CN103866344A - Method for preparing nitric acid through electrolysis - Google Patents
Method for preparing nitric acid through electrolysis Download PDFInfo
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- CN103866344A CN103866344A CN201410087917.XA CN201410087917A CN103866344A CN 103866344 A CN103866344 A CN 103866344A CN 201410087917 A CN201410087917 A CN 201410087917A CN 103866344 A CN103866344 A CN 103866344A
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- anolyte
- nitric acid
- electrolytic
- nitrate
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- 238000000034 method Methods 0.000 title claims abstract description 45
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 31
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 20
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 3
- 239000010935 stainless steel Substances 0.000 claims abstract description 3
- 239000012528 membrane Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical group [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 239000013589 supplement Substances 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 229940001516 sodium nitrate Drugs 0.000 claims description 4
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 210000000952 spleen Anatomy 0.000 claims description 2
- 210000002784 stomach Anatomy 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003792 electrolyte Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 32
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 239000003014 ion exchange membrane Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- -1 hydrogen sodium oxide Chemical class 0.000 description 4
- 239000002253 acid Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000618 nitrogen fertilizer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229910017840 NH 3 Inorganic materials 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- DVARTQFDIMZBAA-UHFFFAOYSA-O ammonium nitrate Chemical class [NH4+].[O-][N+]([O-])=O DVARTQFDIMZBAA-UHFFFAOYSA-O 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- OMBRFUXPXNIUCZ-UHFFFAOYSA-N dioxidonitrogen(1+) Chemical compound O=[N+]=O OMBRFUXPXNIUCZ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
Abstract
The invention discloses a method for preparing nitric acid through electrolysis. A device adopted in the method comprises a diaphragm type electrolytic cell reactor. The method comprises the following steps: (1) respectively putting a nickel screen serving as an anode and stainless steel or a nickel screen as a cathode in an anode chamber and a cathode chamber; (2) respectively supplying anolyte and catholyte to the anode chamber and the cathode chamber, wherein the anolyte is a nitrate aqueous solution, and the catholyte is aqueous alkali to which positive ions in nitrate correspond; (3) carrying out constant current electrolysis by using direct current while controlling the temperature of electrolyte at 20-60 DEG C and electric current density at 0.8-4.5kA/m<2>; (4) when the concentration of positive ions in the anolyte is less than 3M, taking out the anolyte, and distilling at the temperature of 150 DEG C so as to obtain a nitric acid solution with the mass percentage concentration of 38-42%; (5) evaporating the obtained nitric acid solution again so as to remove water for purifying, and thus obtaining the nitric acid product with the mass percentage concentration of 65-68%. The method is high in electrolytic efficiency, short in technological process and environment-friendly, and byproducts are high in economic value.
Description
Technical field
The present invention relates to a kind of mineral acid electrochemical method for synthesizing, a kind of particularly method of electrolytic preparation nitric acid, belongs to electrochemical synthesis field.
Background technology
Nitric acid molecular formula HNO
3, be one of staple product of basic chemical industry, be also a kind of important industrial chemicals.At present, nearly 5,400 ten thousand tons/day of world's nitric acid output (Chinese nitric acid output has also reached approximately 5,500,000 tons/day), wherein, about more than 70% as the intermediates of nitrogenous fertilizer, acid massfraction is 42～60%, mainly for the production of products such as the ammonium nitrates in nitrogenous fertilizer.
Current all nitric acid production technique is to be all based upon on the heterogeneous catalytic oxidation basis of air and gas ammonia, and airborne oxygen and ammonia first generate nitrogen protoxide, are further oxidized to nitrogen peroxide and then in water, are absorbed and obtain nitric acid.But in actual production process, this technique exists waste gas and wastewater discharge is large, liquefied ammonia consumption is large, catalyzer (platinum) is expensive and working pressure needs the problems such as accurately control.This present situation has not only hindered the Sustainable development of nitric acid industry, is also unfavorable for the sound development of national economy, in the urgent need to developing new production technology, in meeting the need of market, reduces environmental pollution.
From domestic and international production technology development trend, Green Chemistry is trend of the times.Its core connotation is exactly that existing chemical production technical route is changed into from " pollution is eradicated in source " from " first pollute, improvement ", reduce or eliminate the generation to the poisonous and hazardous raw material of ecotope, catalyzer and by product from source, make every effort to make chemical reaction to there is " Atom economy ", realize " zero release " of refuse.
