack; the bipolar membrane stack consists of an anode electrode, a cathode electrode and at least 1 set of three-compartment electrodialysis units arranged between the anode and cathode electrodes. The invention couples the functions of seawater decalcification and flue gas carbon fixation, desulfurization and denitrification, reduces energy consumption, saves production cost and protects ecological environment.

Description

Device and method for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification
Technical Field
The invention belongs to the technical field of flue gas purification, relates to a flue gas carbon-fixation desulfurization and denitrification method, and particularly relates to a device and a method for coupling seawater decalcification and flue gas carbon-fixation desulfurization and denitrification.
Background
With the acceleration of the industrialization process of China, the atmospheric pollution is increased. Researches show that carbon dioxide, sulfur dioxide and nitrogen oxide discharged by fossil fuel combustion are main sources of air pollution and are also main reasons of extreme weather such as greenhouse effect, acid rain, photochemical smog and the like. The emission of these harmful gases not only causes great harm to the ecological environment, but also seriously threatens the life and health of human beings.
Carbon capture and sequestration technology (CCS) can effectively capture carbon dioxide from emissions sources and then permanently store it in suitable geological locations. However, the process has potential leakage risk, and the investment of long-distance transportation is huge, so that the production cost is high. The wet desulphurization is the most widely applied flue gas desulphurization technology at present, and has the advantages of strong reaction activity, high reaction speed and high desulphurization rate (which can reach more than 90%). But requires the treatment of the waste liquidThe equipment corrosion degree is high, and the maintenance cost is high. For NO in flue gasXAt present, the mature denitration technology is a Selective Catalytic Reduction (SCR) method which is stable in operation and high in denitration efficiency. With industrial NOXDue to strict requirements of emission standards, development of an SCR denitration catalyst with stable performance and high efficiency at low temperature is a future research hotspot. The traditional treatment process has the problems of single technology, high cost, impurity byproducts and the like, so that the development of an efficient flue gas carbon fixation desulfurization and denitrification technology is not slow.
In addition, calcium ions are easy to cause scaling in the process of seawater utilization, so that the equipment is damaged, and the method is a great obstacle to seawater desalination and resource utilization. Calcium ions in seawater are removed through the pretreatment process, so that the normal use of equipment is maintained, the service life of the equipment is prolonged, the energy consumption is reduced, and the cost is saved.
CN110038440A discloses a bipolar membrane electrodialysis device and a method for sea water decalcification, wherein acid gas is introduced into an alkali chamber, and then the bipolar membrane electrodialysis is started after the acid gas is electrified, so that the contents of carbon dioxide and sulfur dioxide in flue gas and the contents of calcium ions in sea water are reduced. The method can effectively remove carbon dioxide and sulfur dioxide which are easy to be absorbed by alkali liquor, but has little effect on absorbing nitric oxide in flue gas.
CN111905544A discloses an ozone treatment nitrogen oxide oxidation high-efficiency flue gas mixing device, the invention can carry out full mixing and stirring on input materials, after the feeding is finished, a feeding hole at the upper part is closed and steam inactivation is carried out, after the inactivation is finished, stirring is carried out again, the materials in the device are crushed, and then the materials are conveyed out from a discharging hole. This method can oxidize nitrogen oxides well, but nitrogen oxides are toxic gases and cannot be discharged directly into the environment, and proper post-treatment is necessary after oxidation.
CN211537215U discloses a desulfurization and denitrification integrated flue gas purification device, which combines the existing denitration technology outside the oxidation furnace to integrally absorb desulfurization and denitrification processes in a spray tower by ammonia water. The method can simultaneously remove sulfur dioxide and nitric oxide in the flue gas, but needs additional alkali sources, and has high energy consumption and high cost in the implementation process.
Therefore, how to provide a device and a method for flue gas purification treatment, which couple the functions of seawater decalcification and flue gas carbon fixation desulfurization and denitrification, reduce energy consumption, save production cost and protect ecological environment becomes a problem to be solved urgently by technical personnel in the field at present.
Disclosure of Invention
The invention aims to provide a device and a method for coupling seawater decalcification with flue gas carbon fixation desulfurization and denitration.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for coupling seawater decalcification and flue gas carbon fixation, desulfurization and denitrification, which comprises the following steps:
(1) carrying out oxidation treatment on the flue gas to obtain oxidized flue gas;
(2) and (3) carrying out bipolar membrane electrodialysis treatment on the seawater and the oxidized flue gas obtained in the step (1) to respectively obtain the decalcified seawater and the purified flue gas.
According to the invention, firstly, nitric oxide in the flue gas is oxidized into high-valence oxynitride which is easy to absorb, then carbon fixation, desulfurization and denitration of the flue gas are realized through bipolar membrane electrodialysis treatment, and decalcification treatment of seawater is synchronously realized, so that the two are mutually promoted, the energy consumption is reduced, the production cost is saved, and the ecological environment is protected.
Preferably, the concentration of carbon dioxide in the flue gas of step (1) is 1-100 wt%, for example 1 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt% or 100 wt%, but not limited to the recited values, and other non-recited values in the range of values are also applicable.
Preferably, the concentration of sulphur dioxide in the flue gas of step (1) is 0-2500ppm, but not 0, and may for example be 1ppm, 10ppm, 100ppm, 300ppm, 500ppm, 700ppm, 900ppm, 1000ppm, 1300ppm, 1500ppm, 1700ppm, 1900ppm, 2000ppm, 2300ppm or 2500ppm, but is not limited to the values listed, and other values not listed in this range of values are equally applicable.
