CN114314884B - Method and device for treating waste electrolyte of cadmium-nickel storage battery - Google Patents
Method and device for treating waste electrolyte of cadmium-nickel storage battery Download PDFInfo
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- CN114314884B CN114314884B CN202210004543.5A CN202210004543A CN114314884B CN 114314884 B CN114314884 B CN 114314884B CN 202210004543 A CN202210004543 A CN 202210004543A CN 114314884 B CN114314884 B CN 114314884B
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- heavy metal
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- metal separation
- waste electrolyte
- cadmium
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- 239000002699 waste material Substances 0.000 title claims abstract description 125
- 239000003792 electrolyte Substances 0.000 title claims abstract description 121
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 174
- 238000000926 separation method Methods 0.000 claims abstract description 106
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 238000005070 sampling Methods 0.000 claims abstract description 19
- 238000001556 precipitation Methods 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 8
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 238000012360 testing method Methods 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims description 106
- 238000004140 cleaning Methods 0.000 claims description 37
- 239000012528 membrane Substances 0.000 claims description 11
- 239000000084 colloidal system Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- 238000001728 nano-filtration Methods 0.000 claims description 5
- 230000001376 precipitating effect Effects 0.000 claims description 5
- 238000000108 ultra-filtration Methods 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052793 cadmium Inorganic materials 0.000 abstract description 19
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052759 nickel Inorganic materials 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 244000005700 microbiome Species 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for treating waste electrolyte of a cadmium-nickel storage battery, which comprises the following steps: step one, concentrating waste electrolyte in a waste cadmium-nickel storage battery into a precipitation tank for precipitation; step two, the precipitated waste electrolyte is concentrated into a first charging bucket for storage after primary filtration and secondary filtration in sequence; step three, separating or adsorbing heavy metals contained in the waste electrolyte to be treated in the first charging bucket through heavy metal separation treatment; step four, sampling the waste electrolyte after the heavy metal separation treatment for a set time, and carrying out a censoring test or field detection; and fifthly, discharging when the concentration of the detected heavy metals reaches the standard, otherwise, repeatedly carrying out heavy metal separation treatment on the waste electrolyte. The method provides guidance operation for treating the waste electrolyte of the cadmium-nickel storage battery for technicians, reduces the heavy metal content in the waste electrolyte, and ensures that the nickel and cadmium heavy metals contained in the waste electrolyte reach the emission standard and reach the emission standard.
Description
Technical Field
The invention relates to the technical field of waste battery recovery treatment, in particular to a method and a device for treating waste electrolyte of a cadmium-nickel storage battery.
Background
The active material on the positive plate of the nickel-cadmium battery consists of nickel oxide powder and graphite powder, and the graphite does not participate in chemical reaction and has the main function of enhancing conductivity. The active material on the negative plate is composed of cadmium oxide powder and ferric oxide powder, and the ferric oxide powder has the functions of enabling the cadmium oxide powder to have higher diffusivity, preventing caking and increasing the capacity of the negative plate. The electrolyte mainly comprises sodium hydroxide or potassium hydroxide. After charging, the positive plate reacts to produce nickel hydroxide [ Ni (OH) 3 ] and the negative plate produces cadmium (Cd) atoms. After discharge, cadmium hydroxide (Cd (OH) 2) is deposited on the negative plate, and nickel (Ni (OH 2)) hydroxide crystals are bonded on the positive plate. The conventional treatment method for the waste nickel-cadmium battery is to mechanically disassemble a bracket, a shell and the like of the battery, discharge electrolyte, neutralize the electrolyte into potassium salt or sodium salt, discard the potassium salt or sodium salt, for example, the prior art is a treatment method (publication number is CN 102945992A) for the waste nickel-cadmium battery and a recovery method (publication number is CN 108179275B) for cadmium and nickel in the waste nickel-cadmium battery, treat positive and negative electrode materials, positive electrode leftover materials and the like with higher heavy metals containing cadmium and nickel, and lack the treatment for waste electrolyte of the cadmium-nickel battery.