Ion-exchange membrane electrolysis is the new technology growing up on the basis of ion exchange resin.Utilize ion-exchange membrane to allow the moon or positively charged ion to reach the object of concentrated, desalination, purification, purification and electrochemical synthesis by the characteristic that limits opposite charges ion and pass through.Ion-exchange membrane electrolysis is now successfully for aspects such as chlor-alkali production, sea water desaltination, electroplating effluents.But the method that up to now, adopts ion-exchange membrane electrolysis to prepare nitric acid not yet has open report.
Summary of the invention
The object of the invention is to propose a kind of method of electrolytic preparation nitric acid, this method has advantages of that electrolytic efficiency is high, flow process is short, environmental friendliness, byproduct economic worth are high.
For achieving the above object, the present invention is by the following technical solutions:
A method for electrolytic preparation nitric acid, the device of employing comprises diaphragm electrolytic cell reactor, this electrolyzer reaction device is divided into cathode compartment and anolyte compartment by cationic exchange membrane; Specifically comprise the following steps:
(1), using nickel screen as anode, using stainless steel or nickel screen as negative electrode, be placed in respectively anolyte compartment and cathode compartment;
(2) anolyte and catholyte are supplied to respectively in anolyte compartment and cathode compartment, wherein, anolyte is nitrate aqueous solution, and catholyte is the corresponding alkaline solution of the positively charged ion in this nitrate;
(3) carry out constant-current electrolysis with direct current, the temperature of controlling electrolytic solution is 20～60 DEG C, and current density is 0.8～4.5kA/m
2;
(4) in the time that the cation concn in anolyte is less than 3M, stop electrolytic reaction, take out anolyte, obtaining mass percent concentration 150 DEG C of distillations is 38～42% salpeter solution;
(5) evaporation again of salpeter solution step (4) the being obtained purification of anhydrating, obtains mass percent concentration and is 65～68% nitric acid product.
Wherein, the further method of purification of the distillation of anolyte and salpeter solution adopts the ordinary method in the preparation of nitric acid technique of this area.
The principle of foundation of the present invention be nitrate aqueous solution in electrolyzer anode chamber under the effect of electrical forces, the monovalent cation in solution moves to cathode direction.Meanwhile, due to the selection perviousness of cationic exchange membrane, inorganic anion cannot spread through cationic exchange membrane, only has monovalent cation could select to see through and enters cathode compartment, and being enriched in wherein.Water molecules in electric tank cathode chamber is decomposed into hydrogen and hydroxide ion on negative electrode, and water molecules in anolyte compartment is decomposed into oxygen and hydrogen ion on anode.The hydroxide ion that cathode compartment generates is with being moved the monovalent cation coming by anolyte compartment in conjunction with generating alkali.And anolyte compartment generate hydrogen ion be combined with nitrate radical generation nitric acid.Therefore, the essence of this electrolytic reaction is brine electrolysis.Electrolytic reaction equation is:
In the method for the invention, in described anolyte, be added with additive, this additive is the nitrite that nitrate middle-jiao yang, function of the spleen and stomach ion pair is answered, and the concentration of this additive in anolyte is 0.01～0.07M.
In the method for the invention, the mass percent concentration of described nitrate aqueous solution is preferably 8～45%.Preferably use SODIUMNITRATE, saltpetre or ammonium nitrate as nitrate.
In the method for the invention, the mass percent concentration of described alkaline solution is preferably 1～20%; Described cationic exchange membrane is perfluorinated ionic membrane, is preferably perfluorinated sulfonic acid-perfluorocarboxylic acid composite ionic membrane; Distance between negative electrode and positive electrode is preferably 0.5～10cm.
In the method for the invention, the residual solution in described step (4) after distillation is after adjusting nitrate concentration and additive concentration wherein, and circulation is supplemented in anolyte.
In the method for the invention, the alkaline solution of the high density that after electrolytic reaction, cathode compartment obtains can supplement liquid as negative electrode after dilution, also can concentrate and produce alkali product; Hydrogen and oxygen that in electrolytic process, cathode and anode generates, can be used as by product and collect use.