Preferably, the concentration of nitric oxide in the flue gas of step (1) is 0-500ppm, but not 0, and may be, for example, 1ppm, 10ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm or 500ppm, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the oxidation treatment of step (1) comprises ozone oxidation and/or catalytic oxidation, and further preferably ozone oxidation.
Preferably, the ozone oxidation is to mix ozone with flue gas for oxidation treatment.
Preferably, the ozone is produced from oxygen via an ozone generating device.
Preferably, the oxygen concentration is 99.99 wt.% or more, and may be, for example, 99.99 wt.%, 99.999 wt.%, or 99.9999 wt.%, although not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the ozone generating device includes any one of a high-voltage discharge ozone generating device, an ultraviolet irradiation ozone generating device, or an electrolytic ozone generating device.
Preferably, the mixing ratio of the ozone to the nitric oxide in the flue gas is n (O)3) Examples of 1 include 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 and 2:1, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned numerical range are also applicable.
Preferably, the specific process of the bipolar membrane electrodialysis treatment in the step (2) comprises the following steps:
(a) preparing polar liquid, acid liquid and alkali liquid, and respectively and correspondingly pouring the polar liquid, the acid liquid and the alkali liquid into a polar chamber, an acid chamber and an alkali chamber in the bipolar membrane electrodialysis device;
(b) pouring seawater into a salt chamber in a bipolar membrane electrodialysis device, and adding calcium carbonate seed crystals into the salt chamber;
(c) starting the bipolar membrane electrodialysis device, keeping the current constant, introducing the oxidized flue gas into an alkali chamber, and simultaneously performing decalcification of seawater and carbon fixation, desulfurization and denitration on the flue gas.
The oxidized flue gas is introduced into an alkali chamber, and the bipolar membrane is used for producing alkali to absorb acid gases such as carbon dioxide, sulfur dioxide, oxynitride and the like in the flue gas; carbonate generated in the alkali chamber migrates to the salt chamber through the anion exchange membrane, combines with calcium ions in the seawater and generates calcium carbonate, thereby realizing the decalcification of the seawater and the carbon fixation of the flue gas. Meanwhile, sulfur dioxide and oxynitride are ionized under the action of hydroxyl, and the desulfurization and denitrification of the flue gas are further realized.
Preferably, the polar liquid of step (a) comprises a sodium nitrate solution.
Preferably, the concentration of the sodium nitrate solution is 0.22 to 0.26mol/L, and may be, for example, 0.22mol/L, 0.225mol/L, 0.23mol/L, 0.235mol/L, 0.24mol/L, 0.245mol/L, 0.25mol/L, 0.255mol/L, or 0.26mol/L, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the acid solution of step (a) comprises a hydrochloric acid solution.
Preferably, the concentration of the hydrochloric acid solution is 0.008 to 0.012mol/L, for example, 0.008mol/L, 0.009mol/L, 0.01mol/L, 0.011mol/L or 0.012mol/L, but not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the lye of step (a) comprises sodium hydroxide solution.
Preferably, the concentration of the sodium hydroxide solution is 0.008 to 0.012mol/L, for example 0.008mol/L, 0.009mol/L, 0.01mol/L, 0.011mol/L or 0.012mol/L, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the current in step (c) is 0.28-0.45A, such as 0.28A, 0.29A, 0.3A, 0.31A, 0.33A, 0.35A, 0.37A, 0.39A, 0.4A, 0.41A, 0.43A or 0.45A, but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the rate of introducing the oxidized flue gas into the alkaline chamber in step (c) is 18-30L/h, such as 18L/h, 19L/h, 20L/h, 22L/h, 24L/h, 26L/h, 28L/h or 30L/h, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, step (2) is followed by analyzing the components of the purified flue gas and performing tail gas treatment.
As a preferred technical solution of the first aspect of the present invention, the method comprises the steps of:
(1) mixing ozone and flue gas, and carrying out oxidation treatment to obtain oxidized flue gas; the concentration of carbon dioxide in the flue gas is 1-100 wt%, the concentration of sulfur dioxide is 0-2500ppm but does not contain 0, and the concentration of nitric oxide is 0-500ppm but does not contain 0; the ozone is prepared by oxygen with the concentration of more than or equal to 99.99 wt% through an ozone generating device, and the mixing ratio of the ozone to the nitric oxide in the flue gas is n (O)3):n(NO)＝(1-2):1；
(2) Carrying out bipolar membrane electrodialysis treatment on the seawater and the oxidized flue gas obtained in the step (1) to respectively obtain decalcified seawater and purified flue gas; the specific process of the bipolar membrane electrodialysis treatment comprises the following steps:
(a) preparing a sodium nitrate solution with the concentration of 0.22-0.26mol/L, a hydrochloric acid solution with the concentration of 0.008-0.012mol/L and a sodium hydroxide solution with the concentration of 0.008-0.012mol/L, and respectively and correspondingly pouring the sodium nitrate solution, the hydrochloric acid solution and the sodium hydroxide solution into a polar chamber, an acid chamber and an alkali chamber in the bipolar membrane electrodialysis device;
(b) pouring seawater into a salt chamber in a bipolar membrane electrodialysis device, and adding calcium carbonate seed crystals into the salt chamber;
(c) starting the bipolar membrane electrodialysis device, keeping the current constant at 0.28-0.45A, introducing the oxidized flue gas into an alkali chamber at the speed of 18-30L/h, and simultaneously performing decalcification of seawater and carbon fixation, desulfurization and denitrification of the flue gas;
(3) and (3) analyzing the components of the purified flue gas obtained in the step (2), and treating tail gas.