As known from the charge-discharge reaction of the battery, cadmium hydroxide and nickel hydroxide generated by the reaction are solid precipitates and are deposited on the polar plate, the electrolyte contains small amount of cadmium and nickel, but the cadmium has high toxicity to the environment, the national standard requires extremely low discharge amount of cadmium, and the electrolyte is directly discharged into the environment, so that potential safety hazard exists. Particularly, the waste alkaline cadmium-nickel storage battery is difficult to discard, and is usually placed in a waste warehouse for a long time, so that the concentration of electrolyte is increased, and polar plates soaked in the electrolyte are reacted or dissolved, so that the content of cadmium and nickel in the electrolyte is increased, the waste electrolyte is difficult to meet the discharge requirement of extremely low concentration, and the treatment method of the waste electrolyte of the cadmium-nickel storage battery is lacking at present, so that research on a method and a device for treating the waste electrolyte of the cadmium-nickel storage battery is needed, the discharge requirement of extremely low concentration of cadmium heavy metals is met, and environmental pollution is reduced.
Disclosure of Invention
It is an object of the present invention to address at least the above-mentioned drawbacks and to provide at least the advantages to be described later.
The invention also aims to provide a treatment method and a device for the waste electrolyte of the cadmium-nickel storage battery, and the treatment method for the waste electrolyte of the cadmium-nickel storage battery is provided, so that a guiding operation for treating the waste electrolyte of the cadmium-nickel storage battery is provided for a technician, the heavy metal content in the waste electrolyte is reduced, and the heavy metals of Ni (nickel) and Ge (cadmium) contained in the waste electrolyte reach the emission standard and reach the emission standard.
To achieve these objects and other advantages and in accordance with the purpose of the invention, a method for treating waste electrolyte of a cadmium-nickel storage battery, comprising:
step one, concentrating waste electrolyte in a waste cadmium-nickel storage battery into a precipitation tank for precipitation;
step two, the precipitated waste electrolyte is concentrated into a first charging bucket for storage after primary filtration and secondary filtration in sequence;
step three, separating or adsorbing heavy metals contained in the waste electrolyte to be treated in the first charging bucket through heavy metal separation treatment;
step four, sampling the waste electrolyte after the heavy metal separation treatment for a set time, and carrying out a censoring test or field detection;
and fifthly, discharging when the concentration of the detected heavy metals reaches the standard, otherwise, repeatedly carrying out heavy metal separation treatment on the waste electrolyte.
Preferably, the primary filtration, the secondary filtration and the heavy metal separation treatment are respectively carried out by adopting a coarse filter, a precise filter and a heavy metal separator; the fifth step further includes: when the concentration of the heavy metals does not reach the standard in the assay or detection, the heavy metal separator is cleaned and reused, and the cleaned cleaning liquid is discharged and collected.
The invention also provides a device for the treatment method of the waste electrolyte of the cadmium-nickel storage battery, which is used in the treatment method as claimed in claim 1 or 2, and the treatment device comprises: a precipitation tank, a filtering device and a heavy metal separator;
the precipitation tank is a tank body with an opening at the upper part and is used for intensively precipitating waste electrolyte taken out from the waste cadmium-nickel storage battery;
the filtering device comprises a coarse filter, a precise filter and a first charging bucket, wherein the sedimentation tank is communicated with the coarse filter through a telescopic pipeline, then the coarse filter is sequentially communicated with the precise filter and the first charging bucket, and the first charging bucket is used for storing waste electrolyte to be treated after being filtered by the precise filter;
the heavy metal separator comprises a shell, a telescopic filter element and a second charging bucket;
the shell is a sealed container with an upper opening, a sampling port is arranged on the side wall of the shell, a liquid inlet, a liquid outlet and a collecting port are arranged at the bottom end of the shell, and switching valves are respectively arranged on the liquid inlet, the liquid outlet, the collecting port and the sampling port;
the telescopic filter piece is arranged in the shell, a filter medium is arranged on the telescopic filter piece and used for separating or adsorbing heavy metals in waste electrolyte to be treated, and the filter medium is a nanofiltration membrane, an ultrafiltration membrane or graphene oxide colloid;
the second charging bucket is used for storing cleaning liquid to clean and regenerate the filter medium in the shell, the cleaning liquid is acid solution with concentration of more than 0.2mol/L, and a second liquid supply pipe for supplying liquid to the shell is arranged on the second charging bucket;
the heavy metal separator comprises a first charging tank, a second charging tank, a valve, a pump body, a first liquid supply pipe, a second liquid supply pipe, a return pipe and a valve, wherein the first charging tank is provided with the first liquid supply pipe and the return pipe which are communicated with a liquid inlet of the heavy metal separator; one end of the return pipe is communicated with the upper end of the first charging bucket, and the other end of the return pipe is communicated with the liquid inlet through a valve.
