CN104211098B - For carrying out device and the treatment process of electrodialysis and the integrated process of electrolytic electro-dialysis to the alkaline feed liquid in alumina producing - Google Patents
For carrying out device and the treatment process of electrodialysis and the integrated process of electrolytic electro-dialysis to the alkaline feed liquid in alumina producing Download PDFInfo
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Abstract
The invention discloses device and the treatment process for carrying out electrodialysis and the integrated process of electrolytic electro-dialysis to the alkaline feed liquid in alumina producing, feature adopts public feed liquid room tank and alkali collection room tank, electrodialysis unit and electrolytic electro-dialysis device are connected, form an integrating device that alumina producing neutral and alkali feed liquid is separated, electrodialysis unit is wherein utilized to carry out initial gross separation to alkaline feed liquid, carry out degree of depth separation by electrolytic electro-dialysis device again, directly can be separated OH in conjunction with electrodialysis
-the advantage of ion and the advantage such as velocity of separation is fast and electrolytic electro-dialysis " zero " aluminium leakage rate, with being effectively separated with sodium metaaluminate the sodium hydroxide in alkaline feed liquid compared with less energy-consumption, obtains high alkali recovery and low aluminium leakage rate.The meaning of follow-up seeded precipitation operation is, the productive rate of aluminium hydroxide, minimizing time can be improved, reduce energy consumption, also significantly can improve purity and the concentration of alkali in mother liquor, be conducive to it and recycle.
Description
Technical field
The invention belongs to the separation technology field of alumina producing neutral and alkali feed liquid, be specifically related to carry out electrodialysis and electrolytic electro-dialysis integrated processing method and device to this alkaline feed liquid.
Background technology
The production method of aluminum oxide mainly contains Bayer process, soda-lime sintering process and Bayer-sintering integrated process etc.Wherein, Bayer process is the main method of producing aluminum oxide always, output accounts for 95% of whole world aluminum oxide ultimate production, principle be first bauxite is pulverized, wet-milling, then the aluminum oxide in caustic soda (NaOH) solution heating stripping bauxite is used, after being separated residue (red mud), obtain the alkaline feed liquid containing sodium hydroxide and sodium metaaluminate.Be generally the treating processes of this alkaline feed liquid: reduce temperature, add aluminium hydroxide and make crystal seed, through stirring for a long time, sodium metaaluminate divides and parses aluminum hydroxide precipitation.Through filtering, after the mother liquor of liquid phase namely containing NaOH suitably processes, return the operation such as wet-milling, stripping of bauxite; And solid phase, namely aluminum hydroxide precipitation then washs, and in 950-1200 DEG C of calcining, obtains aluminum oxide finished product.In above process, before introducing decomposition of crystal seed sodium metaaluminate, do not carry out separation to alkaline feed liquid to concentrate, in feed liquid alkali and NaOH content very high, be unfavorable for the decomposition of sodium metaaluminate, except needing long-time stirring, consume the energy, extending beyond technical process, degree of decomposition also can be subject to obvious impact, and the productive rate of aluminium hydroxide also can reduce thus.In addition, the mother liquor after filtration can remain more sodium metaaluminate component, and the purity of alkali is not high, and then affects recycling of mother liquor.
For above problem, the Chinese patent (CN 104016388 A) announced proposes before introducing crystal seed, with electrodialytic membranes tripping device, the sodium hydroxide in alkaline feed liquid is separated with sodium metaaluminate, and demonstrates the feasibility of membrane sepn.Be separated early stage and alkali recovery lower time, comparatively fast, energy consumption is lower, and aluminium leakage rate is not high yet for velocity of separation.Such as, when use 7 useful area are 20cm
2ion-exchange membrane time, running 3 hours alkali recoveries is 60-70%, and energy consumption is ~ 3kW h/kg, and aluminium leakage rate is ~ 15%.But be separated the later stage and obviously decline due to alkali concn in feed liquid, meta-aluminic acid radical ion is accelerated by the speed of film, so aluminium leakage rate can quick rising, separation efficiency obviously declines.Such as, when alkali recovery reaches 81.6%, aluminium leakage rate is up to 25.5%, so premature termination of having to is separated.Therefore, alkali recovery and recovery concentration of lye cannot improve further, and the alkali lye of recovery can not directly recycle, and also needs to add new alkali (NaOH), improves production cost, too increases the consumption of chemical.