In a second aspect, the invention provides a device for performing seawater decalcification and flue gas carbon fixation desulfurization and denitrification coupling by using the method of the first aspect, and the device comprises a flue gas input unit, an electrodialysis unit and a tail gas treatment unit.
The electrodialysis unit comprises a bipolar membrane electrodialysis device.
The bipolar membrane electrodialysis device comprises a bipolar membrane stack, and a polar chamber, an acid chamber, an alkali chamber and a salt chamber which are respectively and independently connected with the bipolar membrane stack.
The bipolar membrane stack consists of an anode electrode, a cathode electrode and at least 1 set of three-compartment electrodialysis units arranged between the anode and cathode electrodes.
The electrodialysis unit consists of a bipolar membrane, an anion exchange membrane and an anion exchange membrane which are sequentially arranged at intervals.
The flue gas input unit and the tail gas treatment unit are respectively and independently connected with the alkali chamber.
According to the invention, the flue gas input unit is used for oxidation and preheating treatment of flue gas, the electrodialysis unit is used for carbon fixation, desulfurization and denitrification of flue gas and decalcification treatment of seawater, and the tail gas treatment unit is used for subsequent analysis and absorption treatment of flue gas, so that the organic combination of the three units reduces energy consumption, saves production cost and protects ecological environment.
Preferably, the flue gas input unit comprises a flue gas input device, an ozone generation device, a gas mixing device, a gas preheating device and an ozone analysis device.
Preferably, the flue gas input device, the ozone generating device and the gas preheating device are respectively and independently connected with the gas mixing device.
Preferably, the ozone analysis device and the alkali chamber are respectively and independently connected with the gas preheating device.
Preferably, the tail gas treatment unit comprises a flue gas analysis device and a tail gas treatment device which are connected in sequence.
Preferably, the flue gas analysis device is connected with the alkali chamber.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, firstly, nitric oxide in the flue gas is oxidized into high-valence oxynitride which is easy to absorb, then carbon fixation, desulfurization and denitration of the flue gas are realized through bipolar membrane electrodialysis treatment, and decalcification treatment of seawater is synchronously realized, the highest absorption rate of carbon dioxide in the flue gas can reach 90.02%, the highest absorption rate of sulfur dioxide can reach 99.99%, the highest absorption rate of nitric oxide can reach 80.55%, the highest decalcification rate of seawater can reach 95.47%, the two are mutually promoted, so that the energy consumption is reduced, the production cost is saved, and the ecological environment is protected.
Drawings
FIG. 1 is a schematic view of a device for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification provided by the invention.
Wherein: 1-N2A gas cylinder; 2-CO2A gas cylinder; 3-O2A gas cylinder; a 4-NO gas cylinder; 5-SO2A gas cylinder; 6-O2A gas cylinder; 7-an ozone generating device; 8-a gas mixing tube; 9-a preheater; 10-an ozone analyzer; 11-a flue gas analyzer; 12-bipolar membrane stack; 13-an alkali chamber; 14-an acid chamber; 15-salt chamber; 16-a filter; 17-pole chamber; and 18-a tail gas absorption tank.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The invention provides a device for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification, which comprises a flue gas input unit, an electrodialysis unit and a tail gas treatment unit, as shown in figure 1.
In the invention, the electrodialysis unit comprises a bipolar membrane electrodialysis device; the bipolar membrane electrodialysis device comprises a bipolar membrane stack 12, and a polar chamber 17, an acid chamber 14, an alkali chamber 13 and a salt chamber 15 which are respectively and independently connected with the bipolar membrane stack 12; the bipolar membrane stack 12 consists of an anode electrode, a cathode electrode and 1 set of three-compartment electrodialysis cells arranged between the anode and cathode electrodes; the electrodialysis unit consists of bipolar membranes BPM, anion exchange membranes AEM and anion exchange membranes AEM which are sequentially arranged at intervals; the flue gas input unit and the tail gas treatment unit are respectively and independently connected with the alkali chamber 13.
In the invention, the flue gas input unit comprises a flue gas input device (N)2Gas cylinder 1, CO2Gas cylinder 2, O2Gas cylinder 3, NO gas cylinder 4 and SO2Gas cylinder 5 and O2A gas cylinder 6), an ozone generating device 7, a gas mixing pipe 8, a preheater 9 and an ozone analyzer 10; the flue gas input device, the ozone generating device 7 and the preheater 9 are respectively and independently connected with a gas mixing pipe 8; the ozone analyzer 10 and the alkali chamber 13 are independently connected to the preheater 9.
In the invention, the tail gas treatment unit comprises a flue gas analyzer 11 and a tail gas absorption tank 18 which are connected in sequence; the flue gas analyzer 11 is connected with an alkali chamber 13.