Compared with prior art, beneficial effect of the present invention is as follows:
1, method of the present invention has been avoided using the loaded down with trivial details technological process such as catalyzer, pressurized operation in existing method, and method of the present invention is simple, easily realizes industrial amplification production;
2, method of the present invention is utilized ion-exchange membrane electrolyzer for chlor-alkali production, both brought into play the advantage that fluoro-containing macromolecule material electrochemical corrosion resistant is strong, can stop again the infiltration of negatively charged ion from negative electrode anode, can realize high current efficiency and low power consumption, technological process current efficiency is more than 96%;
3, method of the present invention adopts ion-exchange membrane electrolysis to prepare nitric acid, the electric energy that the energy used is clean and effective, in production process without waste gas discharge of wastewater, safety and environmental protection;
4, method byproduct of the present invention is high value alkali (NaOH, KOH or NH
3h
2o), hydrogen and oxygen, these byproducts both can be used as merchandise sales, also can directly in nitric plant, apply.
Brief description of the drawings
Fig. 1 is process flow diagram of the present invention.
Fig. 2 is the structural representation of the electrolyzer that uses of the present invention.
Embodiment
By the following examples the present invention is further described, but the present invention is not limited only to following examples.
As shown in Figure 1, be process flow diagram of the present invention.As shown in Figure 2, for the structural representation of electrolyzer used in the present invention, wherein the material of electrolyzer adopts synthetic glass, electrolyzer is divided into cathode compartment and anolyte compartment by cationic exchange membrane 1, anode 2 and negative electrode 3 are placed in respectively anolyte compartment and cathode compartment, anolyte is imported and exported 4 from anolyte and is added or take out, and catholyte is imported and exported 5 from catholyte and added or take out, and the oxygen that electrolysis generates and hydrogen are discharged from pneumatic outlet 6,7.
Perfluorinated sulfonic acid-perfluorocarboxylic acid the composite ionic membrane using in embodiment is commercial goods film, DF2801 type (Shandong Dongyue Polymer Material Co., Ltd.), F8020 type (Japan AGC company) and N966 type (E.I.Du Pont Company's production) perfluorochemical ion membrane in chlor-alkali industry.In embodiment, various mesh electrodes are the conventional products that chlorine industry is used, and Suzhou Bo Rui company provides.
Data processing:
(1) product nitric acid and cathode product (NaOH, KOH or NH in embodiment
3h
2o) concentration determination is measured according to acid base titration.
(2) the present invention can use formula (I) to calculate the cathode efficiency η (%) of electrolytic process in for some time
In formula, taking sodium hydroxide as cathode materials liquid as example:
η---current efficiency, %;
F---Faraday's number, 96485C/mol;
M---in electrolytic process, for some time inner cathode is collected the quality of product sodium hydroxide, g;
In n---electrolysis for some time, pass through electrolyzer electric weight, Amin;
The molecular weight of M---sodium hydroxide, 40g/mol.
In the present embodiment, adopt DF2801 type perfluorinated ionic membrane that electrolyzer is divided into cathode compartment and anolyte compartment, anode and negative electrode adopt respectively nickel screen electrode and stainless (steel) wire electrode, and the useful area of anode and negative electrode is all 64cm
2, the spacing of negative electrode and positive electrode is 1cm.
The sodium nitrate aqueous solution that is 30% using mass percent concentration is as anolyte, mass percent concentration is that 3% sodium hydroxide solution is as catholyte, after being preheated to 40 DEG C, add respectively anolyte compartment and cathode compartment, connect direct supply, by constant voltage dc source control current density at 1KA/m
2electrolysis 60min under condition, now Na in anolyte
+concentration is about 2.1M, collects anolyte, and obtaining mass percent concentration through distillation, purification processes is 67% salpeter solution, and it is 5.5% sodium hydroxide solution that cathode compartment obtains mass percent concentration.Current efficiency η is 96.1% as calculated.The hydrogen that the oxygen that anolyte compartment produces and cathode compartment produce reclaims by gas extractor respectively.The high-concentration sodium hydroxide that cathode compartment obtains can supplement liquid as negative electrode after dilution, also can concentrate preparing hydrogen sodium oxide product.
In the present embodiment, adopt F8020 type perfluorinated ionic membrane that electrolyzer is divided into cathode compartment and anolyte compartment, anode and negative electrode all adopt nickel screen electrode, and the useful area of anode and negative electrode is all 64cm
2, the spacing of negative electrode and positive electrode is 5cm.
