CN102304723A - Three-membrane four-chamber chlorine-free alkali-producing electrolytic tank consisting of anion and cation exchange membranes and bipolar membrane - Google Patents
Three-membrane four-chamber chlorine-free alkali-producing electrolytic tank consisting of anion and cation exchange membranes and bipolar membrane Download PDFInfo
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- CN102304723A CN102304723A CN201110279777A CN201110279777A CN102304723A CN 102304723 A CN102304723 A CN 102304723A CN 201110279777 A CN201110279777 A CN 201110279777A CN 201110279777 A CN201110279777 A CN 201110279777A CN 102304723 A CN102304723 A CN 102304723A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
Abstract
The invention relates to an environment-friendly, high-efficiency and energy-saving electrolytic tank, in particular to a three-membrane four-chamber chlorine-free alkali-producing electrolytic tank modified by a metal phthalocyanine derivative, with a high ionic conductivity anion exchange membrane, a high ionic conductivity cation exchange membrane and a bipolar membrane and consisting of the anion exchange membrane, the cation exchange membrane and the bipolar membrane. The three-membrane four-chamber chlorine-free alkali-producing electrolytic tank is characterized in that: the anion exchange membrane, the cation exchange membrane and the bipolar membrane are arranged between the electrolytic tank anode and the electrolytic tank cathode sequentially; an electrolytic chamber I is arranged between the electrolytic tank anode and the anion exchange membrane; an electrolytic chamber II is arranged between the anion exchange membrane and the cation exchange membrane; an electrolytic chamber III is arranged between the cation exchange membrane and the bipolar membrane; and an electrolytic chamber IV is arranged between the bipolar membrane and the electrolytic tank cathode. According to the scheme, the electrode reaction on the anode is oxygen evolution; the electrode reaction on the cathode is hydrogen evolution; the oxygen evolution and the hydrogen evolution are non-toxic and chlorine evolution reaction is avoided; the environment-friendly, high-efficiency and energy-saving electrolytic tank is environment-friendly and mild in production condition; production can be performed at the temperature of between 20 and 65 DEG C; and the current efficiency is over 70 percent.
Description
Technical field
The present invention relates to a kind of environmental protection, energy-efficient electrolyzer.Be specifically related to the metal phthalocyanine derivative modification have high ion-conductivity anion-exchange membrane, cationic exchange membrane and a Bipolar Membrane, and do not have chlorine based on three films, four Room that anion and cation exchange membrane and Bipolar Membrane constitute and produce the alkali electrolyzer.
Background technology
Chlorine industry is the basis of traditional electrical chemical industry, and its product caustic soda, hydrochloric acid, chlorine are the basic materials of chemical industry.In traditional chlor-alkali production technology, the equilibrium problem of chlor-alkali is the key that is related to chlor-alkali factory safety and High-efficient Production.That is to say that the output of chlor-alkali is mutual restriction, voluminous alkali just means voluminous chlorine, so the market of chlorine products has just become the bottle footpath of chlor-alkali production.Along with human living standard's raising, green production technology nuisanceless, environmental protection is more and more paid close attention to.Therefore having found many organochlorine products in recent years is carinogenicity materials, and the sales volume as the chlorine raw material of the chlorine products of water factory's sterilizing agent and life kind plastics falls sharply, and the chlor-alkali balance in traditional chlor-alkali production technology has been broken.
For this reason, can design a kind of to use the cationic exchange membrane and the electrolyzer of three films, four Room of Bipolar Membrane assembling to realize not having the target of chlorine product alkali.
The present invention intends proposition with the metal phthalocyanine derivative modified ion exchange membrane, improving its loading capacity, and then reduces membrane impedance and electric bath voltage.In this technology, owing to use the barrier film of ion-exchange membrane as electrodialysis cell, therefore low membrane impedance, high ionic conduction efficient are the main keys of this technical energy saving consumption reduction.
Summary of the invention
The purpose of this invention is to provide a kind ofly, and do not have chlorine based on combined three films, four Room of anion-exchange membrane, cationic exchange membrane and Bipolar Membrane and produce the alkali electrolyzer with the metal phthalocyanine derivative modification.
