CN113620458A - Process and equipment for recovering aluminum-containing and heavy metal-containing waste alkali liquor - Google Patents

Process and equipment for recovering aluminum-containing and heavy metal-containing waste alkali liquor Download PDF

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CN113620458A
CN113620458A CN202110786085.0A CN202110786085A CN113620458A CN 113620458 A CN113620458 A CN 113620458A CN 202110786085 A CN202110786085 A CN 202110786085A CN 113620458 A CN113620458 A CN 113620458A
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tank
waste
alkali
aluminum
solution
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CN113620458B (en
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邹松华
尚洪帅
王帅东
张昕宇
彭建昌
陈龙
徐猛
王建军
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Beijing Hanchang Luyuan Environmental Protection Technology Co ltd
Tianjin Aerospace Changzheng Rocket Manufacturing Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5281—Installations for water purification using chemical agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention provides a process and equipment for recovering aluminum-containing and heavy metal-containing waste alkali liquor, which are used for recovering the waste alkali liquor generated in the aluminum alloy chemical milling treatment process; the method comprises the following steps: removing impurities; removing aluminum; disassembling the bipolar membrane to obtain an acid solution and an alkali solution; the recovery equipment is used for recovering waste alkali liquor generated in the aluminum alloy chemical milling treatment process; the method comprises the following steps: the device comprises a chemical milling groove, an impurity removal tank, a pH adjusting tank, a first salt tank, a second salt tank, a bipolar membrane stack, an acid tank and an alkali tank. The acid solution is used for pH adjustment in the aluminum removal step, and the alkali solution is used for chemical milling treatment of aluminum alloy.

Description

Process and equipment for recovering aluminum-containing and heavy metal-containing waste alkali liquor
Technical Field
The invention relates to the technical field of waste liquid treatment in chemical milling treatment, in particular to a process and equipment for recovering aluminum-containing and heavy metal-containing waste alkali liquid.
Background
In the prior art, aluminum alloy is widely applied due to excellent performance, and particularly widely applied in the aerospace industry.
For example, in an aerospace system, in order to control the total weight of a spacecraft, an aluminum alloy material with low density and strong structure is mostly used for the outer shell of the spacecraft. Wherein, part of the aluminum alloy structure needs further chemical milling treatment for further reducing the weight:
1. according to the required shape, a layer of organic glue is smeared on the surface of the flat aluminum alloy, and the glue can be combined with the aluminum alloy secret;
2. then, putting the aluminum alloy into a chemical milling solution for reaction, wherein the chemical milling solution mainly comprises NaOH (sodium hydroxide aqueous solution), and the initial content is about 140 g/L:
2Al+2NaOH+2H2O→2NaAlO2+3H2↑
3. the above reaction only occurs on the bare aluminum alloy surface, and the aluminum alloy of the gummed part is protected. After chemical milling, the part which is not coated is corroded, the ribs with the supporting function are reserved, and the other parts are thinned, so that the weight is reduced.
However, the concentration of Na and Al in the milling solution are not changed along with the progress of the milling process3+When the concentration of Al increases with the corrosion3+When the concentration exceeds 80g/L, the chemical milling speed is obviously reduced to influence the process and reach the rejection standard. At present, most of the treatment methods are as follows: part (about 2/3) of the lye is taken out and discarded completely as hazardous waste. Meanwhile, NaOH (120-150g/L) supplement with the formula content is prepared. The method for preparing new alkali liquor from the waste alkali liquorThe cost is higher.
Disclosure of Invention
In view of the above-mentioned drawbacks and problems of the prior art, an object of the present invention is to provide a process and an apparatus for recovering aluminum-containing heavy metal-containing waste lye.
In order to achieve the purpose, the invention provides the following technical scheme:
a recovery process of waste lye containing aluminum and heavy metal is used for recovering the waste lye generated in the chemical milling treatment process of aluminum alloy;
the method comprises the following steps:
removing impurities;
removing aluminum;
disassembling the bipolar membrane to obtain an acid solution and an alkali solution;
the acid solution is used for adjusting the pH value in the aluminum removing step, and the alkali solution is used for chemical milling treatment of the aluminum alloy.
