CN100441276C - Method for regenerating organic amine desulfurizer by bipolar membrane electrodialysis - Google Patents
Method for regenerating organic amine desulfurizer by bipolar membrane electrodialysis Download PDFInfo
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- CN100441276C CN100441276C CNB2005100382083A CN200510038208A CN100441276C CN 100441276 C CN100441276 C CN 100441276C CN B2005100382083 A CNB2005100382083 A CN B2005100382083A CN 200510038208 A CN200510038208 A CN 200510038208A CN 100441276 C CN100441276 C CN 100441276C
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Abstract
The present invention relates to a method for regenerating an organic amine desulfurizer by bipolar membrane electrodialysis, which is characterized in that a thermal-stability salt solution formed from organic amine capable of generating reaction with sulfur dioxide in a desulfurizing process is perfused into one of partition chambers of a bipolar membrane electrodialysis device composed of at least one set of membrane cell units, such as a salt chamber, a salt/alkali chamber, a salt/acid chamber or an anode chamber, electrolytic solutions are perfused in other partition chambers, the cathode and the anode of the bipolar membrane electrodialysis device are respectively connected with the negative pole and the positive pole of a direct-current power supply, and then the current density of the direct-current field of the direct-current power supply is controlled as 10 to 200 mA/cm<2>; the positive ions of the thermal-stability salt formed from the organic amine in the desulfurizing process is combined with hydroxide radical ions hydrolyzed and separated from a bipolar membrane to form the organic amine, and therefore, the instant regeneration of the organic amine is realized. The method of the present invention has the advantages of simplified operation procedure, low energy consumption, convenient device assembly and easy combination to the existing organic amine desulfurizing process, and is favorable to promoting the popularization of an organic amine desulfurizing technique.
Description
Technical field:
The invention belongs to the membrane technology field, particularly the method for regenerating organic amine desulfurizer by bipolar membrane electrodialysis.
Background technology:
For environmental protection and sustainable development, strict day by day standard has all been formulated to the discharging of sulfur dioxide in countries in the world.Explore through years of researches, existing many alternative method of smoke dissipation and desulfurization, for example " Air Pollution Control Engineering " (Beijing: the absorption process of mentioning the .1996 of Higher Education Publishing House), absorption method, oxidizing process, " american chemical IEEE magazine " (AIChE Journal, 1994,40:143-151; 1998,44:323-331; 2004, electrochemical membrane conversion method and the radio frequency plasma conversion method mentioned in 50:524-529).The wet absorption method is because small investment, operation and maintenance are simple, thereby becomes the common method of exhaust gas desulfurization.Wherein organic amine exhaust gas desulfurization technology is easy and simple to handle, desulfuration efficiency is high, desulfurizing agent can recycle by heat regeneration, has bigger practical value and good benefits in environment.But in running, because oxidation, increasing desulfurizing agent has changed into thermal-stable salt, and this has not only reduced desulfuration efficiency, and has caused the loss of secondary pollution and organic amine, thereby has limited applying of this technology.An approach that improves this technology is that the thermal-stable salt that forms in the sweetening process is regenerated, and realizes the resource circulation utilization.
Existing researcher attempts the regeneration of the thermal-stable salt that forms in the sweetening process.For example, " water technology " (2003,29 (4): 230-232) reported the method for the flue gas desulfurization absorbent being carried out electrodialysis regeneration, its principle is: with sulfurous acid (H
2SO
3) and thermal-stable salt (RN)
2SO
4Place the different compartments of conventional electrodialysis, under effect of electric field, sulphite and sulfuric acid (organic amine salt of sulfite ion and organic amine cation formation sulfurous acid, the SO of organic amine takes place to form respectively by the directional migration of ionic membrane in zwitterion
4 2-With H
+In conjunction with generating H
2SO
4), and then the sulphite of organic amine carried out thermal regeneration.Its weak point is: only having formed by conventional electrodialysis can hot regenerant salt RNHSO
3, needing further, heat regeneration just can change into organic amine; The waste that needs to use other material sulfurous acid and cause resource, and sulfurous acid instability are relatively more difficult in the operation.
Summary of the invention:
The invention provides a kind of method of regenerating organic amine desulfurizer by bipolar membrane electrodialysis, to overcome the above-mentioned deficiency of prior art.