For realizing that the technical scheme that the object of the invention adopts is:
Between anode electrolytic cell and negative electrode; Be disposed with anion-exchange membrane, cationic exchange membrane and the Bipolar Membrane of passing through the metal phthalocyanine derivative modification respectively; It wherein between anode electrolytic cell and the anion-exchange membrane tank room I; It between anion-exchange membrane and the cationic exchange membrane tank room II; It between cationic exchange membrane and the Bipolar Membrane tank room III; Be the tank room IV between Bipolar Membrane and the electric tank cathode, form the no chlorine product alkali electrolyzer that three films, four Room macroion conductive membranes are formed.The cavity block layer of Bipolar Membrane is towards cationic exchange membrane, and the anode membrane layer of Bipolar Membrane is towards cathode; Electric tank cathode electrode, anode electrolytic cell electrode can adopt DSA electrode, lead electrode or Graphite Electrodes respectively.In electrolysis was used, the electrode reaction on anode was to analyse oxygen, and the electrode reaction on negative electrode is a liberation of hydrogen.
The present technique scheme is provided with anion-exchange membrane between cationic exchange membrane and anode, make H in the tank room I
+Ion can't get in the tank room II through anion-exchange membrane, thereby has guaranteed to have only in the tank room II Na of sodium sulfate
+The energising back is under electric field action, and the sulfate anion in the tank room II sees through anion-exchange membrane and gets into tank room I, Na
+Positively charged ion gets into the tank room III, constitutes the ionic charge path in the solution.Na in the tank room II
+Positively charged ion gets in the tank room III through cationic exchange membrane.Under effect of electric field, the water in the Bipolar Membrane middle layer dissociates, hydroxide ion (OH
) see through anion exchange membrane facing and arrive the tank room III, with the Na that from the tank room II, infiltrates through the tank room III through cationic exchange membrane
+In conjunction with generating sodium hydroxide NaOH.
Cathode and anode electrode: can adopt DSA electrode, lead electrode or Graphite Electrodes respectively.
Cationic exchange membrane:
Accurately take by weighing 4～6 g Xylo-Mucines (CMC), be mixed with the CMC aqueous solution of 200～280 mL, take by weighing carboxyl carboxyl metal (metal representes with the M) phthalocyanine derivates [MPc (COOH) of 0.08～0.1 g in addition
X]; With the dissolving of 10mL tetrahydrofuran (THF), slowly join in the CMC aqueous solution, stir; Vacuum deaerator; Obtain thickness film liquid, curtain coating in smooth culture dish, at room temperature air-dry film forming; After using weight fraction to be chromium chloride solution immersion 30～40min of 8% (down together); Use distilled water flushing, natural air drying promptly obtains MPc (COOH)
X-CMC cationic exchange membrane, wherein X is amino quantity.
Anion-exchange membrane:
Accurately take by weighing 3～6g chitosan,, be mixed with weight fraction and be 3.0～4.5% chitosan acetic acid aqueous solution, take by weighing ammonobase (metal representes with the M) phthalocyanine derivates [MPc (NH of 0.06～0.08 g in addition with the dissolving of 2.0% acetic acid aqueous solution
2)
X], with 10mL tetrahydrofuran (THF) dissolving, slowly drip 3 mL volume fractions and be 0.25% glutaraldehyde, stir, vacuum deaerator obtains anion-exchange membrane liquid.The anion-exchange membrane flow is prolonged in smooth culture dish, and at room temperature air-dry film forming is promptly processed anion-exchange membrane MPc (NH
2)
X-CS.Wherein X is amino quantity.
Bipolar Membrane:
According to the preparation method of described cationic exchange membrane, the MPc for preparing earlier (COOH)
X-CMC cationic exchange membrane; Then, obtain anion-exchange membrane liquid MPc (NH again according to the preparation method of described anion-exchange membrane
2)
X-CS.This film flow is prolonged in the above-mentioned MPc that makes (COOH)
XOn-CMC the cationic exchange membrane, at room temperature air-dry, can obtain MPc (COOH)
X-CMC/MPc (NH
2)
X-CS Bipolar Membrane.Wherein X is amino quantity.
Metal in the described metal phthalocyanine derivative (M) is a kind of among Fe, Co, Cu, Ni, Sn, Bi, Pb, Ce, Cf or the Yb.
Behind the bipolar rete of metal phthalocyanine derivative modification; The hydrophilicity of Bipolar Membrane increases; The outer water of Bipolar Membrane can in time replenish the consumption behind the water decomposition in the Bipolar Membrane middle layer; Thereby avoided the appearance of depletion layer; Bipolar Membrane can be worked under higher current density; Increase the product alkali number, improved electric groove efficient.