Wherein, the edulcoration includes:
obtaining waste alkali liquor, adding Na into the waste alkali liquor2S；
And (4) carrying out solid-liquid separation to obtain copper-containing sludge and primary waste liquid.
Wherein Na is added into the waste alkali liquor2After S, before solid-liquid separation, the method comprises the following steps:
adding Ca into the waste alkali liquor;
addition of H2O2The redox electrode of the solution is adjusted to above 0V.
Wherein the removing aluminum comprises:
taking the supernatant of the primary waste liquid;
the pH of the supernatant was adjusted to 12, Al (OH) was obtained for the first time3A solid;
adjusting the pH of the supernatant to 7, and obtaining Al (OH) for the second time3A solid;
obtaining secondary waste liquid.
Wherein the bipolar membrane dismantling comprises:
adding Na into the secondary waste liquid2SO4And water to make Na in secondary waste liquor2SO4The mass concentration is 6-8%;
obtaining the following product after disassembling the bipolar membrane:
salt solution: less than 1% concentration as initial water of acid solution;
acid solution: h2SO4The concentration is more than 8 percent;
alkali solution: the concentration of NaOH is 6-10%.
A recovery plant containing aluminum and heavy metal waste lye is used for recovering the waste lye generated in the aluminum alloy chemical milling process;
the method comprises the following steps: the device comprises a chemical milling groove, an impurity removal tank, a pH adjusting tank, a first salt tank, a second salt tank, a bipolar membrane stack, an acid tank and an alkali tank;
the chemical milling groove, the impurity removal tank, the pH adjusting tank, the first salt tank, the second salt tank, the bipolar membrane stack, the acid tank and the alkali tank are sequentially connected.
Wherein, the acid tank is connected with the pH adjusting tank, and the alkali tank is connected with the chemical milling groove.
Wherein an ultrafiltration group is arranged between the first salt tank and the second salt tank.
The recovery process and the recovery equipment for the waste alkali liquor containing aluminum and heavy metal provided by the invention have the advantages of reducing the recovery cost, being small in occupied area of the process equipment, flexible and convenient to operate, being capable of being started and stopped at any time and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic view of the structural connection of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As an embodiment, the recycling process of the waste alkali liquid containing aluminum and heavy metal is used for recycling the waste alkali liquid generated in the chemical milling treatment process of the aluminum alloy;
the method specifically comprises the following steps:
removing impurities, namely removing metal elements except aluminum, such as copper, zinc, manganese and the like in the scrapped alkali liquor in the chemical milling groove;
more specifically, the impurity removing step comprises: and taking out the scrapped alkali liquor in the chemical milling groove, and pumping the alkali liquor into an impurity removal tank so as to obtain waste alkali liquor. The concentration of Na in the waste alkali liquor is 80g/L, the concentration of the waste alkali liquor is 140g/L in terms of NaOH, and the content of Al is about 80 g/L. The other metals containing Cu, Zn, Mn and the like are about 5g/L, wherein heavy metals mainly exist in a complex ion form in a high-concentration alkali liquor, such as the copper exists in the form of: [ Cu (OH)4]2-. Adding Na into waste alkali liquor2S, removing Cu, Zn and Mn;
Cu+S——CuS↓(Ksp＝6.3×10-36)
Zn+S——ZnS↓(Ksp＝2.93×10-25)
Mn+S——MnS↓(Ksp＝2.93×10-13)
among them, the Ksp was low in the above reaction, and the reaction was considered complete. Generating precipitate, carrying out solid-liquid separation, and separating the precipitate from liquid by a filter press or a filter to generate copper-containing sludge (copper sludge) and primary waste liquid.
The copper-containing sludge needs to be treated as hazardous waste because the copper content is high, and the copper-containing sludge can be sold in copper recovery enterprises with hazardous waste treatment qualification.
Removing aluminum;
the aluminum removing step comprises: taking the supernatant of the primary waste liquid, introducing the supernatant into a pH adjusting tank through a pump, wherein the concentrations of Na and Al in the solution are almost unchanged after the impurity removal step, and only trace heavy metal elements exist and can be ignored. Adding sulfuric acid into the supernatant to adjust the pH value.