Preferably, two circulation pipelines are arranged on the side wall of the shell, one end of each pipeline is communicated with the upper part of the shell, and the other end of each pipeline is communicated with the lower part of the shell; one end of the other pipeline is communicated with the middle part of the shell, and the other end of the other pipeline is communicated with the lower part of the shell; each pipeline is provided with a pump body and a valve for controlling the opening and closing of the circulating pipeline.
Preferably, the telescoping filter comprises:
the heavy metal separation plates are net plates or frame bodies through which water molecules can pass, the filter medium is uniformly covered on each heavy metal separation plate body, the heavy metal separation plates are arranged in the shell at intervals along the longitudinal direction of the shell to divide the shell into a plurality of cavities, the heavy metal separation plate body positioned at the bottommost part of the shell is fixedly connected with the shell, and the other heavy metal separation plate bodies can be connected in a sliding way along the longitudinal direction of the shell;
the cover plate can be connected in the shell in a sliding manner along the longitudinal direction of the shell, the cover plate is positioned above the heavy metal separation plate bodies, a first air vent communicated with outside air and a liquid level sensor for detecting the liquid level in the shell are arranged on the cover plate, and an electric switch valve is arranged on the first air vent;
the plurality of groups of connecting rod bodies are used for enabling the plurality of heavy metal separation plate bodies and the cover plate to be in linkage close to the heavy metal separation plate body at the bottommost part of the shell and enabling the plurality of heavy metal separation plate bodies and the cover plate to be in linkage far away from the heavy metal separation plate body at the bottommost part of the shell when the cover plate is driven by an external telescopic device to move along the longitudinal direction of the shell;
and the controller is electrically connected with the liquid level sensor, the electric switch valve, the pump body and the telescopic device.
Preferably, the connection relation between the plurality of groups of connecting rod bodies and the plurality of heavy metal separation plate bodies and the cover plate is specifically as follows: the upper end of one group of connecting rod bodies is hinged with the bottom of the cover plate, the lower end of each connecting rod body is provided with a sliding block, and the sliding blocks are in sliding connection with sliding grooves on the upper surfaces of the adjacent heavy metal separation plate bodies; the upper end of each group of other multiunit connecting rod bodies is hinged with the bottom of a plurality of heavy metal separation bodies in turn, and the lower extreme slider of connecting rod body is connected with the spout sliding connection of next adjacent heavy metal separation plate body upper surface.
Preferably, the number of the sliding grooves on the upper surface of each heavy metal separation plate body is the same as that of the connecting rod bodies of each group, and the sliding grooves are uniformly distributed, and the sliding grooves on the upper surface of each heavy metal separation plate body extend from the center of the heavy metal separation plate body to the edge of the heavy metal separation plate body.
Preferably, a positioning block is arranged on the sliding chute on the upper surface of the heavy metal separation plate body and used for controlling the sliding distance of the lower end sliding block of the connecting rod body to the central position of the heavy metal separation plate body so as to control the compression distance of the telescopic filter.
Preferably, the shell is of a cylindrical or rectangular box structure, the telescopic device is arranged at the top of the shell, and the telescopic end of the telescopic device is connected with the cover plate; the heavy metal separation plate body and the cover plate are longitudinally linked and telescopic in the shell; the upper end hinge point of each group of connecting rod bodies is arranged on the first sliding block, and the sliding groove on the upper surface of the heavy metal separation plate body does not pass through the first sliding block.