Example 1
The embodiment provides a method for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification by adopting a device shown in fig. 1, wherein an ozone generator 7 in the device is a high-voltage discharge ozone generator, and the method comprises the following steps:
(1) preparing a solution of four chambers of a bipolar membrane electrodialysis device: the polar liquid in the polar chamber 17 is 0.24mol/L sodium nitrate solution, the acid liquid in the acid chamber 14 is 0.01mol/L hydrochloric acid solution, the alkali liquid in the alkali chamber 13 is 0.01mol/L sodium hydroxide solution, and seawater is poured into the salt chamber 15; the seawater comprises the following main components: na (Na)+(10.780g·kg-1)、Mg2+(1.280g·kg-1)、Ca2+(0.412g·kg-1)、K+(0.400g·kg-1)、Sr2+(0.008g·kg-1)、Cl-(19.350g·kg-1)、SO4 2-(2.710g·kg-1)、HCO3 -(0.107g·kg-1)、Br-(0.067g·kg-1)、CO3 2-(0.016g·kg-1)、B(OH)3(0.0193g·kg-1)、B(OH)4(0.0079g·kg-1) (ii) a And adding calcium carbonate seed crystals into the salt chamber 15;
(2) configuring simulated smoke, wherein dioxygen in the simulated smokeThe concentrations of carbon monoxide, sulfur dioxide and nitric oxide are respectively 10 wt%, 2000ppm and 100ppm, and the concentration of each gas is analyzed by a flue gas analyzer 11; the ozone generating device 7 is opened, the generated ozone is utilized to oxidize the nitric oxide in the simulated smoke into nitrogen dioxide which is easy to absorb, and n (O)3) N (no) ═ 2:1, and the concentration of each gas was analyzed again by the flue gas analyzer 11;
(3) starting the bipolar membrane electrodialysis device, keeping the current constant at 0.45A, introducing the oxidized flue gas into an alkali chamber 13 through a 9cm air refining disc, wherein the introduction rate is 18L/h; absorbing acidic gases such as carbon dioxide, sulfur dioxide, oxynitride and the like in the flue gas by using bipolar membrane to generate alkali; the flue gas analyzer 11 is used for analyzing the components of the treated flue gas, and then the flue gas is introduced into a tail gas absorption tank 18 filled with 0.01mol/L sodium hydroxide solution for absorbing the flue gas.
The analysis results of the components of the treated flue gas and the seawater decalcification rate obtained in this example are shown in table 1.
TABLE 1
Figure BDA0002978417660000091
In Table 1, CO2Absorption rate (PhiCO)2)、SO2Absorption rate (. phi.SO)2) NO oxidation rate (ω NO), NO absorption rate
Figure BDA0002978417660000092
And the decalcification rate
Figure BDA0002978417660000093
The calculation formulas of (a) and (b) are respectively as follows:
Figure BDA0002978417660000101
Figure BDA0002978417660000102
Figure BDA0002978417660000103
Figure BDA0002978417660000104
Figure BDA0002978417660000105
wherein the content of the first and second substances,
Figure BDA0002978417660000106
is the molar increase of carbonate in the alkali chamber 13 and the salt chamber 15;
Figure BDA0002978417660000107
the molar increase of bicarbonate in the base chamber 13 and the salt chamber 15; l is0(L/h) is the flow of the introduced simulated flue gas;
Figure BDA0002978417660000108
simulating the initial volume fraction of carbon dioxide in the flue gas; delta t (h) is the time for introducing the flue gas; 22.4(L/mol) is the gas molar volume;
Figure BDA0002978417660000109
is the molar increase of sulfate radicals in the alkali chamber 13 and the salt chamber 15;
Figure BDA00029784176600001010
the molar increase of bicarbonate in the base chamber 13 and the salt chamber 15;
Figure BDA00029784176600001011
simulating the initial volume fraction of sulfur dioxide in the flue gas; cNO primarySimulating the initial concentration of nitric oxide in the flue gas; cNO powderThe concentration of nitric oxide after ozone oxidation of the flue gas is simulated;
Figure BDA00029784176600001012
the concentration of nitrogen dioxide in the simulated flue gas after passing through the alkali chamber 13;
Figure BDA00029784176600001013
is the initial calcium ion concentration in the salt compartment 15;
Figure BDA00029784176600001014
is the concentration of calcium ions in the salt compartment 15 at a certain moment.
Example 2
The embodiment provides a method for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification by adopting a device shown in fig. 1, wherein an ozone generator 7 in the device is an ultraviolet irradiation ozone generator, and the method comprises the following steps:
(1) preparing a solution of four chambers of a bipolar membrane electrodialysis device: the polar liquid in the polar chamber 17 is 0.24mol/L sodium nitrate solution, the acid liquid in the acid chamber 14 is 0.01mol/L hydrochloric acid solution, the alkali liquid in the alkali chamber 13 is 0.01mol/L sodium hydroxide solution, and seawater is poured into the salt chamber 15; the seawater comprises the following main components: na (Na)+(10.780g·kg-1)、Mg2+(1.280g·kg-1)、Ca2+(0.412g·kg-1)、K+(0.400g·kg-1)、Sr2+(0.008g·kg-1)、Cl-(19.350g·kg-1)、SO4 2-(2.710g·kg-1)、HCO3 -(0.107g·kg-1)、Br-(0.067g·kg-1)、CO3 2-(0.016g·kg-1)、B(OH)3(0.0193g·kg-1)、B(OH)4(0.0079g·kg-1) (ii) a And adding calcium carbonate seed crystals into the salt chamber 15;
(2) preparing simulated flue gas, wherein the concentrations of carbon dioxide, sulfur dioxide and nitric oxide in the simulated flue gas are respectively 12.5 wt%, 2100ppm and 200ppm, and analyzing the concentration of each gas by using a flue gas analyzer 11; the ozone generating device 7 is opened, the generated ozone is utilized to oxidize the nitric oxide in the simulated smoke into nitrogen dioxide which is easy to absorb, and n (O)3) 1.8:1, and smoking againThe gas analyzer 11 analyzes the concentration of each gas;
(3) starting the bipolar membrane electrodialysis device, keeping the current constant at 0.39A, introducing the oxidized flue gas into the alkali chamber 13 through an air refining disc of 9cm, wherein the introduction rate is 24L/h; absorbing acidic gases such as carbon dioxide, sulfur dioxide, oxynitride and the like in the flue gas by using bipolar membrane to generate alkali; the flue gas analyzer 11 is used for analyzing the components of the treated flue gas, and then the flue gas is introduced into a tail gas absorption tank 18 filled with 0.01mol/L sodium hydroxide solution for absorbing the flue gas.