US Patent No. 5,141,610 and US 5,198,085 report and process with the etching waste liquor of the electrodialytic method of electrolysis to Al and Alalloy.The main component of this etching solution is sodium hydroxide and sodium metaaluminate etc., similar with alumina producing neutral and alkali material liquid component.In operational process, waste liquid passes into anolyte compartment or reaction chamber, under the effect of DC electric field, and OH wherein
-ion electrolysis generates oxygen, or the H generated with electrode reaction
+with generation water in ion; Sodium ion moves to cathode compartment by cationic exchange membrane, the OH produced with cathode compartment brine electrolysis
-ionic bond, generates NaOH; Meta-aluminic acid radical ion then remains on anolyte compartment or reaction chamber, and leakage rate is close to zero.Because in operational process, this room ionic concn obviously declines, for reducing later stage resistance and running voltage, strong electrolytic solution need be introduced as Na
2sO
4.To running the later stage, along with NaOH concentration reduces, meta-aluminic acid root plasma can be hydrolyzed gradually and generate solid precipitation as aluminium hydroxide, intermittent by all components extraction in this room, by processes such as cooling, crystallization and filtrations by precipitate and separate such as aluminium hydroxides, solution then returns and proceeds electrolytic electro-dialysis experiment, until Na
+ion (comprises all Na that NaOH and sodium metaaluminate dissociation go out
+ion) rate of recovery is close to 100%.This method is very high to the rate of recovery of alkali, and aluminium leakage rate is close to zero.But operating process be interval, discontinuous, be unfavorable for actual production process.Although the strong electrolytic solution introduced in anolyte compartment or reaction chamber obviously can reduce running voltage, be unfavorable for the processes such as the isolation andpurification that aluminum hydroxide precipitation is follow-up.In addition, repeatedly carry out electrolytic electro-dialysis separation with a collection of waste liquid, the precipitation such as the aluminium hydroxide repeatedly produced in anolyte compartment or reaction chamber also can cause comparatively serious pollution to film, so be difficult to the process being applicable to the higher alkaline feed liquid of aluminium content.In addition, the OH in waste liquid
-ion can not directly be recycled, and on the contrary, needs to generate OH by electrode reaction
-ion, process is comparatively complicated, and disengaging time is longer.
Therefore, the electrodialysis process of report has velocity of separation comparatively fast at present, directly can be separated, utilize OH
-the advantage of ion, aluminium leakage rate is lower the phase before separation, but there is the defect that high alumina leaks when the degree of depth is separated, so cannot obtain higher alkali recovery; Electrolytic electro-dialysis has the advantage of " zero " aluminium leakage rate when the degree of depth is separated, can reach very high alkali recovery, but it is comparatively serious to there is pollution, directly can not be separated, utilize OH
-the defects such as ion.So far there is no the report of sodium hydroxide and sodium metaaluminate in alkalescence feed liquid when being produced by electrodialysis and the integrated method separation of oxygenated aluminium of electrolytic electro-dialysis.
Summary of the invention
The object of the invention is to propose the method and apparatus that a kind of electrodialysis is separated with sodium metaaluminate the sodium hydroxide in alkalescence feed liquid during alumina producing with electrolytic electro-dialysis integrating device, to overcome the above-mentioned defect of prior art.
For realizing the object of foregoing invention, adopt following technical scheme:
The present invention is used for the device alkaline feed liquid in alumina producing being carried out to electrodialysis and the integrated process of electrolytic electro-dialysis, it is characterized in that: be made up of electrodialysis unit and electrolytic electro-dialysis device:
Described electrodialysis unit is by membrane stack-ED and be fixed on the ED negative electrode of described membrane stack-ED both sides respectively by ED front splint and ED rear plate and ED positive electrode is formed, described membrane stack-ED is arranged by cationic exchange membrane and anion-exchange membrane alternate intervals and forms (cationic exchange membrane and anion-exchange membrane add the subsidiary material such as Upper gasket after alternately laminating and form), and be cationic exchange membrane near the ion-exchange membrane of ED negative electrode and ED positive electrode, ED cathode compartment is formed between ED negative electrode and the cationic exchange membrane be adjacent, ED anolyte compartment is formed between ED positive electrode and the cationic exchange membrane be adjacent, the cationic exchange membrane arranged by alternate intervals between ED cathode compartment to ED anolyte compartment and anion-exchange membrane form the repeating unit of one or more ED feed liquid room and ED alkali collection room, described ED cathode compartment and the series connection of described ED anolyte compartment, and the ED electrode vessel import of described ED cathode compartment and described ED anolyte compartment and the outlet of ED electrode vessel are communicated in electrode vessel tank inside respectively by silicone tube, the ED of ED feed liquid room expects that anolyte chamber