Preferably, the heavy metal separation plate body includes:
the hard round or square outer frame body is provided with the first sliding block at the periphery, and the upper end surface of the outer frame body is provided with a sliding groove;
the dialysis bag is of a double-bag structure, a plurality of cavities are formed in each layer of bag at intervals along the filtering direction, the cavities between the two layers of bags are staggered, and graphene oxide colloid is arranged in each cavity.
The invention at least comprises the following beneficial effects:
1. the invention provides a treatment method for the waste electrolyte of the cadmium-nickel storage battery, provides guidance operation for treating the waste electrolyte of the cadmium-nickel storage battery for technicians, reduces the heavy metal content in the waste electrolyte, and ensures that the heavy metals of Ni (nickel) and Ge (cadmium) contained in the waste electrolyte reach the emission standard and reach the emission standard.
2. The invention deposits the waste electrolyte first and then carries out coarse filtration, thus not only removing a small amount of solid particles and deposits in the waste electrolyte, but also reducing the blocking probability of the coarse filter; then, the micro suspended particles, colloid, microorganisms and the like in the waste electrolyte can be filtered out by precise filtration, thereby providing favorable conditions for the subsequent separation of heavy metals in the waste electrolyte and reducing the blockage probability of a heavy metal separator. In the actual treatment process of the waste electrolyte, the cadmium content is usually used as an index, namely, the cadmium content of the waste electrolyte after heavy metal separation treatment is lower than 0.1mg/L, the waste electrolyte can be discharged after reaching standards, and if the cadmium content is detected to be not reaching standards, the heavy metal separator is cleaned, and after the cleaning liquid is discharged cleanly, the heavy metal separation treatment is repeatedly carried out on the waste electrolyte.
3. For the treatment device, the telescopic filter piece is controlled to be contracted, so that the cleaning liquid for soaking the telescopic filter piece is less, the consumption of the cleaning liquid is reduced, and the subsequent treatment procedure of the used cleaning liquid is reduced. After the telescopic filter piece is stretched, the large-scale adsorption of the low-concentration heavy metal solution is facilitated, and the adsorption efficiency of the heavy metal in the waste electrolyte is improved. Heavy metals adsorbed by the telescopic filter element are separated and desorbed through the cleaning solution, so that the filter medium of the telescopic filter element can be regenerated and used.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a schematic flow chart of an embodiment of a method for treating spent electrolyte of a cadmium-nickel battery according to the present invention;
FIG. 2 is a schematic diagram of an implementation form of the treatment device for the waste electrolyte of the cadmium-nickel storage battery according to the present invention;
FIG. 3 is a schematic diagram of the structure of the telescopic filter in a compressed state in one implementation form of the device for treating waste electrolyte of a cadmium-nickel battery according to the present invention;
FIG. 4 is a schematic view of a part of the telescopic filter of the treatment device for the waste electrolyte of the cadmium-nickel storage battery, which is an enlarged structure;
wherein, the first charging bucket 1; a first valve 2; a first pump body 3; a second valve 4; a third valve 5; a liquid inlet 6; a collection port 7; a liquid outlet 8; a second pump body 9; a seventh valve 10; a sampling port 11; a first slider 12; a second slider 13; a connecting rod body 14; a second chute 15; a hinge point 16; a heavy metal separation plate 17; an upper opening 18; a telescopic device 19; a liquid level sensor 20; a first vent 21; a cover plate 22; a ninth valve 23; a third pump body 24; a tenth valve 25; a fourth pump body 26; a second bucket 27; a blow-down valve 28; a first chute 29; an outer frame 30; a positioning block 31; a precipitation tank 32; a coarse filter 33; a precision filter 34.
Detailed Description
The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.
It should be noted that the experimental methods described in the following embodiments, unless otherwise specified, are all conventional methods, and the reagents and materials, unless otherwise specified, are all commercially available; in the description of the present invention, it should be noted that, unless explicitly stated and limited otherwise, the terms "mounted," "connected," and "disposed" are to be construed broadly, and may be fixedly connected, disposed, or detachably connected, disposed, or integrally connected, disposed, for example. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art. The terms "transverse," "longitudinal," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used for convenience in describing and simplifying the description of the present invention based on the orientation or positional relationship shown in the drawings, and do not denote or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus are not to be construed as limiting the present invention.