Al is an amphoteric substance in alkaliUnder the condition of sexual activity using AlO2In the presence of ions, with Al under acidic conditions3+Ions are present. And Al (OH) under neutral conditions3And (4) form precipitation. The following equilibrium reaction of Al exists under different acid and alkali conditions:
Al(OH)3→Al3-+3OH-，Ksp＝1.3×10-33
Al(OH)3→AlO2 -+H++H2O，Ksp＝1.4×10-14
considering the above balance, the pH is related to the solubility of Al in solution as follows:
Figure BDA0003158858750000051
Figure BDA0003158858750000061
it can be seen that the solubility of aluminum is lowest at pH 6, and when the solubility of aluminum is reduced, the excess Al is expressed as Al (oh)3The precipitate is generated in the form of the aluminum oxide, thereby achieving the purpose of removing Al ions in the solution. During the process, when the pH is adjusted directly to 7, Al (OH) is formed3The presence of a large amount of sulfur in the alloy affects Al (OH)3The quality of (2).
The pH adjustment is therefore carried out in two steps:
firstly, the pH value of the supernatant is adjusted to 12, at the moment, the solution is still alkaline, the sulfur anions are not separated out, and the generated Al (OH)3The solid quality is high, more than 90% of Al is precipitated when the pH value is 12, the solid and the liquid are separated by a filter press, and the separated liquid is returned to a pH adjusting tank after being circulated, so that Al (OH) is obtained for the first time3A solid;
the pH of the supernatant was then adjusted to 7, and the remaining Al precipitated, although this portion was Al (OH)3The quality is lower but only a small fraction of the total product. Solid-liquid separation is carried out by a filter press, and secondary waste liquid is introduced into a subsequent first salt tank, so as to obtain Al (OH) for the second time3And (3) a solid.
The secondary waste liquid generated after the treatment process is mainly Na2SO4Solution, pH 7. The secondary waste liquid is transferred to a first salt tank. Because the solid-liquid separation and the electrolysis in the whole process have solute loss, namely: the Na element which is the main body of the recovery is lost in a certain proportion, and the loss is actually estimated to be about 20-30%. Adding proper amount of low-cost chemical raw material Na2SO4As a supplement to the losses. Then regulating the concentration to Na by replenishing water2SO4The mass concentration is 6-8%.
Disassembling the bipolar membrane to obtain an acid solution and an alkali solution;
more specifically, the bipolar membrane disassembling step comprises: adding Na into the secondary waste liquid2SO4And water to make Na in secondary waste liquor2SO4The mass concentration is 6-8%; prepared Na for protecting a subsequent membrane system2SO4The solution enters a second salt tank after being filtered by a first-stage ultrafiltration membrane of the ultrafiltration group, and is disassembled by a bipolar membrane after being filtered by the ultrafiltration group, and the concentration of each element of the secondary waste liquid is detected as follows:
detecting items Unit of Detection value
Sodium salt mg/L 1.71×104
Magnesium alloy mg/L 0.285
Manganese oxide mg/L 0.015
Copper (Cu) mg/L 0.043
Zinc mg/L 0.025
Aluminium mg/L 18.2
Silicon mg/L 2.63
Iron mg/L 1.21
Sulfates of sulfuric acid mg/L 3.93×104
And the impurities except Al in the secondary waste liquid are controlled within 1 mg/L. The remaining aluminum has a slow effect on the membrane over the course of the run, wherein the effect may be irreversible, so that the membrane life can usually only reach 1 year. The bipolar membrane process is a 'salt splitting' process, acid-base salt solutions are respectively circulated in respective chambers, and cations are transferred to a negative electrode and anions are transferred to a positive electrode under the action of an electric field. Thereby obtaining an alkali solution and an acid solution. The membrane stack of the bipolar membrane process is composed of an anionic membrane, a cationic membrane and a bipolar membrane.
Anion and cation membranes: the purpose is to allow specific ions to pass through, so as to achieve the purpose of acid-base separation.
Bipolar membrane: the two sides are respectively attached with an anion membrane and a cation membrane, and the middle interlayer is a catalytic membrane. In the process of electrocatalytic activity. The catalytic membrane will permeate H in the membrane2Electrolysis of O to H+Ions and OH-Ions. The ions enter the cavities at the two sides of the bipolar membrane from the anion and cation membranes at the two sides respectively.