Adopt scheme of the present invention, the electrode reaction on anode is to analyse oxygen, and the electrode reaction on negative electrode is a liberation of hydrogen; Be nontoxic, tasteless environmental friendliness gas; Whole technology environmental protection, and compare with traditional chloralkali process, the production of caustic soda NaOH is not subjected to the restriction of chlorine output.With the use that is in parallel of traditional chlor-alkali electrolytic cells, can be used for regulating the chlor-alkali balance of chlor-alkali plant.Negative and positive two Room all with sodium sulfate as electrolytic solution, do not have and to analyse the chlorine reaction, environmental protection, working condition are gentle, can produce down at 20 ℃～65 ℃, current efficiency is greater than 70%.
Description of drawings
Fig. 1 is that three films of the present invention, four Room do not have chlorine product alkali cell construction synoptic diagram.
Fig. 2 is FePc (COOH)
4-CMC/ FePc (NH
2)
4-CS Bipolar Membrane cross section pattern sem photograph.
Fig. 3 is the molecular structure of anion-exchange membrane.
Fig. 4 is the molecular structure of cationic exchange membrane.
Among Fig. 1, the 1st, the electrolyzer cell body; The 2nd, anode electrolytic cell; The 3rd, anion-exchange membrane; The 4th, cationic exchange membrane; The 5th, Bipolar Membrane; The 6th, electric tank cathode.
Among Fig. 2, the upper strata is FePc (COOH)
4-CMC cationic exchange membrane, lower floor is FePc (NH
2)
4-CS anion-exchange membrane, two retes combine closely, and interlayer is seamless and tiny bubble occurs.The intermediate interface layer thickness of film is a nanometer scale.Under the DC electric field effect, can produce high strength of electric field (～10 at the Bipolar Membrane intermediate layer
8-10
9V/m), cause water wherein to dissociate, produce H
+Ion and OH
Ion.
Embodiment
Embodiment 1
The preparation of cationic exchange membrane:
Accurately take by weighing 6 g Xylo-Mucines (CMC), be mixed with the CMC aqueous solution of 200 mL, take by weighing the tetracarboxylic iron-phthalocyanine [FePc (COOH) of 0.1 g in addition
4]; With the dissolving of 10mL tetrahydrofuran (THF), slowly join in the CMC aqueous solution, stir; Vacuum deaerator; Obtain thickness film liquid, curtain coating in smooth culture dish, at room temperature air-dry film forming; After using weight fraction to be the chromium chloride solution immersion 30min of 8% (down together); Use distilled water flushing, natural air drying promptly obtains FePc (COOH)
4-CMC cationic exchange membrane.
The preparation of anion-exchange membrane:
Accurately take by weighing the 6g chitosan,, be mixed with weight fraction and be 3.0% chitosan acetic acid aqueous solution, take by weighing the tetramino iron-phthalocyanine [FePc (NH of 0.08 g in addition with the dissolving of 2.0% acetic acid aqueous solution
2)
4], with 10mL tetrahydrofuran (THF) dissolving, slowly drip 3 mL volume fractions and be 0.25% glutaraldehyde, stir, vacuum deaerator obtains anion-exchange membrane liquid.Faint yellow thickness anion-exchange membrane flow is prolonged in smooth culture dish, and at room temperature air-dry film forming is promptly processed anion-exchange membrane FePc (NH
2)
4-CS.
PREPARATIOM OF BIPOLAR MEMBRANE:
According to the preparation method of described cationic exchange membrane, prepare jade-green FePc (COOH) earlier
4-CMC cationic exchange membrane; Then, obtain faint yellow thickness anion-exchange membrane liquid FePc (NH again according to the preparation method of described anion-exchange membrane
2)
4-CS.This faint yellow thickness film flow is prolonged the Fe Pc (COOH) that makes in above-mentioned
4On-CMC the cationic exchange membrane, at room temperature air-dry, can obtain cationic exchange membrane is FePc (COOH)
4-CMC, anion-exchange membrane are FePc (NH
2)
4The FePc of-CS (COOH)
4-CMC/ FePc (NH
2)
4-CS Bipolar Membrane.
After the preparation of above-mentioned ionic membrane, cutting, on press from both sides subsequent use.
Choose 1500mm (length) * 1000 mm (wide) * 800 mm (height) electrolyzer that ABS plastic is processed, after the quartern,, the DSA anode electrode is installed, the graphite cathode electrode respectively in electrolyzer in the groove according to accompanying drawing 1 described structure.Between anode electrolytic cell and negative electrode; Be disposed with and prepare subsequent use anion-exchange membrane, cationic exchange membrane and Bipolar Membrane in advance; It wherein between anode electrolytic cell and the anion-exchange membrane tank room I; It between anion-exchange membrane and the cationic exchange membrane tank room II; It between cationic exchange membrane and the Bipolar Membrane tank room III; Be the tank room IV between Bipolar Membrane and the electric tank cathode, form the electrolyzer of three films, four Room.