The analysis results of the components of the treated flue gas and the seawater decalcification rate obtained in this example are shown in table 2.
TABLE 2
Figure BDA0002978417660000111
Figure BDA0002978417660000121
In Table 2, CO2Absorption rate (PhiCO)2)、SO2Absorption rate (. phi.SO)2) NO oxidation rate (ω NO), NO absorption rate
Figure BDA0002978417660000122
And the decalcification rate
Figure BDA0002978417660000123
The calculation formula is the same as that in table 1, and therefore, is not described herein.
Example 3
The embodiment provides a method for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification by adopting a device shown in fig. 1, wherein an ozone generator 7 in the device is an electrolytic ozone generator, and the method comprises the following steps:
(1) preparing a solution of four chambers of a bipolar membrane electrodialysis device: the polar liquid in the polar chamber 17 is 0.24mol/L sodium nitrate solution, the acid liquid in the acid chamber 14 is 0.01mol/L hydrochloric acid solution, and the alkali liquid in the alkali chamber 13 is 0.01mol/L hydrogenSodium oxide solution, and seawater is poured into the salt chamber 15; the seawater comprises the following main components: na (Na)+(10.780g·kg-1)、Mg2+(1.280g·kg-1)、Ca2+(0.412g·kg-1)、K+(0.400g·kg-1)、Sr2+(0.008g·kg-1)、Cl-(19.350g·kg-1)、SO4 2-(2.710g·kg-1)、HCO3 -(0.107g·kg-1)、Br-(0.067g·kg-1)、CO3 2-(0.016g·kg-1)、B(OH)3(0.0193g·kg-1)、B(OH)4(0.0079g·kg-1) (ii) a And adding calcium carbonate seed crystals into the salt chamber 15;
(2) preparing simulated flue gas, wherein the concentrations of carbon dioxide, sulfur dioxide and nitric oxide in the simulated flue gas are respectively 15 wt%, 2200ppm and 300ppm, and analyzing the concentration of each gas by using a flue gas analyzer 11; the ozone generating device 7 is opened, the generated ozone is utilized to oxidize the nitric oxide in the simulated smoke into nitrogen dioxide which is easy to absorb, and n (O)3) N (no) ═ 1.6:1, the concentration of each gas was analyzed again by the flue gas analyzer 11;
(3) starting the bipolar membrane electrodialysis device, keeping the current constant at 0.39A, introducing the oxidized flue gas into the alkali chamber 13 through an air refining disc of 8cm, wherein the introduction rate is 24L/h; absorbing acidic gases such as carbon dioxide, sulfur dioxide, oxynitride and the like in the flue gas by using bipolar membrane to generate alkali; the flue gas analyzer 11 is used for analyzing the components of the treated flue gas, and then the flue gas is introduced into a tail gas absorption tank 18 filled with 0.01mol/L sodium hydroxide solution for absorbing the flue gas.
The analysis results of the components of the treated flue gas and the seawater decalcification rate obtained in this example are shown in table 3.
TABLE 3
Figure BDA0002978417660000131
In Table 3, CO2Absorption rate (PhiCO)2)、SO2Absorption rate (. phi.SO)2) NO oxidation rate(omega NO), NO absorption rate
Figure BDA0002978417660000132
And the decalcification rate
Figure BDA0002978417660000133
The calculation formula is the same as that in table 1, and therefore, is not described herein.
Example 4
The embodiment provides a method for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification by adopting a device shown in fig. 1, wherein an ozone generator 7 in the device is a high-voltage discharge ozone generator, and the method comprises the following steps:
(1) preparing a solution of four chambers of a bipolar membrane electrodialysis device: the polar liquid in the polar chamber 17 is 0.24mol/L sodium nitrate solution, the acid liquid in the acid chamber 14 is 0.01mol/L hydrochloric acid solution, the alkali liquid in the alkali chamber 13 is 0.01mol/L sodium hydroxide solution, and seawater is poured into the salt chamber 15; the seawater comprises the following main components: na (Na)+(10.780g·kg-1)、Mg2+(1.280g·kg-1)、Ca2+(0.412g·kg-1)、K+(0.400g·kg-1)、Sr2+(0.008g·kg-1)、Cl-(19.350g·kg-1)、SO4 2-(2.710g·kg-1)、HCO3 -(0.107g·kg-1)、Br-(0.067g·kg-1)、CO3 2-(0.016g·kg-1)、B(OH)3(0.0193g·kg-1)、B(OH)4(0.0079g·kg-1) (ii) a And adding calcium carbonate seed crystals into the salt chamber 15;
(2) preparing simulated flue gas, wherein the concentrations of carbon dioxide, sulfur dioxide and nitric oxide in the simulated flue gas are respectively 17.5 wt%, 2300ppm and 400ppm, and analyzing the concentration of each gas by using a flue gas analyzer 11; the ozone generating device 7 is opened, the generated ozone is utilized to oxidize the nitric oxide in the simulated smoke into nitrogen dioxide which is easy to absorb, and n (O)3) N (no) ═ 1.4:1, the concentration of each gas was analyzed again by the flue gas analyzer 11;
(3) starting the bipolar membrane electrodialysis device, keeping the current constant at 0.34A, introducing the oxidized flue gas into the alkali chamber 13 through an air refining disc of 8cm, wherein the introduction rate is 27L/h; absorbing acidic gases such as carbon dioxide, sulfur dioxide, oxynitride and the like in the flue gas by using bipolar membrane to generate alkali; the flue gas analyzer 11 is used for analyzing the components of the treated flue gas, and then the flue gas is introduced into a tail gas absorption tank 18 filled with 0.01mol/L sodium hydroxide solution for absorbing the flue gas.