inlet and ED expect that chamber outlet is communicated in tank inside, feed liquid room respectively by silicone tube, the ED alkali collection room import of ED alkali collection room and the outlet of ED alkali collection room are communicated in the inside of alkali collection room tank respectively by silicone tube, electrode vessel tank, in feed liquid room tank and alkali collection room tank, solution enters flow in electrodialysis unit respectively by ED electrode vessel peristaltic pump, ED feed liquid room peristaltic pump and ED alkali collection room peristaltic pump control, form ED electrode vessel circulation loop, ED feed liquid room circulation loop and the respective independently circulation loop of ED alkali collection room circulation loop three, described ED negative electrode and ED positive electrode are connected negative pole and the positive pole of ED direct supply respectively by wire,
Described electrolytic electro-dialysis device is by membrane stack-EED and be fixed on the EED negative electrode of described membrane stack-EED both sides respectively by EED front splint and EED rear plate and EED positive electrode is formed, membrane stack-EED in described electrolytic electro-dialysis device is made up of cationic exchange membrane, pad and runner graticule mesh, and wherein EED positive electrode and cationic exchange membrane form EED feed liquid room, and EED negative electrode and cationic exchange membrane form EED alkali collection room, the EED of described EED feed liquid room expects that anolyte chamber inlet and EED expect that chamber outlet is communicated in tank inside, feed liquid room respectively by silicone tube, the EED alkali collection room import of described EED alkali collection room and the outlet of EED alkali collection room are communicated in the inside of alkali collection room tank respectively by silicone tube, the flow that in feed liquid room tank and alkali collection room tank, solution enters in electrolytic electro-dialysis device controls respectively by EED feed liquid room peristaltic pump and EED alkali collection room peristaltic pump, form EED feed liquid room circulation loop and the respective independently circulation loop of EED alkali collection room circulation loop two, described EED negative electrode and EED positive electrode are connected negative pole and the positive pole of EED direct supply respectively by wire,
Described electrodialysis unit and described electrolytic electro-dialysis device share feed liquid room tank and alkali collection room tank, form the device alkaline feed liquid in alumina producing being carried out to electrodialysis and the integrated process of electrolytic electro-dialysis.
Utilize the method that above-mentioned device processes the alkaline feed liquid in alumina producing, be characterized in: first in electrode vessel tank, add the 10-90% of strong electrolytic solution to electrode vessel tank volume respectively, the 10-90% of alkaline feed liquid to feed liquid room tank volume is added in the tank of feed liquid room, the 10-90% of sig water to alkali collection room tank volume is added in the tank of alkali collection room, then ED electrode vessel peristaltic pump is opened, ED feed liquid room peristaltic pump and ED alkali collection room peristaltic pump, respectively to electrode vessel tank, solution in feed liquid room tank and alkali collection room tank carries out the bubble circulating to get rid of electrodialysis unit inside, opening ED direct supply after bubble is drained again makes electrodialysis unit run certain hour under galvanostatic conditions, close ED direct supply, electrodialysis unit out of service, regulate ED electrode vessel peristaltic pump, ED feed liquid room peristaltic pump and ED alkali collection room peristaltic pump are reversion, by the strong electrolytic solution in electrodialysis unit, alkalescence feed liquid and alkali collection liquid are oppositely conveyed into corresponding electrode vessel tank respectively, feed liquid room tank and alkali collection room tank, then EED feed liquid room peristaltic pump and EED alkali collection room peristaltic pump is opened, respectively the bubble getting rid of electrolytic electro-dialysis device inside is circulated to the solution in feed liquid room tank and alkali collection room tank, opening EED direct supply after bubble is drained again makes electrolytic electro-dialysis device run under galvanostatic conditions, it is out of service when the voltage moved in electrolytic electro-dialysis device is elevated to limit voltage.
Above-mentioned method, its feature is also: by the processing power regulating the size of current of ED direct supply and EED direct supply to control electrodialysis unit and electrolytic electro-dialysis device respectively.
Described strong electrolytic solution selects concentration to be metabisulfite solution or the sodium nitrate solution of 0.1-1mol/L.
Described alkaline feed liquid is the mixing solutions of sodium hydroxide and sodium metaaluminate, and the concentration of sodium hydroxide is 0.5-6.0mol/L, and the concentration of sodium metaaluminate is 0.25-3.0mol/L, and the mol ratio of sodium hydroxide and sodium metaaluminate is 1-3:1.
Described sig water is the aqueous sodium hydroxide solution of concentration at 0.1-0.5mol/L, to reduce the resistance of electrodialysis unit initial launch, reduces energy consumption.
It is move to the time used when aluminium leakage rate is 2-10% that described electrodialysis unit runs certain hour under galvanostatic conditions, and preferably moving to aluminium leakage rate was ~ 5% time used.