A salt room: na (Na)2SO4The solution is disassembled under the action of an electric field and anion and cation membranes on two sides. Na (Na)+Ions leaving the cation membrane, SO4 2-Away from the anion membrane. The concentration is continuously reduced, and finally low salinity water is generated.
Acid chamber: the initial solution is water, the acid chamber side is a bipolar membrane, and the acid chamber side is an anionic membrane. Continuously receiving H supplied by bipolar membrane+Ions and SO passing through the anion membrane4 2-Form H2SO4And (3) solution.
An alkali chamber: the initial solution is water, the acid chamber side is a bipolar membrane, and the acid chamber side is a cationic membrane. The initial solution is water, continuously receiving OH supplied by bipolar membrane-Ions and Na passing through the cation membrane+A NaOH solution was formed.
An electrode water chamber: configuring 2-4% of Na2SO4The solution is used for electrode protection and electric conduction. The process has no consumption.
Bipolar membrane supply of H+Ions and OH-Ions. Compared with the common electrolysis and electrodialysis, when NaOH and H2SO4At higher concentrations, the chemical reaction potential will be greater than the electric field potential, at which time resolution is more difficult. While the addition of a bipolar membrane in the middle can mitigate direct neutralization reactions. Simultaneous generation of H+Ions and OH-Ions are used for pairing. Thus, although the initial salt solution is 6%, the recovered acid and alkali can be concentrated to 8% circularly.
And the solution in the second salt tank is obtained after the bipolar membrane of the bipolar membrane stack is disassembled:
salt solution: the concentration is less than 1 percent, and the water is used as process water for supplementing and is used as initial water of acid solution;
acid solution: h2SO4The concentration is more than 8 percent; introducing into an acid tank.
Alkali solution: the concentration of NaOH is 6-10%. Na ion 30-40 g/L. Introducing into an alkali tank.
The acid solution is used for adjusting the pH value in the aluminum removing step, and the alkali solution is used for chemical milling treatment of the aluminum alloy.
The concentration of each element of the alkali solution is detected as follows:
Figure BDA0003158858750000091
in an alternative embodiment, 2g/L sulfate radicals are also present in the alkaline solution for the above detection parameters, and if the quality of the subsequent production process is to be improved, a purification step may be further included.
Firstly, a proper amount of barium hydroxide octahydrate, Ba (OH) is added2·8H2O, the following reaction is present:
Ba(OH)2+Na2SO4→BaSO4↓+2NaOH
generated BaSO4Insoluble in alkali to form precipitate, filtering to remove precipitate, and adding Na2CO3Ensuring no Ba ions remain:
Ba2++CO3 2-→BaCO3↓
in an alternative embodiment, Na is added to the spent lye2After S, before solid-liquid separation, the method comprises the following steps: adding Ca into the waste alkali liquor; addition of H2O2The redox electrode of the solution is adjusted to above 0V.
The waste alkali liquor may contain potassium sodium tartrate and S2SO3 2-Wherein Ca can be added, the following reaction Ca + C is carried out4H4O6 2-——CaC4H4O6↓(Ksp＝7.7×10-7) Removing tartaric acid by adding H2O2Regulating oxygen of solutionThe reduction electrode is raised to more than 0V to completely oxidize the sulfide to SO4 2-。
As shown in figure 1, the invention provides a recovery device of waste alkali liquid containing aluminum and heavy metal, which is used for recovering the waste alkali liquid generated in the chemical milling treatment process of aluminum alloy;
the method comprises the following steps: the device comprises a chemical milling groove, an impurity removal tank, a pH adjusting tank, a first salt tank, a second salt tank, a bipolar membrane stack, an acid tank and an alkali tank;
the chemical milling groove, the impurity removal tank, the pH adjusting tank, the first salt tank, the second salt tank, the bipolar membrane stack, the acid tank and the alkali tank are sequentially connected.
The acid tank is connected with the pH adjusting tank, and the alkali tank is connected with the chemical milling groove.
An ultrafiltration group is arranged between the first salt tank and the second salt tank.