The analysis results of the components of the treated flue gas and the seawater decalcification rate obtained in this example are shown in table 4.
TABLE 4
Figure BDA0002978417660000141
Figure BDA0002978417660000151
In Table 4, CO2Absorption rate (PhiCO)2)、SO2Absorption rate (. phi.SO)2) NO oxidation rate (ω NO), NO absorption rate
Figure BDA0002978417660000152
And the decalcification rate
Figure BDA0002978417660000153
The calculation formula is the same as that in table 1, and therefore, is not described herein.
Example 5
The embodiment provides a method for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification by adopting a device shown in fig. 1, wherein an ozone generator 7 in the device is an ultraviolet irradiation ozone generator, and the method comprises the following steps:
(1) preparing a solution of four chambers of a bipolar membrane electrodialysis device: the polar liquid in the polar chamber 17 is 0.24mol/L sodium nitrate solution, the acid liquid in the acid chamber 14 is 0.01mol/L hydrochloric acid solution, the alkali liquid in the alkali chamber 13 is 0.01mol/L sodium hydroxide solution, and seawater is poured into the salt chamber 15; the seawater comprises the following main components: na (Na)+(10.780g·kg-1)、Mg2+(1.280g·kg-1)、Ca2+(0.412g·kg-1)、K+(0.400g·kg-1)、Sr2+(0.008g·kg-1)、Cl-(19.350g·kg-1)、SO4 2-(2.710g·kg-1)、HCO3 -(0.107g·kg-1)、Br-(0.067g·kg-1)、CO3 2-(0.016g·kg-1)、B(OH)3(0.0193g·kg-1)、B(OH)4(0.0079g·kg-1) (ii) a And adding calcium carbonate seed crystals into the salt chamber 15;
(2) preparing simulated flue gas, wherein the concentrations of carbon dioxide, sulfur dioxide and nitric oxide in the simulated flue gas are respectively 15 wt%, 2400ppm and 500ppm, and analyzing the concentration of each gas by using a flue gas analyzer 11; the ozone generating device 7 is opened, the generated ozone is utilized to oxidize the nitric oxide in the simulated smoke into nitrogen dioxide which is easy to absorb, and n (O)3) N (no) ═ 1.2:1, the concentration of each gas was analyzed again by the flue gas analyzer 11;
(3) starting the bipolar membrane electrodialysis device, keeping the current constant at 0.28A, introducing the oxidized flue gas into the alkali chamber 13 through an air refining disc of 7cm, wherein the introduction rate is 27L/h; absorbing acidic gases such as carbon dioxide, sulfur dioxide, oxynitride and the like in the flue gas by using bipolar membrane to generate alkali; the flue gas analyzer 11 is used for analyzing the components of the treated flue gas, and then the flue gas is introduced into a tail gas absorption tank 18 filled with 0.01mol/L sodium hydroxide solution for absorbing the flue gas.
The analysis results of the components of the treated flue gas and the seawater decalcification rate obtained in this example are shown in table 5.
TABLE 5
Figure BDA0002978417660000161
In Table 5, CO2Absorption rate (PhiCO)2)、SO2Absorption rate (. phi.SO)2) NO oxidation rate (ω NO), NO absorption rate
Figure BDA0002978417660000162
And the decalcification rate
Figure BDA0002978417660000163
The calculation formula is the same as that in table 1, and therefore, is not described herein.
Example 6
The embodiment provides a method for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification by adopting a device shown in fig. 1, wherein an ozone generator 7 in the device is an electrolytic ozone generator, and the method comprises the following steps:
(1) preparing a solution of four chambers of a bipolar membrane electrodialysis device: the polar liquid in the polar chamber 17 is 0.24mol/L sodium nitrate solution, the acid liquid in the acid chamber 14 is 0.01mol/L hydrochloric acid solution, the alkali liquid in the alkali chamber 13 is 0.01mol/L sodium hydroxide solution, and seawater is poured into the salt chamber 15; the seawater comprises the following main components: na (Na)+(10.780g·kg-1)、Mg2+(1.280g·kg-1)、Ca2+(0.412g·kg-1)、K+(0.400g·kg-1)、Sr2+(0.008g·kg-1)、Cl-(19.350g·kg-1)、SO4 2-(2.710g·kg-1)、HCO3 -(0.107g·kg-1)、Br-(0.067g·kg-1)、CO3 2-(0.016g·kg-1)、B(OH)3(0.0193g·kg-1)、B(OH)4(0.0079g·kg-1) (ii) a And adding calcium carbonate seed crystals into the salt chamber 15;
(2) preparing simulated flue gas, wherein the concentrations of carbon dioxide, sulfur dioxide and nitric oxide in the simulated flue gas are respectively 20 wt%, 2500ppm and 500ppm, and analyzing the concentration of each gas by using a flue gas analyzer 11; the ozone generating device 7 is opened, the generated ozone is utilized to oxidize the nitric oxide in the simulated smoke into nitrogen dioxide which is easy to absorb, and n (O)3) N (no) ═ 1:1, and the concentration of each gas was analyzed again by the flue gas analyzer 11;
(3) starting the bipolar membrane electrodialysis device, keeping the current constant at 0.28A, introducing the oxidized flue gas into an alkali chamber 13 through an air refining disc of 7cm, wherein the introduction rate is 30L/h; absorbing acidic gases such as carbon dioxide, sulfur dioxide, oxynitride and the like in the flue gas by using bipolar membrane to generate alkali; the flue gas analyzer 11 is used for analyzing the components of the treated flue gas, and then the flue gas is introduced into a tail gas absorption tank 18 filled with 0.01mol/L sodium hydroxide solution for absorbing the flue gas.