Compared with the prior art, beneficial effect of the present invention is embodied in:
Electrodialysis is applied to being separated of alumina producing neutral and alkali feed liquid with the integrated approach of electrolytic electro-dialysis with device by the present invention first, with Chinese patent (CN 104016388 A) with compared with the alkaline feed liquid in single electrodialysis unit process alumina producing, greatly increase the rate of recovery of alkali, reduce the leakage rate of aluminium, and energy consumption also remains on lower scope, avoid the separation of the premature termination alkalescence feed liquid because aluminium leakage rate is higher, cause alkali recovery this problem low.Therefore the alkaline feed liquid after integrating device process, alkali concn is very low, and aluminium content is very high, in the production process of carrying out subsequent oxidation aluminium, the productive rate that obviously can reduce the energy consumption of seeded precipitation process, reduce the operating time, improve aluminium hydroxide; In addition, the high alkali recovery of integrating device can improve purity and the concentration of alkali in alkali collection liquid, is conducive to it and recycles.With US Patent No. 5,141,610 and US5,198,085 compares by the method for electrolysis electrodialysis process aluminum or aluminum alloy etching waste liquor, the present invention utilize the integrating device of electrodialysis and electrolytic electro-dialysis come separation of oxygenated aluminium produce in alkaline feed liquid, use electrolytic electro-dialysis before, first with electrodialysis unit, initial gross separation is carried out to alkaline feed liquid, the OH in alkaline feed liquid
-ion can directly be reclaimed, and does not need to generate OH by electrode reaction
-ion, so process is simple, velocity of separation is faster; In addition, in integrating process, the feed liquid room (i.e. anolyte compartment) in electrolytic electro-dialysis does not add strong electrolytic solution, and after aluminium hydroxide, the process such as postprecipitation, isolation andpurification is simplified; Electrolytic electro-dialysis device moves to when voltage is elevated to limit voltage out of service under the condition of continuous current, and alkaline feed liquid can be sent to the conventional process such as follow-up seeded precipitation, filtration, does not need repeatedly to carry out electrolytic electro-dialysis separation, Na wherein
+do not need to be essentially completely recovered, do not have a large amount of aluminum hydroxide precipitations to produce thus, reduce fouling membrane, be beneficial to the continuous operation of integrating device, avoid interval, digital process to the disadvantageous effect of actual production yet.
Accompanying drawing explanation
Fig. 1 is electrodialysis unit schematic diagram;
Fig. 2 is electrolytic electro-dialysis device schematic diagram;
Fig. 3 is the process flow sheet that the integrated treatment unit of electrodialysis unit of the present invention and electrolytic electro-dialysis device and separation of oxygenated aluminium thereof produce neutral and alkali feed liquid.
Number in the figure: 1 electrodialysis unit; 2 electrolytic electro-dialysis devices; 3ED direct supply; 4EED direct supply; 5 electrode vessel tanks; 6 feed liquid room tanks; 7 alkali collection room tanks; 8ED electrode vessel peristaltic pump; 9ED feed liquid room peristaltic pump; 10ED alkali collection room peristaltic pump; 11EED feed liquid room peristaltic pump; 12EED alkali collection room peristaltic pump; 13ED negative electrode; 14ED positive electrode; 15EED negative electrode; 16EED positive electrode; The import of 17ED electrode vessel; 18ED electrode vessel exports; 19ED expects anolyte chamber inlet; 20ED expects chamber outlet; The room import of 21ED alkali collection; 22ED alkali collection room exports; 23EED expects anolyte chamber inlet; 24EED expects chamber outlet; The room import of 25EED alkali collection; 26EED alkali collection room exports; 27ED front splint; 28ED rear plate; 29EED front splint; 30EED rear plate; 31 membrane stack-ED; 32 membrane stack-EED.
Specific embodiment
Further describe the method that separation of oxygenated aluminium of the present invention produces neutral and alkali feed liquid by the following examples.