The Alkitrate that is 10% using mass percent concentration is as anolyte, mass percent concentration is that 8% potassium hydroxide solution is as catholyte, after being preheated to 60 DEG C, add respectively anolyte compartment and cathode compartment, connect direct supply, by constant voltage dc source control current density at 3KA/m
2electrolysis 30min under condition, now K in anolyte
+concentration is about 2.7M, collects anolyte, and obtaining mass percent concentration through distillation, purification processes is 65% salpeter solution, and it is 11.5% potassium hydroxide solution that cathode compartment obtains mass percent concentration.Current efficiency η is 97.8% as calculated.The hydrogen that the oxygen that anolyte compartment produces and cathode compartment produce reclaims by gas extractor respectively.The high concentration of hydrogen potassium oxide that cathode compartment obtains can supplement liquid as negative electrode after dilution, also can concentrate preparing hydrogen potassium oxide product.
Embodiment 3
In the present embodiment, adopt N966 type perfluorinated ionic membrane that electrolyzer is divided into cathode compartment and anolyte compartment, anode and negative electrode adopt respectively nickel screen electrode and titanium net electrode, and the useful area of anode and negative electrode is all 64cm
2, the spacing of negative electrode and positive electrode is 9cm.
The sodium nitrate aqueous solution that is 44% using mass percent concentration is as anolyte, mass percent concentration is that 20% sodium hydroxide solution is as catholyte, after being preheated to 50 DEG C, add respectively anolyte compartment and cathode compartment, connect direct supply, by constant voltage dc source control current density at 4.5KA/m
2electrolysis 30min under condition, now Na in anolyte
+concentration is about 2.8M, collects anolyte, and obtaining mass percent concentration through distillation, purification processes is 65% salpeter solution, and it is 25.5% sodium hydroxide solution that cathode compartment obtains mass percent concentration.Current efficiency η is 98.1% as calculated.The hydrogen that the oxygen that anolyte compartment produces and cathode compartment produce reclaims by gas extractor respectively.The high-concentration sodium hydroxide that cathode compartment obtains can supplement liquid as negative electrode after dilution, also can concentrate preparing hydrogen sodium oxide product.
In the present embodiment, adopt F8020 type perfluorinated ionic membrane that electrolyzer is divided into cathode compartment and anolyte compartment, anode and negative electrode all adopt nickel screen electrode, and the useful area of anode and negative electrode is all 64cm
2, the spacing of negative electrode and positive electrode is 1cm.
The aqueous ammonium nitrate solution that is 10% using mass percent concentration is as anolyte, mass percent concentration is that 10% ammoniacal liquor is as catholyte, after being preheated to 30 DEG C, add respectively anolyte compartment and cathode compartment, connect direct supply, by constant voltage dc source control current density at 4KA/m
2electrolysis 20min under condition, now NH in anolyte
4 +concentration is about 2.9M, collects anolyte, and obtaining mass percent concentration through distillation, purification processes is 65% salpeter solution, and it is 15.1% ammonia soln that cathode compartment obtains mass percent concentration.Current efficiency η is 97.4% as calculated.The hydrogen that the oxygen that anolyte compartment produces and cathode compartment produce reclaims by gas extractor respectively.The high density ammoniacal liquor that cathode compartment obtains can supplement liquid as negative electrode after dilution, also can concentrate preparing ammonia fishery products.
Claims (9)
1. a method for electrolytic preparation nitric acid, is characterized in that, the device of employing comprises diaphragm electrolytic cell reactor, and this electrolyzer reaction device is divided into cathode compartment and anolyte compartment by cationic exchange membrane; Specifically comprise the following steps:
(1), using nickel screen as anode, using stainless steel or nickel screen as negative electrode, be placed in respectively anolyte compartment and cathode compartment;
(2) anolyte and catholyte are supplied to respectively in anolyte compartment and cathode compartment, wherein, anolyte is nitrate aqueous solution, and catholyte is the corresponding alkaline solution of the positively charged ion in this nitrate;
(3) carry out constant-current electrolysis with direct current, the temperature of controlling electrolytic solution is 20～60 DEG C, and current density is 0.8～4.5kA/m
2;
(4) in the time that the cation concn in anolyte is less than 3M, stop electrolytic reaction, take out anolyte, obtaining mass percent concentration 150 DEG C of distillations is 38～42% salpeter solution;
(5) evaporation again of salpeter solution step (4) the being obtained purification of anhydrating, obtains mass percent concentration and is 65～68% nitric acid product.