Description of recovery: mass flow for the treatment of aluminium-containing spent lye (Na ion balance);
waste alkali liquor: NaOH 140g/L, Al 80g/L, 1 volume;
recovering alkali: 70g/L NaOH, 1g/L Al, 2 volumes;
there is some loss of Na ions during system recovery, but a small amount of Na passes through2SO4Addition of (A) Na2SO4As a Na source, the Na ion balance of an inlet and an outlet can be achieved;
although the concentration of NaOH for recovering alkali is low, the alkali liquor needs to be heated to 90 ℃ in the chemical milling process, a large amount of water vapor overflows at the moment, and the system needs to continuously add supplementary water. Under the condition of ensuring the balance of the recovered NaOH solute, the excessive water with low concentration can be used as make-up water, and other processes can be subjected to certain evaporation according to the conditions to reach the required level.
Take a certain chemical milling factory as an example:
in a chemical milling workshop, a chemical washing tank dissolves 110m3Normal bath solution 100m3. Chemically milling about 240kg Al per day while evaporating 3.65m3Water;
the initial concentration of the chemical milling liquid is NaOH 140g/L (14t), Al ion 65g/L (6.5t), 100m3；
Three days after chemical milling, 157g/L (14t) of NaOH, 81g/L (7.22t) of Al ions and 89m of NaOH3The Al ion concentration exceeds the scrap standard, wherein the Al ion increment is 720 kg;
readjusting the alkali liquor, taking out 9m3The alkali liquor is recycled, 157g/L (12.6t) of NaOH, 81g/L (6.5t) of Al ions and 80m of NaOH are reserved in the chemical milling groove3；
157g/L (1.41t) of NaOH, 81g/L (0.73t) of Al ions, and 9m of NaOH were taken out3The waste alkali liquor enters a recovery system, and the capacity of the recovery equipment is 3m3Day, conversion of spent lye to NaOH70g/L (1.41t) after three days, Al ions not exceeding 1g/L (0.02t), 20m3(ii) a Wherein: in actual operation, the recovered alkali liquor has a volume of 20m3The buffer tank of (1). Get 9m3The waste alkali liquor can be supplemented from the buffer tank, and the production time is not influenced. And 9m3The spent lye of (1) can be used for the next batch of conditioning after three days of treatment.
The total amount of the recovered alkali liquor NaOH is 9m3The amount of the waste alkali liquor is the same (1.41t), and the total amount of the removed Al ions is equal to the total amount of chemical milling aluminum in three days (0.72 t);
the solution generated by mixing the recovered alkali liquor and the alkali liquor in the chemical washing tank after replenishing is as follows: NaOH 140g/L (14t), Al ion 65g/L (6.5t), 100m3The parameters are the same as the initial milling liquid.
The cost accounting of the prior waste alkali liquid scrapping is as follows:
annual milling of the total aluminum: 64t
The aluminum in the milling solution can be continuously lifted, and when the dissolved aluminum reaches 80 g/L. The chemical milling speed is obviously reduced;
at this time, the 1/3 lye taken out is discarded, and the treatment cost of the dangerous waste is about 4,500/t;
the total discard volume per year is 60 t/80 g/L-800 m3
The lye allocation costs were about 5,000/t after the filling of the washing liquor with 40% NaOH;
the prepared chemical milling liquid is equivalent to 1/3 aluminum removal and reaches the standard use working condition of 53 g/L;
in the prior art, the treatment/supplement cost is about 6,400/t of chemical milling solution scrapping under the condition of not comprising manpower;
the annual cost of scrapping the waste alkali liquor: this is 510 ten thousand/a.
Figure BDA0003158858750000121
The cost of the waste lye recovery is calculated as follows:
annual milling of the total aluminum: 64 t.
According to the field experiment result, the operation efficiency is 0.4-0.5kg- (sodium sulfate)/m2-hr, set at 0.4kg/m for long run2-hr；
Conversion to NaOH production, 0.225kg- (NaOH)/m2-hr
The power per unit membrane area was 0.8kw/m2
The power consumption of NaOH solute recovery per kilogram is 3.56KWH/kg
1m per treatment3The amount of NaOH to be electrolyzed from the waste alkali solution is 140kg, which corresponds to 248.5kg of sodium sulfate.