Embodiment 1
Fig. 1 is electrodialysis unit schematic diagram used in the present embodiment.This electrodialysis unit assembles by with under type: adopt the anion-exchange membrane AMV (3) that produced by Japan AGC Co., Ltd. and cationic exchange membrane CMV (4) to be alternately bolted together to add dividing plate and pad to be formed with the membrane stack-ED 31 of three repeating units, the useful area often opening film is 20cm
2, block board thickness is 10mm.Membrane stack-ED 31 and the ED negative electrode 13, the ED positive electrode 14 that are separately positioned on its two ends, and be placed in the ED front splint 27 at electrode two ends and ED rear plate 28 is clamped by bolt, form electrodialysis unit 1.Its anolyte compartment and cathode compartment series connection, form ED electrode vessel import 17 and an ED electrode vessel outlet 18, and it is inner to be connected to electrode vessel tank 5 by silicone tube, ED expects anolyte chamber inlet 19, ED expects chamber outlet 20 and ED alkali collection room import 21, ED alkali collection room outlet 22 is connected to corresponding feed liquid room tank 6 and the inside of alkali collection room tank 7 respectively by silicone tube, in these three tank bodies, solution enters the flow of electrodialysis unit respectively by ED electrode vessel peristaltic pump 8, ED feed liquid room peristaltic pump 9, ED alkali collection room peristaltic pump 10 controls, uninterrupted is 380mL/min, form electrode vessel circulation loop, feed liquid room circulation loop and the respective independently circulation loop of alkali collection room circulation loop three, the ED negative electrode 13 of this electrodialysis unit 1 and ED positive electrode 14 are connected negative pole and the positive pole of ED direct supply 3 respectively by wire.
Fig. 2 is electrolytic electro-dialysis device schematic diagram used in the present embodiment.This electrolytic electro-dialysis device assembles by with under type: adopt cationic exchange membrane CMV (1), the pad produced by Japan AGC Co., Ltd. to become membrane stack-EED 32 with runner lattice net-shape, this membrane stack comprises a feed liquid room and an alkali collection room, and the useful area of film is 90cm
2, spacer thickness is 0.8mm.Membrane stack-EED 32 and the EED negative electrode 15, the EED positive electrode 16 that are separately positioned on membrane stack two ends, and be placed in the EED front splint 29 at electrode two ends and EED rear plate 30 is clamped by bolt, form electrolytic electro-dialysis device 2.Its EED expects anolyte chamber inlet 23, EED expects chamber outlet 24 and EED alkali collection room import 25, EED alkali collection room outlet 26 is connected to corresponding feed liquid room tank 6 and the inside of alkali collection room tank 7 respectively by silicone tube, the flow that in tank body, solution enters electrolytic electro-dialysis device controls respectively by EED feed liquid room peristaltic pump 11 and EED alkali collection room peristaltic pump 12, uninterrupted is 240mL/min, form feed liquid room circulation loop and the respective independently circulation loop of alkali collection room circulation loop two, the EED negative electrode 15 of this electrolytic electro-dialysis device 2 and EED positive electrode 16 are connected negative pole and the positive pole of EED direct supply 4 respectively by wire,
Fig. 3 is that the present embodiment utilizes above-mentioned existing electrodialysis unit and electrolytic electro-dialysis device to carry out the integrating device of integrated formation, and utilizes the process flow sheet of this integrating device process alumina producing neutral and alkali feed liquid.
The integrating device of the present embodiment is on the basis of electrodialysis unit 1 and electrolytic electro-dialysis device 2, the respective feed liquid room tank of two devices and alkali collection room tank are merged into a feed liquid room tank 6 and an alkali collection room tank 7, so forms an integrated treating device that alumina producing neutral and alkali feed liquid is separated.In treating processes, first carry out initial gross separation by electrodialysis unit 1, then carry out degree of depth separation by electrolytic electro-dialysis device 2.
Alkaline feed liquid in utilizing the above-mentioned integrating device separation of oxygenated aluminium assembled to produce, first adds the metabisulfite solution of 250mL 0.3mol/L in 500mL electrode vessel tank 5, the alkaline feed liquid that 250mL consists of 1.5mol/L sodium hydroxide and 0.81mol/L sodium metaaluminate is added in 500mL feed liquid room tank 6, the sodium hydroxide solution of 250mL 0.2mol/L is added in 500mL alkali collection room tank 7, open ED electrode vessel peristaltic pump 8, ED feed liquid room peristaltic pump 9, ED alkali collection room peristaltic pump 10, respectively by electrode vessel tank 5, feed liquid room tank 6, solution in alkali collection room tank 7 carries out the bubble circulating to get rid of electrodialysis unit 1 inside, opening ED direct supply 3 after bubble is drained again makes electrodialysis unit 1 run under galvanostatic conditions, after being separated for some time, close direct supply 3, regulate ED electrode vessel peristaltic pump 8, ED feed liquid room peristaltic pump 9, ED alkali collection room peristaltic pump 10 is reversion, solution in electrodialysis unit 1 is oppositely conveyed into respectively corresponding electrode vessel tank 5, feed liquid room tank 6, alkali collection room tank 7, open EED feed liquid room peristaltic pump 11 again, EED alkali collection room peristaltic pump 12 pairs of feed liquid room tanks 6, solution in alkali collection room tank 7 carries out the bubble circulating to get rid of electrolytic electro-dialysis device 2 inside, opening EED direct supply 4 after bubble is drained again makes electrolytic electro-dialysis device 2 run under galvanostatic conditions, when the voltage moved in electrolytic electro-dialysis device 2 is elevated to limit voltage (limit voltage is the magnitude of voltage corresponding to voltage curve rising flex point) out of service.The current density provided in electrodialysis unit in the present embodiment is 60mA/cm
2, the current density provided in electrolytic electro-dialysis device is 30mA/cm
2, in sepn process, electrodialysis unit to be respectively 90 working time, 120,150min, experimental result is as table 1.As a comparison, the result that independent electrodialysis process (EED working time be 0) and independent electrolytic electro-dialysis process (ED working time be 0) obtain also arranges in Table 1.