The method of regenerating organic amine desulfurizer by bipolar membrane electrodialysis of the present invention, at least one group of membrane cisterna unit to forming according to the membrane cisterna configuration of setting by dividing plate, Bipolar Membrane, cation-exchange membrane and anion-exchange membrane, be assembled between the pair of electrodes, form the bipolar membrane electrodialysis device; It is characterized in that: the heat endurance salting liquid that organic amine is formed in sweetening process is filled in the wherein class compartment in this four classes compartment of salt chamber, salt/alkali chamber, salt/sour chamber or anode chamber, in other compartment, pour into electrolyte solution, the negative electrode of this device is connected with positive pole with the negative pole of dc source respectively with anode, and the current density of controlling its DC electric field is 10-200mA/cm
2Described organic amine be meant can with the amino-compound of sulfur dioxide reaction; Described Bipolar Membrane is meant the ion-exchange composite membranes that is composited by cation exchange layer and anion exchange layer.
The membrane cisterna unit of described composition bipolar membrane electrodialysis device, a kind of in following four kinds of configurations: dividing plate-Bipolar Membrane-dividing plate-cation-exchange membrane-dividing plate-anion-exchange membrane, dividing plate-Bipolar Membrane-dividing plate-cation-exchange membrane, dividing plate-Bipolar Membrane-dividing plate-anion-exchange membrane or dividing plate-Bipolar Membrane-dividing plate-anion-exchange membrane-dividing plate-anion-exchange membrane.
Described electrolyte solution generally uses strong electrolyte, preferably sulfuric acid sodium.
The method of regenerating organic amine desulfurizer by bipolar membrane electrodialysis of the present invention, its principle is: the cation of the thermal-stable salt that forms in the organic amine sweetening process combines with the hydroxide ion that the Bipolar Membrane water decomposition goes out and forms organic amine, and the sulfate ion in the solution combines formation sulfuric acid with the hydrogen ion that the Bipolar Membrane water decomposition goes out.With " water technology " (2003,29 (4): 230-232) method that the flue gas desulfurization absorbent is carried out electrodialysis regeneration of report is compared, the present invention has realized the instant regeneration of organic amine on the basis with Bipolar Membrane water decomposition and two technology integration of conventional electrodialysis, operation sequence is simplified, and is easy to be incorporated in the existing amine process sulfur removal technology; Adopt stable strong electrolytes such as sodium sulphate to replace unsettled sulfurous acid, can make the electricity of solution lead increase, energy consumption reduces, and operational stability strengthens.
Description of drawings:
Fig. 1 is the BP-C-A membrane cisterna configuration schematic diagram in four kinds of configurations of bipolar membrane electrodialysis regeneration piperazine membrane cisterna;
Fig. 2 is the BP-C membrane cisterna configuration schematic diagram in four kinds of configurations of bipolar membrane electrodialysis regeneration piperazine membrane cisterna;
Fig. 3 is the BP-A membrane cisterna configuration schematic diagram in four kinds of configurations of bipolar membrane electrodialysis regeneration piperazine membrane cisterna;
Fig. 4 is the BP-C-C membrane cisterna configuration schematic diagram in four kinds of configurations of bipolar membrane electrodialysis regeneration piperazine membrane cisterna.
The specific embodiment:
Further describe the method for the present invention by the following examples with regenerating organic amine desulfurizer by bipolar membrane electrodialysis.