2. the method for electrolytic preparation nitric acid according to claim 1, it is characterized in that, in described anolyte, be added with additive, this additive is the nitrite that nitrate middle-jiao yang, function of the spleen and stomach ion pair is answered, and the concentration of this additive in anolyte is 0.01～0.07M.
3. the method for electrolytic preparation nitric acid according to claim 1 and 2, is characterized in that, the mass percent concentration of described nitrate aqueous solution is 8～45%.
4. the method for electrolytic preparation nitric acid according to claim 1 and 2, is characterized in that, described nitrate is SODIUMNITRATE, saltpetre or ammonium nitrate.
5. the method for electrolytic preparation nitric acid according to claim 1 and 2, is characterized in that, the mass percent concentration of described alkaline solution is 1～20%.
6. the method for electrolytic preparation nitric acid according to claim 1 and 2, is characterized in that, described cationic exchange membrane is perfluorinated sulfonic acid-perfluorocarboxylic acid composite ionic membrane.
7. the method for electrolytic preparation nitric acid according to claim 1 and 2, is characterized in that, the distance between negative electrode and positive electrode is 0.5～10cm.
8. the method for electrolytic preparation nitric acid according to claim 2, is characterized in that, the residual solution in described step (4) after distillation is after adjusting nitrate concentration and additive concentration wherein, and circulation is supplemented in anolyte.
9. the method for electrolytic preparation nitric acid according to claim 1 and 2, is characterized in that, the alkaline solution of the high density that after electrolytic reaction, cathode compartment obtains supplements liquid as negative electrode after dilution, or the concentrated alkali product of producing.
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| CN106191910A (en) * | 2016-09-19 | 2016-12-07 | 上海应用技术大学 | A kind of it is electrolysed the method that hexafluosilicic acid prepares fluosilicate |
| CN106731557A (en) * | 2016-12-27 | 2017-05-31 | 中国环境科学研究院 | Absorbing liquid circulation utilization method and system during a kind of denitrating flue gas |
| CN110066012A (en) * | 2019-03-28 | 2019-07-30 | 华南师范大学 | A kind of process for reclaiming cooperateing with recycling nitrogen and phosphorus from sludge using anaerobic digestion |
| CN110387574A (en) * | 2018-04-19 | 2019-10-29 | 台湾积体电路制造股份有限公司 | The control method and semiconductor equipment of chemical concentrations in electrolyte |
| CN112047546A (en) * | 2020-08-10 | 2020-12-08 | 何学文 | Treatment process for wastewater containing nitrate nitrogen through anodic oxidation |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106191910A (en) * | 2016-09-19 | 2016-12-07 | 上海应用技术大学 | A kind of it is electrolysed the method that hexafluosilicic acid prepares fluosilicate |
| CN106731557A (en) * | 2016-12-27 | 2017-05-31 | 中国环境科学研究院 | Absorbing liquid circulation utilization method and system during a kind of denitrating flue gas |
| CN110387574A (en) * | 2018-04-19 | 2019-10-29 | 台湾积体电路制造股份有限公司 | The control method and semiconductor equipment of chemical concentrations in electrolyte |
| CN110387574B (en) * | 2018-04-19 | 2021-10-26 | 台湾积体电路制造股份有限公司 | Method for controlling chemical concentration in electrolyte and semiconductor device |
| US11280021B2 (en) | 2018-04-19 | 2022-03-22 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method of controlling chemical concentration in electrolyte and semiconductor apparatus |
| US11668019B2 (en) | 2018-04-19 | 2023-06-06 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method of controlling chemical concentration in electrolyte |
| CN110066012A (en) * | 2019-03-28 | 2019-07-30 | 华南师范大学 | A kind of process for reclaiming cooperateing with recycling nitrogen and phosphorus from sludge using anaerobic digestion |
| CN112047546A (en) * | 2020-08-10 | 2020-12-08 | 何学文 | Treatment process for wastewater containing nitrate nitrogen through anodic oxidation |
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