Table 1 electrodialysis unit produces the impact of neutral and alkali feed liquid working time on integrating device separation of oxygenated aluminium.
Note: ED represents electrodialysis, EED represents electrolytic electro-dialysis.EED be working time electrolytic electro-dialysis plant running to the voltage in electrolytic electro-dialysis device reach capacity voltage time required time.
From the data of table 1, independent electrodialysis unit is separated feed liquid, very fast to the recovery speed of alkali, 180min can obtain the more high-alkali rate of recovery (92.6%), but now aluminium leakage rate is very high, be 15.1%, this is very disadvantageous to the production of aluminum oxide and the recycle of mother liquor.When independent electrolytic electro-dialysis device is separated feed liquid, although be " zero " aluminium leakage rate, velocity of separation is comparatively slow, needs 220min, is unfavorable for Industrial processes.The alkaline feed liquid in alumina producing is processed with the integrating device of electrodialysis unit and electrode electrodialysis unit, higher alkali recovery, velocity of separation and lower aluminium leakage rate can be obtained, so be better than the treating processes of single electrodialysis unit or single electrolytic electro-dialysis device simultaneously.
In addition, as can be known from the results of Table 1, during integrating device process feed liquid, along with the increase of electrodialysis unit working time, aluminium leakage rate rises to some extent, and after 120min, aluminium leakage rate rises comparatively obvious, is unfavorable for the production of follow-up aluminum oxide and the recycle of mother liquor; On the other hand, electrodialysis unit shortening working time, the working time of electrolytic electro-dialysis device correspondingly will extend, and is unfavorable for OH in alkaline feed liquid
-the direct recovery of ion.Considering, can working time of preferred electrodialysis unit be 120min.With this understanding, alkali recovery up to 90.9%, the 60-70% in Chinese patent (CN 104016388 A); Aluminium leakage rate is ~ 5%, much smaller than in Chinese patent (CN 104016388 A) ~ 15%; Energy consumption is 2.25kW h/kg, lower than in Chinese patent (CN 104016388 A) ~ 3kW h/kg.Wherein, high alkali recovery can reduce paper mill wastewater in alkaline feed liquid greatly, alkaline feed liquid after separation can be sent to the conventional process such as follow-up seeded precipitation, filtration, does not need repeatedly to carry out electrolytic electro-dialysis separation, thus avoid interval, digital process to the disadvantageous effect of actual production.In addition, with US Patent No. 5,141,610 and US 5,198,085 repeatedly generates the precipitated phase ratios such as aluminium hydroxide with electrolysis electrodialytic method in anolyte compartment or reaction chamber, in the alkaline feed liquid of the present embodiment process, aluminium content is higher, does not but have obvious aluminum hydroxide precipitation to produce, reduces fouling membrane.
Embodiment 2
It is identical with embodiment 1 that this implements integrating device used, and experimentation is on the basis of embodiment 1, by the current density that provides electrodialysis unit from 60mA/cm
2be reduced to 45mA/cm
2, electrodialysis unit working time is 150min, and other operational conditions and process are all identical with embodiment 1, and experimental result is as table 2.
In table 2 electrodialysis unit, low current density produces the impact of neutral and alkali feed liquid on integrating device separation of oxygenated aluminium.
As can be known from the results of Table 2, during alkaline feed liquid in the integrating device process alumina producing of electrodialysis unit and electrolytic electro-dialysis device, after reducing the current density that electrodialysis unit is provided, under control aluminium leakage rate is the condition of ~ 5%, by increasing the working time of electrodialysis unit and electrolytic electro-dialysis device respectively, the value (~ 90%) that alkali recovery reaches higher can be made equally.In addition, compare with treating processes preferred in embodiment 1 (electrodialysis unit working time be 120min), energy consumption have dropped about 13%, i.e. decline 0.3kW h/kg; The total run time of integrating device adds about 22%, namely increases 40min.In a word, after reducing the current density provided electrodialysis unit, when reaching identical separating effect, energy consumption reduces, and total run time increases.Therefore, in actual production process, when considering energy consumption and velocity of separation, by the processing power regulating the current density of electrodialysis unit to carry out control integration device, reach required separating effect.