Example 1
The invention provides a method for treating waste electrolyte of a cadmium-nickel storage battery, which is shown in a flow chart of fig. 1 and comprises the following steps:
step one, concentrating waste electrolyte in a waste cadmium-nickel storage battery into a precipitation tank for precipitation;
step two, the precipitated waste electrolyte is concentrated into a first charging bucket for storage after primary filtration and secondary filtration in sequence;
step three, separating or adsorbing heavy metals contained in the waste electrolyte to be treated in the first charging bucket through heavy metal separation treatment;
step four, sampling the waste electrolyte after the heavy metal separation treatment for a set time, and carrying out a censoring test or field detection;
and fifthly, discharging when the concentration of the detected heavy metals reaches the standard, otherwise, repeatedly carrying out heavy metal separation treatment on the waste electrolyte.
The invention provides a treatment method for the waste electrolyte of the cadmium-nickel storage battery, provides guidance operation for treating the waste electrolyte of the cadmium-nickel storage battery for technicians, reduces the heavy metal content in the waste electrolyte, and ensures that the heavy metals of Ni (nickel) and Ge (cadmium) contained in the waste electrolyte reach the emission standard and reach the emission standard.
Wherein, the primary filtration, the secondary filtration and the heavy metal separation treatment are respectively carried out by adopting a coarse filter, a precise filter and a heavy metal separator; the fifth step further includes: when the concentration of the heavy metals does not reach the standard in the assay or detection, the heavy metal separator is cleaned and then used, and the cleaned cleaning liquid is discharged and collected.
The invention deposits the waste electrolyte first and then carries out coarse filtration, so that not only can a small amount of solid particles in the waste electrolyte be removed, but also the blocking probability of the coarse filter 33 is reduced; then, the micro suspended particles, colloid, microorganisms and the like in the waste electrolyte can be filtered out by precise filtration, thereby providing favorable conditions for the subsequent separation of heavy metals in the waste electrolyte and reducing the blockage probability of a heavy metal separator. In the actual treatment process of the waste electrolyte, the cadmium content is usually used as an index, namely, the cadmium content of the waste electrolyte after heavy metal separation treatment is lower than 0.1mg/L, the waste electrolyte can be discharged after reaching standards, and if the cadmium content is detected to be not reaching standards, the heavy metal separator is cleaned, and after the cleaning liquid is discharged cleanly, the heavy metal separation treatment is repeatedly carried out on the waste electrolyte.
Fig. 2-3 show an embodiment of the present invention of a treatment device for waste electrolyte of a cadmium-nickel battery, which can be applied to the treatment method of example 1, and the present invention comprises: a precipitation tank 32, a filtering device and a heavy metal separator;
the precipitation tank 32 is a tank body with an upper opening and is used for intensively precipitating the waste electrolyte taken out from the waste cadmium-nickel storage battery;
the filtering device comprises a coarse filter 33, a precise filter 34 and a first charging bucket 1, wherein the sedimentation tank 32 is communicated with the coarse filter 33 through a telescopic pipeline, then the coarse filter 33 is sequentially communicated with the precise filter 34 and the first charging bucket 1, and the first charging bucket is used for storing waste electrolyte to be treated after being filtered by the precise filter 34; the coarse filter 33 and the precise filter 34 can filter out a small amount of solid particles, micro suspended particles, colloid, microorganisms and the like by adopting the existing filters;
the heavy metal separator comprises a shell, a telescopic filter element and a second charging bucket;
the shell is a sealed container with an upper opening 18, a sampling port 11 is arranged on the side wall of the shell, the sampling port 11 can be arranged in the middle or lower part of the side wall of the shell and is used for periodically sampling and detecting heavy metal content of treatment liquid in the shell, or a detection probe is inserted into the sampling port 11 so as to judge when a cleaning liquid is introduced to clean and regenerate a filter medium in the shell, a liquid inlet 6, a liquid outlet 8 and a collecting port 7 are arranged at the bottom end of the shell, for example, a four-way pipe is arranged at the bottom end of the container, one of the four-way pipe is communicated with the bottom end of the container, the other ports are the liquid inlet 6, the collecting port 7 and the liquid outlet 8, and the collecting port 7 is used for collecting and treating separated heavy metals; switch valves are respectively arranged on the liquid inlet 6, the liquid outlet 8, the collecting port 7 and the sampling port 11, and as shown in the figure, a fourth valve, a sixth valve, a fifth valve and an eighth valve are respectively arranged on the liquid inlet 6, the liquid outlet 8, the collecting port 7 and the sampling port 11;