Embodiment 1
Bipolar membrane electrodialysis device by assembling BP-C-A membrane cisterna configuration shown in Figure 1, that is: successively titanium is plated the bipolar membrane electrodialysis device that ruthenium electrode, lucite pole plate, lucite spacer, Viton sealing gasket and Bipolar Membrane (BP), cation-exchange membrane (C) and anion-exchange membrane (A) are assembled into a membrane cisterna repetitive by order from negative electrode (-) to anode (+), form corresponding four compartments and be respectively cathode chamber, alkali chamber, salt chamber and anode chamber, the volume of each compartment is 6.3cm
3Again each compartment is formed four independently closed circuits by emulsion tube and external immersible pump and beaker (1000mL) respectively.It is that 0.3mol/L, liquor capacity are the sodium sulphate (Na of 0.5L that concentration is all poured into by cathode chamber, alkali chamber and anode chamber
2SO
4) solution, salt chamber perfusion concentration is that 0.18mol/L, liquor capacity are the Piperazine Sulfate (PzH of 0.5L
2SO
4) solution, the solution of four compartments is independent loops separately, and flow rate of liquid is 27L/h.The monofilm of each compartment (Bipolar Membrane, cation-exchange membrane or cation-exchange membrane) effective film area is 7.07cm
2
Do not applying under the DC electric field condition earlier, with the solution of four compartments independent loops separately, the voltage drop until between negative electrode and anode is less than 0.2V.Negative electrode with this device is connected with positive pole with the negative pole of dc source respectively with anode again, and the cation exchange layer of guaranteeing Bipolar Membrane is towards negative electrode, and its anion exchange layer is towards anode.The current density of control DC electric field is 60mA/cm
2After adopting this membrane cisterna configuration power-on servicing certain hour,, adopt the determined by ultraviolet spectrophotometry piperazine concentration from the sampling of alkali chamber.Behind the power-on servicing 5min, alkali chamber piperazine concentration reaches 0.002mol/L; Behind the power-on servicing 30min, alkali chamber piperazine concentration reaches 0.006mol/L; Behind the power-on servicing 1h, alkali chamber piperazine concentration reaches 0.013mol/L; Behind the power-on servicing 12h, alkali chamber piperazine concentration reaches 0.163mol/L.Regeneration piperazine amount increases with the prolongation of operating time.The concrete operations time can be according to the requirement of Piperazine Sulfate conversion ratio is controlled.
Be similar to the membrane cisterna number of assembling steps of embodiment 1, the BP-C membrane cisterna configuration bipolar membrane electrodialysis device by a membrane cisterna repetitive of assembling shown in Figure 2 forms corresponding three compartments and is respectively cathode chamber, alkali chamber and anode chamber.It is that 0.3mol/L, liquor capacity are the sodium sulphate (Na of 0.5L that concentration is all poured in cathode chamber and alkali chamber
2SO
4) solution, anode chamber's perfusion concentration is that 0.18mol/L, liquor capacity are the Piperazine Sulfate (PzH of 0.5L
2SO
4) solution, the solution of three compartments is independent loops separately.Other operating conditions are identical with embodiment 1.
Adopt this device regeneration piperazine, power-on servicing after 1 hour alkali chamber piperazine concentration reach 0.015mol/L.
Embodiment 3
Be similar to the number of assembling steps of embodiment 1, the BP-A membrane cisterna configuration bipolar membrane electrodialysis device by a membrane cisterna repetitive of assembling shown in Figure 3 forms corresponding three compartments and is respectively cathode chamber, salt/alkali chamber and anode chamber.It is that 0.3mol/L, liquor capacity are the sodium sulphate (Na of 0.5L that concentration is all poured into by cathode chamber and anode chamber
2SO
4) solution, salt/alkali chamber perfusion 0.18mol/L, liquor capacity are the Piperazine Sulfate (PzH of 0.5L
2SO
4) solution, the solution of three compartments is independent loops separately.Other operating conditions are identical with embodiment 1.
Adopt this device regeneration piperazine, power-on servicing after 1 hour alkali chamber piperazine concentration reach 0.005mol/L.
Embodiment 4
Be similar to the number of assembling steps of embodiment 1, the BP-C-C membrane cisterna configuration bipolar membrane electrodialysis device by a membrane cisterna repetitive of assembling shown in Figure 4 forms corresponding four compartments and is respectively cathode chamber, alkali chamber, salt chamber and anode chamber.It is that 0.3mol/L, liquor capacity are the sodium sulphate (Na of 0.5L that concentration is all poured into by cathode chamber, alkali chamber and anode chamber
2SO
4) solution, salt chamber perfusion 0.18mol/L, liquor capacity are the Piperazine Sulfate (PzH of 0.5L
2SO
4) solution, the solution of four compartments is independent loops separately.Other operating conditions are identical with embodiment 1.
Adopt this device regeneration piperazine, power-on servicing after 1 hour alkali chamber piperazine concentration reach 0.015mol/L.