Embodiment 3
The present embodiment integrating device used is identical with embodiment 1, and experiment condition is as follows: the metabisulfite solution adding 250mL0.5mol/L in electrode vessel tank 5; The simulation alkalescence feed liquid that 250mL consists of 2.6mol/L sodium hydroxide and 1.3mol/L sodium metaaluminate is added in feed liquid room tank 6; The sodium hydroxide solution of 250mL 0.3mol/L is added in alkali collection room tank 7; The current density provided in electrodialysis unit is 75mA/cm
2; The current density provided in electrolytic electro-dialysis device is 50mA/cm
2; In sepn process, electrodialysis unit working time is 150min; The electrolytic electro-dialysis plant running time is 60min.Other operational conditions and process are all identical with embodiment 1, and result is as shown in table 3.
The alkaline feed liquid of table 3 integrating device process high density.
Compared with Chinese patent (CN 104016388 A), the present embodiment is while reaching relatively high alkali recovery (83.4%), aluminium leakage rate (3.3%) be only its about 1/5, be conducive to significantly improving the purity of alkali in the productive rate of aluminium hydroxide in subsequent process and mother liquor; Energy consumption is also lower, is 2.18kW h/kg, is beneficial to and reduces costs.With US Patent No. 5,141,610 and US 5,198,085 compares, and the present embodiment does not also significantly precipitate generation, and fouling membrane is lower.In addition, can being found out with comparing of embodiment 1 and 2 by the present embodiment, when the concentration of alkaline feed liquid increases, by improving current density, good treatment effect can be reached equally within relatively short working time and 210min.Therefore according to the requirement of actual production, by the processing power regulating the current density of electrodialysis and electrolytic electro-dialysis device to carry out control integration device, the separating effect of expection can be reached.
Claims (4)
1., for carrying out the device of electrodialysis and the integrated process of electrolytic electro-dialysis to the alkaline feed liquid in alumina producing, it is characterized in that:
Be made up of electrodialysis unit (1) and electrolytic electro-dialysis device (2):
Described electrodialysis unit (1) is by membrane stack-ED (31) and be fixed on the ED negative electrode (13) of described membrane stack-ED (31) both sides respectively by ED front splint (27) and ED rear plate (28) and ED positive electrode (14) is formed, described membrane stack-ED (31) is arranged by cationic exchange membrane and anion-exchange membrane alternate intervals and forms, and be cationic exchange membrane near the ion-exchange membrane of ED negative electrode (13) and ED positive electrode (14), ED cathode compartment is formed between ED negative electrode (13) and the cationic exchange membrane be adjacent, ED anolyte compartment is formed between ED positive electrode (14) and the cationic exchange membrane be adjacent, the cationic exchange membrane arranged by alternate intervals between ED cathode compartment to ED anolyte compartment and anion-exchange membrane form the repeating unit of one or more ED feed liquid room and ED alkali collection room, described ED cathode compartment and the series connection of described ED anolyte compartment, and the ED electrode vessel import (17) of described ED cathode compartment and described ED anolyte compartment and ED electrode vessel outlet (18) are communicated in electrode vessel tank (5) inside respectively by silicone tube, the ED of ED feed liquid room expects that anolyte chamber inlet (19) and ED expect that chamber outlet (20) is communicated in inside, feed liquid room tank (6) respectively by silicone tube, the ED alkali collection room import (21) of ED alkali collection room and ED alkali collection room outlet (22) are communicated in the inside of alkali collection room tank (7) respectively by silicone tube, electrode vessel tank (5), feed liquid room tank (6) and alkali collection room tank (7) interior solution enter flow in electrodialysis unit (1) respectively by ED electrode vessel peristaltic pump (8), ED feed liquid room peristaltic pump (9) and ED alkali collection room peristaltic pump (10) control, form ED electrode vessel circulation loop, ED feed liquid room circulation loop and the respective independently circulation loop of ED alkali collection room circulation loop three, described ED negative electrode (13) and ED positive electrode (14) are connected negative pole and the positive pole of ED direct supply (3) respectively by wire,