the telescopic filter piece is arranged in the shell, a filter medium is arranged on the telescopic filter piece and used for separating or adsorbing heavy metals in waste electrolyte to be treated, and the filter medium is a nanofiltration membrane, an ultrafiltration membrane or graphene oxide colloid;
the second charging tank is used for storing cleaning liquid for cleaning and regenerating the filter medium in the shell of the heavy metal separator, the cleaning liquid is an acidic solution with the concentration of more than 0.2mol/L, and a second liquid supply pipe for supplying liquid into the shell of the heavy metal separator is arranged on the second charging tank; for a specific implementation manner, one end of the second liquid supply pipe is shown to be communicated with the bottom of the second material tank 27, the other end of the second liquid supply pipe is shown to be communicated with the middle part or the lower part of the side wall of the shell through a switch valve, the other end of the second liquid supply pipe is shown to be communicated with the middle part or the lower part of the side wall of the shell through a tenth valve 25, a pump body is arranged on the second liquid supply pipe and used for providing a power source for liquid supply in the shell, the pump body arranged on the second liquid supply pipe is shown to be a fourth pump body 26, and a drain valve 28 used for draining is arranged at the bottom of the second material tank 27.
The first charging bucket is provided with a first liquid supply pipe and a return pipe which are communicated with a liquid inlet 6 of the heavy metal separator, one end of the first liquid supply pipe is communicated with the lower part of the first charging bucket 1, and the other end of the first liquid supply pipe is communicated with the liquid inlet 6 through a valve and a pump body; one end of the return pipe is communicated with the upper end of the first charging bucket 1, and the other end of the return pipe is communicated with the liquid inlet 6 through a valve. The figure shows that a first valve 2, a first pump body 3, a second valve 4 and a fourth valve are sequentially arranged on a first liquid supply pipe, and a third valve 5 and a fourth valve are arranged on a return pipe. The first charging bucket is provided with the first pump body 3 for supplying liquid to the heavy metal separator for treatment, and when the waste electrolyte treated in the heavy metal separator does not reach the standard, the waste electrolyte which does not reach the standard is flowed back into the first charging bucket 1 from the heavy metal separator through the return pipe for next treatment.
The implementation process of the invention is as follows: placing the waste electrolyte taken out from the waste cadmium-nickel storage battery in a precipitation tank 32 for precipitating for a certain time, such as precipitating for 2-5 hours or more, then stretching into the liquid surface of the precipitation tank 32 through a telescopic pipeline to extract the precipitated waste electrolyte, sequentially passing through a coarse filter 33 and a fine filter 34, flowing into a first charging tank 1 for storage, then feeding the waste electrolyte to be treated of the first charging tank 1 into a shell of a heavy metal separator from a feed port, after the shell is filled with the waste electrolyte to be treated, controlling the feed port to be closed, stopping the entry of the waste electrolyte to be treated, and adsorbing heavy metals of the waste electrolyte to be treated in the shell by a filter medium, such as graphene oxide colloid (with the publication number of CN 103663601B) prepared by the prior art, wherein the cleaning liquid is an acidic solution with the concentration of more than 0.2 mol/L. After the treatment for a prescribed time, the liquid outlet 8 is opened and the treated waste electrolyte is discharged when the amount of heavy metal contained in the treated waste electrolyte detected from the sampling port 11 meets the national discharge standard. And after the treated waste electrolyte is discharged cleanly, repeating the steps, and carrying out the treatment of the waste electrolyte to be treated in the next round until the heavy metal content in the treated waste electrolyte cannot meet the national emission standard after the treatment for a specified time is detected from the sampling port 11, and then cleaning the filter medium of the telescopic filter piece. The filter medium cleaning operation of the telescopic filter element is as follows: and (3) refluxing the waste electrolyte which does not meet the national discharge standard into an original container for storing the waste electrolyte to be treated, shrinking the telescopic filter element, controlling the cleaning liquid of the second charging bucket 27 to enter the shell, soaking the shrunk telescopic filter element in the cleaning liquid, separating and desorbing heavy metal ions from the filter medium of the telescopic filter element, controlling the collecting port 7 to be opened, discharging the used cleaning liquid from the collecting port 7, and collecting and treating. And after the used cleaning liquid is discharged cleanly, controlling the telescopic filter element to restore the original shape, and then carrying out the waste electrolyte treatment to be treated of the next round.