Tank room I, tank room II and tank room IV add the aqueous sodium persulfate solution 165L of concentration 0.5mol/L as electrolyte solution, and it is the NaOH165L. of 10g/L that the tank room III adds concentration
Under 20 ℃, adjustment cathode and anode current density is 30mAcm
-2, after 10h electrolysis dialysis, the concentration of NaOH is 33.6g/L in the tank room III, current efficiency is 71%.Electricity bath voltage 4.3V.After 20h electrolysis dialysis, the concentration of middle NaOH is 56.8g/L, and current efficiency is 71%.Electricity bath voltage 4.5V.The current efficiency that generates NaOH in the tank room III is constant basically, and concentration continues to increase, and the output of NaOH constantly increases, and electric tank working is in stable condition.
Obviously, compare with traditional electrolyzer, with carboxyl metal phthalocyanine derivative modified cation exchange membrane with behind the ammonobase phthalocyanine derivates modified anion exchange membrane, bath voltage is less in the product alkali electricity groove, and current efficiency is higher.
Embodiment 2
The preparation of cationic exchange membrane:
Accurately take by weighing 4g Xylo-Mucine (CMC), be mixed with the CMC aqueous solution of 280 mL, take by weighing the tetracarboxylic copper phthalocyanine [CuPc (COOH) of 0.08 g in addition
4]; With the dissolving of 10mL tetrahydrofuran (THF), slowly join in the CMC aqueous solution, stir; Vacuum deaerator; Obtain thickness film liquid, curtain coating in smooth culture dish, at room temperature air-dry film forming; After using weight fraction to be the chromium chloride solution immersion 40min of 8% (down together); Use distilled water flushing, natural air drying promptly obtains CuPc (COOH)
4-CMC cationic exchange membrane.
The preparation of anion-exchange membrane:
Accurately take by weighing the 3g chitosan,, be mixed with weight fraction and be 3. 5% chitosan acetic acid aqueous solution, take by weighing the tetramino copper phthalocyanine [CuPc (NH of 0.07 g in addition with the dissolving of 2.0% acetic acid aqueous solution
2)
4], with 10mL tetrahydrofuran (THF) dissolving, slowly drip 3 mL volume fractions and be 0.25% glutaraldehyde, stir, vacuum deaerator obtains anion-exchange membrane liquid.Light blue thickness anion-exchange membrane flow is prolonged in smooth culture dish, and at room temperature air-dry film forming is promptly processed anion-exchange membrane CuPc (NH
2)
4-CS.
PREPARATIOM OF BIPOLAR MEMBRANE:
According to the preparation method of described cationic exchange membrane, prepare nattier blue CuPc (COOH) earlier
4-CMC cationic exchange membrane; Then, obtain thickness anion-exchange membrane liquid CuPc (NH again according to the preparation method of described anion-exchange membrane
2)
4-CS.This thick film flow is prolonged in the above-mentioned CuPc that makes (COOH)
4On-CMC the cationic exchange membrane, at room temperature air-dry, can obtain cationic exchange membrane is CuPc (COOH)
4-CMC, anion-exchange membrane are CuPc (NH
2)
4The FePc of-CS (COOH)
4-CMC/CuPc (NH
2)
4-CS Bipolar Membrane.
After the preparation of above-mentioned ionic membrane, cutting, on press from both sides subsequent use.
The structure of electrolyzer is identical with embodiment 1, the structure of electrolyzer such as embodiment 1, electric tank cathode electrodes use DSA electrode, anode electrolytic cell electrodes use lead electrode.Above-mentioned ionic membrane is packed in the electrolyzer, promptly form the electrolyzer of three films, four Room.
Embodiment 3
The structure of electrolyzer such as embodiment 1, electric tank cathode electrodes use DSA electrode, anode electrolytic cell electrodes use lead electrode.Cationic exchange membrane is PbPc (COOH)
4-CM, anion-exchange membrane are Pb Pc (NH
2)
4-CS.
Under 40 ℃, adjustment cathode and anode current density is 100mAcm
-2, after 7h electrolysis dialysis, the concentration of NaOH is 36.7g/L in the intermediate chamber, current efficiency is 65%.Electricity bath voltage 5.1V.