Embodiment 5
Be similar to the number of assembling steps of embodiment 1, by the bipolar membrane electrodialysis device that the BP-C-A of 3 membrane cisterna repetitives membrane cisterna configuration is arranged between the pair of electrodes that is assembled in shown in Figure 1, forming corresponding compartment number is 10, and its groups of cells is combined into: cathode chamber-alkali chamber-salt chamber-sour chamber-alkali chamber-salt chamber-sour chamber-alkali chamber-salt chamber-anode chamber.It is that 0.3mol/L, liquor capacity are the sodium sulphate (Na of 0.5L that concentration is all poured into by cathode chamber, alkali chamber, sour chamber and anode chamber
2SO
4) solution, salt chamber perfusion 0.18mol/L, liquor capacity are the Piperazine Sulfate (PzH of 0.5L
2SO
4) solution, the solution of ten compartments is independent loops separately.Other operating conditions are identical with embodiment 1.
Adopt this device regeneration piperazine, power-on servicing after 1 hour 3 indoor piperazine concentration of alkali all reach 0.014mol/L.
Claims (1)
1, the method for a kind of bipolar membrane electrodialysis regeneration organic amine desulfurizing agent, at least one group of membrane cisterna unit will being made up of dividing plate, Bipolar Membrane and cation-exchange membrane is assembled between the pair of electrodes formation bipolar membrane electrodialysis device; The heat endurance salting liquid that organic amine is formed in sweetening process is filled in the salt chamber, in other compartment, pour into electrolyte solution, the negative electrode of this device is connected with positive pole with the negative pole of dc source respectively with anode, and the current density of controlling its DC electric field is 10-200mA/cm
2Described organic amine be meant can with the amino-compound of sulfur dioxide reaction; Described Bipolar Membrane is meant the ion-exchange composite membranes that is composited by cation exchange layer and anion exchange layer: it is characterized in that: the described membrane cisterna unit of forming the bipolar membrane electrodialysis device is dividing plate-Bipolar Membrane-dividing plate-cation-exchange membrane-dividing plate-cation-exchange membrane according to negative electrode to the order of anode, forming corresponding four compartments is cathode chamber, alkali chamber, salt chamber and anode chamber, and the solution of four compartments is independent loops separately; The membrane cisterna unit number is 1, and the salt chamber is between adjacent two cation-exchange membranes, the perfusion of described salt chamber be Piperazine Sulfate solution, what pour in other compartment is metabisulfite solution, described organic amine is a piperazine.
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| CN102304722A (en) * | 2011-09-20 | 2012-01-04 | 福建师范大学 | Chlorine-free alkali producing method based on three-film four-chamber electrolytic cell |
| CN103933861B (en) * | 2013-08-02 | 2017-04-26 | 浙江赛特膜技术有限公司 | Method for preparing methionine and sodium hydroxide through bipolar membrane electrodialysis |
| CN103406025B (en) * | 2013-08-28 | 2016-11-09 | 中国石油化工股份有限公司 | A kind of double membrane stack-magnetoelectricity dialysis is utilized to remove the device of heat stable salts in amine desulphurization solvent continuously |
| CN103922980B (en) * | 2014-04-22 | 2016-08-24 | 中国科学技术大学 | A kind of method utilizing bipolar membrane electrodialysis to isolate methionine from the mixed solution of methionine salt and carbonate |
| CN104474862B (en) * | 2014-11-13 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of skid-mounted type desulfidation tail gas purifies oxidative absorption liquid recycling device |
| CN106542680B (en) * | 2016-10-19 | 2022-02-25 | 东莞市霖辉金属表面处理材料有限公司 | Wastewater treatment method for green and environment-friendly electrophoretic paint production |
| JP6882154B2 (en) * | 2017-12-26 | 2021-06-02 | 株式会社東芝 | Carbon dioxide component removing device, carbon dioxide component removing method, and carbon dioxide gas removing device |
| CN109758918A (en) * | 2019-02-26 | 2019-05-17 | 清华大学 | A kind of method of thermal-stable salt in removing Amine Solutions |
| CN113493263A (en) * | 2020-04-01 | 2021-10-12 | 佛山市云米电器科技有限公司 | Household water purifying device and control method thereof |
| CN113025829B (en) * | 2021-04-26 | 2022-12-06 | 福建师范大学 | Method for treating copper ore smelting waste residues by applying bipolar membrane electrodialysis |
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