The invention controls the telescopic filter to shrink, so that the cleaning liquid for soaking the telescopic filter is less, the consumption of the cleaning liquid is reduced, and the subsequent cleaning liquid treatment process after use is reduced. After the telescopic filter piece is stretched, the large-scale adsorption of the low-concentration heavy metal solution is facilitated, and the adsorption efficiency of the heavy metal in the waste electrolyte is improved. Heavy metals adsorbed by the telescopic filter element are separated and desorbed through the cleaning solution, so that the filter medium of the telescopic filter element can be regenerated and used.
On the basis of the embodiment, two circulating pipelines are arranged on the side wall of the shell, one end of one pipeline is communicated with the upper part of the shell, and the other end of the pipeline is communicated with the lower part of the shell; one end of the other pipeline is communicated with the middle part of the shell, and the other end of the other pipeline is communicated with the lower part of the shell; each pipeline is provided with a pump body and a valve for controlling the opening and closing of the circulating pipeline, wherein the first circulating pipeline is provided with a second pump body 9 and a seventh valve 10, and the second circulating pipeline is provided with a third pump body 24 and a ninth valve 23.
In accordance with the above embodiments, the telescoping filter comprises:
the heavy metal separation plates 17 are net plates or frame bodies through which water molecules can pass, the filter medium is uniformly covered on each heavy metal separation plate 17, the heavy metal separation plates 17 are arranged in the shell at intervals along the longitudinal direction of the shell to divide the shell into a plurality of cavities, wherein the heavy metal separation plate 17 at the bottommost part of the shell is fixedly connected with the shell, and the other heavy metal separation plates 17 can be connected in a sliding way along the longitudinal direction of the shell;
the cover plate 22 is slidably connected in the shell along the longitudinal direction of the shell, the cover plate 22 is positioned above the heavy metal separation plate bodies 17, a first air vent 21 communicated with the outside air and a liquid level sensor 20 for detecting the liquid level in the shell are arranged on the cover plate 22, and an electric switch valve is arranged on the first air vent 21; the electric switch valve controls the opening and closing of the liquid level sensor 20 according to the liquid level condition detected by the liquid level sensor, for example: when the liquid level is detected to be close to the cover plate 22, for example, the liquid level is usually set to be less than 4-10 cm away from the cover plate 22 in the treatment process, the first air vent 21 of the electric switch valve is controlled to be closed, and the heavy metal separator is controlled to stop feeding; when the liquid level is detected not to be close to the cover plate 22, for example, the liquid level is more than 4-10 cm away from the cover plate 22, the electric switch valve is controlled to open the first air vent 21; the liquid level sensor 20 can be a floating ball type liquid level sensor 20, which is a module circuit and has the advantages of acid resistance, moisture resistance, shock resistance, corrosion resistance and the like.
The multiple groups of connecting rod bodies 14 are used for enabling the multiple heavy metal separation plate bodies 17 and the cover plate 22 to be linked close to the heavy metal separation plate body 17 at the bottommost part of the shell and enabling the multiple heavy metal separation plate bodies 17 and the cover plate 22 to be linked far away from the heavy metal separation plate body 17 at the bottommost part of the shell when the cover plate 22 is driven to move along the longitudinal direction of the shell through the external telescopic device 19;
and the controller is electrically connected with the liquid level sensor 20, the electric switch valve, the pump body and the telescopic device 19.