Every 1m3The power consumption for recovering the waste alkali liquor is as follows: 498.4KWH, i.e. 500KWH
The average power consumption of the industrial power is 0.7 yuan/KWH.
The actual electricity consumption of each ton of waste alkali liquor is as follows: 350 yuan/m3。
According to calculation and detection, the copper content in the water tank is not more than 4g/L (including suspension), the copper sludge which can be actually discharged from 1t of waste alkali liquor is 4kg (calculated by copper), and the weight ratio of copper in the copper sludge is 20 percent at least and is 20 kg. The water content of the filter pressing is about 50kg about 40%.
With the exception of the bipolar membrane, all equipment was about 56 ten thousand yuan, which is four years old.
The total throughput was 800m3Per year, 330 days per year, 12 hours per day. The efficiency requirement is as follows: 0.1515m3Hr, 21.21kg- (NaOH)/hr. The required membrane area is 200m2. The price is 200 ten thousand;
Figure BDA0003158858750000141
it can be seen that the present invention can bring about lower costs.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention.

Claims (8)

1. A recovery process of waste alkali liquor containing aluminum and heavy metal is characterized in that; used for recovering waste alkali liquor generated in the chemical milling treatment process of the aluminum alloy;
the method comprises the following steps:
removing impurities;
removing aluminum;
disassembling the bipolar membrane to obtain an acid solution and an alkali solution;
the acid solution is used for adjusting the pH value in the aluminum removing step, and the alkali solution is used for chemical milling treatment of the aluminum alloy.
2. The process of claim 1, wherein the recovery of the waste lye containing aluminum and heavy metals comprises: the impurity removal comprises the following steps:
obtaining waste alkali liquor, adding Na into the waste alkali liquor2S；
And (4) carrying out solid-liquid separation to obtain copper-containing sludge and primary waste liquid.
3. The process of claim 2, wherein the recovery of the waste lye containing aluminum and heavy metals comprises: adding Na into waste alkali liquor2After S, before solid-liquid separation, the method comprises the following steps:
adding Ca into the waste alkali liquor;
addition of H2O2The redox electrode of the solution is adjusted to above 0V.
4. The process of claim 3, wherein the recovery of the waste lye containing aluminum and heavy metals comprises: the aluminum removal comprises:
taking the supernatant of the primary waste liquid;
the pH of the supernatant was adjusted to 12, Al (OH) was obtained for the first time3A solid;
adjusting the pH of the supernatant to 7, and obtaining Al (OH) for the second time3A solid;
obtaining secondary waste liquid.
5. The process of claim 4, wherein the recovery of the waste lye containing aluminum and heavy metals comprises: the bipolar membrane disassembling comprises the following steps:
adding Na into the secondary waste liquid2SO4And water to make Na in secondary waste liquor2SO4The mass concentration is 6-8%;
obtaining the following product after disassembling the bipolar membrane:
salt solution: less than 1% concentration as initial water of acid solution;
acid solution: h2SO4The concentration is more than 8 percent;
alkali solution: the concentration of NaOH is 6-10%.
6. The equipment for recovering the waste alkali liquid containing aluminum and heavy metal is characterized by being used for recovering the waste alkali liquid generated in the aluminum alloy chemical milling treatment process;
the method comprises the following steps: the device comprises a chemical milling groove, an impurity removal tank, a pH adjusting tank, a first salt tank, a second salt tank, a bipolar membrane stack, an acid tank and an alkali tank;
the chemical milling groove, the impurity removal tank, the pH adjusting tank, the first salt tank, the second salt tank, the bipolar membrane stack, the acid tank and the alkali tank are sequentially connected.
7. The recycling apparatus of waste alkali liquor containing aluminum and heavy metals according to claim 6, wherein said acid tank is connected to said pH adjusting tank, and said alkali tank is connected to said chemical milling tank.
8. The recycling apparatus of waste lye containing aluminum and heavy metals as claimed in claim 7 wherein an ultrafiltration module is provided between the first salt tank and the second salt tank.
CN202110786085.0A 2021-07-12 2021-07-12 Process and equipment for recovering aluminum-containing and heavy metal-containing waste alkali liquor Active CN113620458B (en)

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