Described electrolytic electro-dialysis device (2) is by membrane stack-EED (32) and be fixed on the EED negative electrode (15) of described membrane stack-EED (32) both sides respectively by EED front splint (29) and EED rear plate (30) and EED positive electrode (16) is formed, membrane stack-EED (32) in described electrolytic electro-dialysis device (2) is made up of cationic exchange membrane, pad and runner graticule mesh, wherein EED positive electrode (16) and cationic exchange membrane form EED feed liquid room, and EED negative electrode (15) and cationic exchange membrane form EED alkali collection room, the EED of described EED feed liquid room expects that anolyte chamber inlet (23) and EED expect that chamber outlet (24) is communicated in inside, feed liquid room tank (6) respectively by silicone tube, the EED alkali collection room import (25) of described EED alkali collection room and EED alkali collection room outlet (26) are communicated in the inside of alkali collection room tank (7) respectively by silicone tube, the flow that feed liquid room tank (6) and alkali collection room tank (7) interior solution enter in electrolytic electro-dialysis device (2) controls respectively by EED feed liquid room peristaltic pump (11) and EED alkali collection room peristaltic pump (12), form EED feed liquid room circulation loop and the respective independently circulation loop of EED alkali collection room circulation loop two, described EED negative electrode (15) and EED positive electrode (16) are connected negative pole and the positive pole of EED direct supply (4) respectively by wire,
Described electrodialysis unit (1) and described electrolytic electro-dialysis device (2) share feed liquid room tank (6) and alkali collection room tank (7), form the device alkaline feed liquid in alumina producing being carried out to electrodialysis and the integrated process of electrolytic electro-dialysis.
2. utilize the method that the device described in claim 1 processes the alkaline feed liquid in alumina producing, it is characterized in that: first in electrode vessel tank (5), add the 10-90% of strong electrolytic solution to electrode vessel tank volume respectively, the 10-90% of alkaline feed liquid to feed liquid room tank volume is added in feed liquid room tank (6), the 10-90% of sig water to alkali collection room tank volume is added in alkali collection room tank (7), then ED electrode vessel peristaltic pump (8) is opened, ED feed liquid room peristaltic pump (9) and ED alkali collection room peristaltic pump (10), respectively to electrode vessel tank (5), solution in feed liquid room tank (6) and alkali collection room tank (7) carries out circulating to get rid of the inner bubble of electrodialysis unit (1), opening ED direct supply (3) after bubble is drained again makes electrodialysis unit (1) run certain hour under galvanostatic conditions, close ED direct supply (3), electrodialysis unit out of service (1), regulate ED electrode vessel peristaltic pump (8), ED feed liquid room peristaltic pump (9) and ED alkali collection room peristaltic pump (10) are reversion, by the strong electrolytic solution in electrodialysis unit (1), alkalescence feed liquid and alkali collection liquid are oppositely conveyed into corresponding electrode vessel tank (5) respectively, feed liquid room tank (6) and alkali collection room tank (7), then EED feed liquid room peristaltic pump (11) and EED alkali collection room peristaltic pump (12) is opened, circulate to get rid of the inner bubble of electrolytic electro-dialysis device (2) to the solution in feed liquid room tank (6) and alkali collection room tank (7) respectively, opening EED direct supply (4) after bubble is drained again makes electrolytic electro-dialysis device (2) run under galvanostatic conditions, it is out of service when the voltage moved in electrolytic electro-dialysis device (2) is elevated to limit voltage,
It is move to the time used when aluminium leakage rate is 2-10% that described electrodialysis unit (1) runs certain hour under galvanostatic conditions;
Described alkaline feed liquid is the mixing solutions of sodium hydroxide and sodium metaaluminate, and the concentration of sodium hydroxide is 0.5-6.0mol/L, and the concentration of sodium metaaluminate is 0.25-3.0mol/L, and the mol ratio of sodium hydroxide and sodium metaaluminate is 1-3:1;
Described sig water is the aqueous sodium hydroxide solution of concentration at 0.1-0.5mol/L.
3. method as claimed in claim 2, is characterised in that: by the processing power regulating the size of current of ED direct supply (3) and EED direct supply (4) to control electrodialysis unit (1) and electrolytic electro-dialysis device (2) respectively.
4. method as claimed in claim 2, is characterised in that: described strong electrolytic solution selects concentration to be metabisulfite solution or the sodium nitrate solution of 0.1-1mol/L.
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| CN113044863B (en) * | 2021-04-25 | 2022-06-21 | 百色学院 | Method for improving decomposition rate of seed precipitation in alumina production |
| CN114560484B (en) * | 2022-03-31 | 2023-08-18 | 大连理工大学 | Method for producing low-sodium alumina by electrodialysis method |
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