The analysis results of the components of the treated flue gas and the seawater decalcification rate obtained in this example are shown in table 6.
TABLE 6
Figure BDA0002978417660000171
Figure BDA0002978417660000181
In Table 6, CO2Absorption rate (PhiCO)2)、SO2Absorption rate (. phi.SO)2) NO oxidation rate (ω NO), NO absorption rate
Figure BDA0002978417660000182
And the decalcification rate
Figure BDA0002978417660000183
The calculation formula is the same as that in table 1, and therefore, is not described herein.
Comparative example 1
The comparative example provides a method for coupling seawater decalcification and flue gas treatment, which is disclosed in application example 3 of CN110038440A, and specifically comprises the following steps:
(1) respectively and independently adjusting the pH value of a sodium hydroxide solution in an alkali liquor storage unit and the pH value of simulated seawater in a brine storage unit to 7.5 by using acid gas, wherein the acid gas is flue gas, the volume fraction of carbon dioxide in the flue gas is 12%, the volume fraction of sulfur dioxide is 2000ppm, and Ca in the simulated seawater2+The concentration of (A) is 0.52 mg/g;
(2) respectively and independently starting circulation of alkali liquor after the pH value is adjusted in the alkali liquor storage unit, simulated seawater after the pH value is adjusted in the brine storage unit, nitric acid solution with the pH value of 1.5 in the acid liquor storage unit and NaCl solution with the concentration of 20g/L in the polar liquid storage unit, and adding calcium carbonate seed crystals with the mass of 15% of that of calcium ions in the simulated seawater into a settling chamber;
(3) after the circulation of the liquid in the alkali liquor storage unit, the brine storage unit, the acid liquor storage unit and the polar liquid storage unit is started, the flue gas is continuously introduced into the alkali liquor storage unit, the volume fraction of carbon dioxide in the flue gas is 12%, the volume fraction of sulfur dioxide is 2000ppm, the liquid-gas ratio of the circulation flow of the alkali liquor to the flue gas is 2.5, the bipolar membrane electrodialysis is carried out by electrifying, and the current density is 20A/m2And the flow velocity on the surface of the membrane is 0.5cm/s, and when the concentration of calcium ions in the simulated seawater in the saline water storage unit is not changed, the power supply is stopped, and the bipolar membrane electrodialysis is finished.
The decalcification rate of the simulated seawater obtained by the comparative example is 81.82%, the carbon fixing rate of the flue gas is 31%, the results are obviously lower than the treatment results of the examples 1-6, and the comparative example can effectively remove carbon dioxide and sulfur dioxide which are easy to be absorbed by alkali liquor, but has little effect on absorbing nitric oxide in the flue gas.
Therefore, the invention firstly oxidizes the nitric oxide in the flue gas into high-valence oxynitride which is easy to absorb, then the bipolar membrane electrodialysis treatment is adopted to realize the carbon fixation, the desulfurization and the denitration of the flue gas, and synchronously realize the decalcification treatment of seawater, the highest absorption rate of carbon dioxide in the flue gas can reach 90.02%, the highest absorption rate of sulfur dioxide can reach 99.99%, the highest absorption rate of nitric oxide can reach 80.55%, the highest decalcification rate of seawater can reach 95.47%, the two are mutually promoted, the energy consumption is reduced, the production cost is saved, and the ecological environment is protected.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A method for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification is characterized by comprising the following steps:
(1) carrying out oxidation treatment on the flue gas to obtain oxidized flue gas;
(2) and (3) carrying out bipolar membrane electrodialysis treatment on the seawater and the oxidized flue gas obtained in the step (1) to respectively obtain the decalcified seawater and the purified flue gas.
2. The method according to claim 1, wherein the concentration of carbon dioxide in the flue gas of step (1) is 1-100 wt%;
preferably, the concentration of the sulfur dioxide in the flue gas in the step (1) is 0-2500ppm, but does not contain 0;
preferably, the concentration of nitric oxide in the flue gas in the step (1) is 0-500ppm, but does not contain 0.
3. The method according to claim 1 or 2, wherein the oxidation treatment of step (1) comprises ozone oxidation and/or catalytic oxidation, further preferably ozone oxidation;
preferably, the ozone oxidation is to mix ozone and flue gas for oxidation treatment;
preferably, the ozone is produced by oxygen through an ozone generating device;
preferably, the concentration of the oxygen is more than or equal to 99.99 wt%;
preferably, the ozone generating device comprises any one of a high-voltage discharge ozone generating device, an ultraviolet irradiation ozone generating device or an electrolytic ozone generating device;
preferably, the mixing ratio of the ozone to the nitric oxide in the flue gas is n (O)3):n(NO)＝(1-2):1。
4. The method according to any one of claims 1-3, characterized in that the specific process of the bipolar membrane electrodialysis treatment of step (2) comprises the following steps:
(a) preparing polar liquid, acid liquid and alkali liquid, and respectively and correspondingly pouring the polar liquid, the acid liquid and the alkali liquid into a polar chamber, an acid chamber and an alkali chamber in the bipolar membrane electrodialysis device;
(b) pouring seawater into a salt chamber in a bipolar membrane electrodialysis device, and adding calcium carbonate seed crystals into the salt chamber;
(c) starting the bipolar membrane electrodialysis device, keeping the current constant, introducing the oxidized flue gas into an alkali chamber, and simultaneously performing decalcification of seawater and carbon fixation, desulfurization and denitration on the flue gas.