Embodiment 4
The structure of electrolyzer such as embodiment 1, electric tank cathode electrodes use lead electrode, anode electrolytic cell electrodes use Graphite Electrodes.Cationic exchange membrane is CePc (COOH)
4-CM, anion-exchange membrane are Ce Pc (NH
2)
4-CS.
Ionogen in the electrolyzer is with embodiment 1.
Under 60 ℃, adjustment cathode and anode current density is 100mAcm
-2, after 14h electrolysis dialysis, the concentration of NaOH is 56.7g/L in the intermediate chamber, current efficiency is 65%.Electricity bath voltage 5.1V.
Claims (7)
1. three films, four Room based on anion and cation exchange membrane and Bipolar Membrane formation do not have chlorine product alkali electrolyzer; Constitute by electrolyzer cell body, cathode electrode and anode electrode; It is characterized in that: between anode electrolytic cell and electric tank cathode, be disposed with anion-exchange membrane, cationic exchange membrane and the Bipolar Membrane of passing through the metal phthalocyanine derivative modification respectively.
2. a kind of three films, four Room based on anion and cation exchange membrane and Bipolar Membrane formation according to claim 1 do not have chlorine and produce the alkali electrolyzer, it is characterized in that described Bipolar Membrane, and its cavity block layer is towards cationic exchange membrane, and the anode membrane layer is towards negative electrode.
3. a kind of three films, four Room based on anion and cation exchange membrane and Bipolar Membrane formation according to claim 1 do not have chlorine and produce the alkali electrolyzer; It is characterized in that described electric tank cathode electrode, anode electrolytic cell electrode can adopt DSA electrode, lead electrode or Graphite Electrodes respectively.
As claimed in claim 1, wherein the ion exchange membrane based film of the bipolar membrane of the three four-room Alcaligenes chlorine cell, characterized in that the anion exchange membrane, preparation process: Weigh 3 ~ 6g? chitosan, with 2.0% aqueous acetic acid solution,? formulated as a weight fraction of 3.0 to 4.5% aqueous acetic acid solution of chitosan, the other weighed 0.06 ~ 0.08? g metal phthalocyanine derivative of the amino group, with 10mL dissolved in tetrahydrofuran was slowly added dropwise 3mL volume fraction of 0.25% glutaraldehyde, stir, vacuum degassing, to obtain an anion exchange membrane solution, the anion exchange membrane flow cast on a flat Petri dish,? dried at room temperature film, that is made of an anion exchange membrane? MPc (NH <sub TranNum="195"> 2 </ sub>) <sub TranNum="196"> X </ sub>-CS, where X is the number of amino groups.
5. a kind of three films, four Room based on anion and cation exchange membrane and Bipolar Membrane formation according to claim 1 do not have chlorine and produce the alkali electrolyzer; It is characterized in that described cationic exchange membrane; The preparation process is: take by weighing 4～6g Xylo-Mucine; Be mixed with the sodium carboxymethyl cellulose solution of 200～280 mL; Take by weighing the carboxyl metal phthalocyanine derivative of 0.08～0.1g in addition; Dissolve with the 10mL tetrahydrofuran (THF); Slowly join in the CMC aqueous solution; Stir; Vacuum deaerator; Obtain thickness film liquid, curtain coating in smooth culture dish, at room temperature air-dry film forming; After using weight fraction to be chromium chloride solution immersion 30～40min of 8% (down together); Use distilled water flushing, natural air drying promptly obtains MPc (COOH)
X-CMC cationic exchange membrane, wherein X is amino quantity.
6. a kind of three films, four Room based on anion and cation exchange membrane and Bipolar Membrane formation according to claim 1 do not have chlorine and produce the alkali electrolyzer, it is characterized in that described Bipolar Membrane, are to obtain anion-exchange membrane liquid MPc (NH
2)
X-CS curtain coating is in MPc (COOH)
XOn-CMC the cationic exchange membrane, the MPc (COOH) that obtains after at room temperature air-dry
X-CMC/MPc (NH
2)
X-CS Bipolar Membrane, wherein X is amino quantity.
7. a kind of three films, four Room that constitute based on anion and cation exchange membrane and Bipolar Membrane according to claim 1 do not have chlorine and produce the alkali electrolyzer, it is characterized in that metal in the described metal phthalocyanine derivative is a kind of among Fe, Co, Cu, Ni, Sn, Bi, Pb, Ce, Cf or the Yb.
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