5. The method of claim 4, wherein the polar liquid of step (a) comprises a sodium nitrate solution;
preferably, the concentration of the sodium nitrate solution is 0.22-0.26 mol/L;
preferably, the acid solution of step (a) comprises a hydrochloric acid solution;
preferably, the concentration of the hydrochloric acid solution is 0.008-0.012 mol/L;
preferably, the lye of step (a) comprises sodium hydroxide solution;
preferably, the concentration of the sodium hydroxide solution is 0.008-0.012 mol/L;
preferably, the current of step (c) is 0.28-0.45A;
preferably, the rate of the oxidized fume in the step (c) to the alkali chamber is 18-30L/h.
6. The method according to any one of claims 1 to 5, wherein the step (2) is followed by performing a composition analysis on the obtained purified flue gas and performing a tail gas treatment.
7. Method according to any of claims 1-6, characterized in that the method comprises the steps of:
(1) mixing ozone and flue gas, and carrying out oxidation treatment to obtain oxidized flue gas; the concentration of carbon dioxide in the flue gas is 1-100 wt%, the concentration of sulfur dioxide is 0-2500ppm but does not contain 0, and the concentration of nitric oxide is 0-500ppm but does not contain 0; the ozone is prepared by oxygen with the concentration of more than or equal to 99.99 wt% through an ozone generating device, and the mixing ratio of the ozone to the nitric oxide in the flue gas is n (O)3):n(NO)＝(1-2):1；
(2) Carrying out bipolar membrane electrodialysis treatment on the seawater and the oxidized flue gas obtained in the step (1) to respectively obtain decalcified seawater and purified flue gas; the specific process of the bipolar membrane electrodialysis treatment comprises the following steps:
(a) preparing a sodium nitrate solution with the concentration of 0.22-0.26mol/L, a hydrochloric acid solution with the concentration of 0.008-0.012mol/L and a sodium hydroxide solution with the concentration of 0.008-0.012mol/L, and respectively and correspondingly pouring the sodium nitrate solution, the hydrochloric acid solution and the sodium hydroxide solution into a polar chamber, an acid chamber and an alkali chamber in the bipolar membrane electrodialysis device;
(b) pouring seawater into a salt chamber in a bipolar membrane electrodialysis device, and adding calcium carbonate seed crystals into the salt chamber;
(c) starting the bipolar membrane electrodialysis device, keeping the current constant at 0.28-0.45A, introducing the oxidized flue gas into an alkali chamber at the speed of 18-30L/h, and simultaneously performing decalcification of seawater and carbon fixation, desulfurization and denitrification of the flue gas;
(3) and (3) analyzing the components of the purified flue gas obtained in the step (2), and treating tail gas.
8. An apparatus for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification by adopting the method as claimed in any one of claims 1 to 7, which comprises a flue gas input unit, an electrodialysis unit and a tail gas treatment unit;
the electrodialysis unit comprises a bipolar membrane electrodialysis device;
the bipolar membrane electrodialysis device comprises a bipolar membrane stack, and a polar chamber, an acid chamber, an alkali chamber and a salt chamber which are respectively and independently connected with the bipolar membrane stack;
the bipolar membrane stack consists of an anode electrode, a cathode electrode and at least 1 set of three-compartment electrodialysis units arranged between the anode electrode and the cathode electrode;
the electrodialysis unit consists of a bipolar membrane, an anion exchange membrane and an anion exchange membrane which are sequentially arranged at intervals;
the flue gas input unit and the tail gas treatment unit are respectively and independently connected with the alkali chamber.
9. The apparatus of claim 8, wherein the flue gas input unit comprises a flue gas input device, an ozone generating device, a gas mixing device, a gas preheating device and an ozone analyzing device;
preferably, the flue gas input device, the ozone generating device and the gas preheating device are respectively and independently connected with the gas mixing device;
preferably, the ozone analysis device and the alkali chamber are respectively and independently connected with the gas preheating device.
10. The device according to claim 8 or 9, wherein the tail gas treatment unit comprises a flue gas analysis device and a tail gas treatment device which are connected in sequence;
preferably, the flue gas analysis device is connected with the alkali chamber.
CN202110281082.1A 2021-03-16 2021-03-16 Device and method for coupling seawater decalcification and flue gas carbon fixation desulfurization and denitrification Pending CN113041812A (en)

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JP2012096975A (en) * 2010-11-05 2012-05-24 Univ Of Tokyo Carbon dioxide fixing apparatus
US20170354926A1 (en) * 2016-06-13 2017-12-14 General Electric Technology Gmbh Integrated desulfurization and carbon dioxide capture system for flue gases
CN110038440A (en) * 2019-05-30 2019-07-23 河北工业大学 A kind of bipolar membrane electrodialysis device and method for seawater decalcification
CN110433622A (en) * 2019-08-28 2019-11-12 广东佳德环保科技有限公司 A kind of smoke gas comprehensive treatment system and method for ozone oxidation collaboration

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4552635A (en) * 1983-05-02 1985-11-12 Allied Corporation Electrodialytic methods for removal of sulfur oxides from waste gases
JP2012096975A (en) * 2010-11-05 2012-05-24 Univ Of Tokyo Carbon dioxide fixing apparatus
US20170354926A1 (en) * 2016-06-13 2017-12-14 General Electric Technology Gmbh Integrated desulfurization and carbon dioxide capture system for flue gases
CN110038440A (en) * 2019-05-30 2019-07-23 河北工业大学 A kind of bipolar membrane electrodialysis device and method for seawater decalcification
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