The implementation process of the invention is as follows: when the liquid level sensor 20 detects that the liquid level is close to the cover plate 22, the first air vent 21 of the electric switch valve is controlled to be closed, the feed inlet is controlled to be closed, the waste electrolyte to be treated is stopped to enter the shell, and then two circulation pipelines are started, so that the waste electrolyte in the shell slowly flows from bottom to top, and the separation and adsorption of heavy metals in the solution by the heavy metal separation plate bodies 17 are facilitated. After the treatment for a specified time, the liquid outlet 8 is opened when the heavy metal content in the treated waste electrolyte is detected to be in accordance with the national discharge standard from the sampling port 11, the treated waste electrolyte is discharged for a certain time, and when the liquid level sensor 20 detects that the liquid level is not close to the cover plate 22, the electric switch valve is controlled to open the first air vent 21, so that the discharge of the treated waste electrolyte is promoted to be clean. After the treated waste electrolyte is discharged cleanly, repeating the steps, and carrying out the treatment of the waste electrolyte to be treated in the next round until the heavy metal content in the treated waste electrolyte cannot meet the national emission standard after the treatment for a specified time is detected from the sampling port 11, and then cleaning the plurality of heavy metal separation plate bodies 17. The plurality of heavy metal separation plate bodies 17 are cleaned as follows: the waste electrolyte which does not meet the national discharge standard is returned to the original container for storing the waste electrolyte to be treated, the output end of the telescopic device 19 is controlled to extend, the cover plate 22 drives the heavy metal separation plates 17 to move towards the bottom of the shell, the distance between the cover plate 22 and the bottom wall of the shell is reduced, the cleaning liquid of the second charging bucket 27 is controlled to enter the space between the cover plate 22 and the bottom wall of the shell, the first circulating pipeline is controlled to be started, namely the circulating pipeline connected with the middle part and the lower part of the shell is controlled, the liquid is driven to flow in the opposite direction, namely the cleaning liquid between the cover plate 22 and the bottom wall of the shell flows from top to bottom, the heavy metal separation plates 17 are backwashed, after the heavy metal ions are separated or desorbed from the heavy metal separation plates 17, the collecting opening 7 is controlled to be opened, the used cleaning liquid is discharged from the collecting opening 7, and the treatment is collected. After the used cleaning liquid is discharged completely, the output end of the telescopic device 19 is controlled to retract to the original position, and then the waste electrolyte to be treated of the next round is processed.
The invention controls the back flushing of the heavy metal separation plate bodies 17 by adding the cleaning liquid after reducing the distance between the cover plate 22 and the bottom wall of the shell, reduces the using amount of the cleaning liquid and reduces the subsequent working procedures of the used cleaning liquid. The cleaning solution is used for back flushing the plurality of heavy metal separation plate bodies 17, so that heavy metal ions are separated or desorbed from the plurality of heavy metal separation plate bodies 17, and the plurality of heavy metal separation plate bodies 17 are regenerated for use.
Based on the above embodiment, the connection relationship between the plurality of connection rod bodies 14 and the plurality of heavy metal separation plate bodies 17 and the cover plate 22 is specifically: the upper end of one group of connecting rod bodies 14 is hinged with the bottom of the cover plate 22, a hinging point 16 is shown in the figure, the lower end of the connecting rod body 14 is provided with a sliding block, the sliding block is in sliding connection with a sliding groove on the upper surface of an adjacent heavy metal separation plate body 17, the sliding block arranged at the lower end of the connecting rod body 14 is shown as a second sliding block 13 in the figure, and the sliding groove on the upper surface of the heavy metal separation plate body 17 is shown as a second sliding groove 15; the upper ends of each group of the other multiple groups of connecting rod bodies 14 are sequentially hinged with the bottoms of the multiple heavy metal separation bodies, and the lower end sliding blocks of the connecting rod bodies 14 are in sliding connection with the sliding grooves on the upper surfaces of the next adjacent heavy metal separation plate bodies 17. If the nanofiltration membrane or ultrafiltration membrane is adopted as the filter medium, the nanofiltration membrane or ultrafiltration membrane is covered on the outer frame body 30 or the screen surface of the heavy metal separation plate body 17 to form a filter screen, and heavy metals are separated from the waste electrolyte by a membrane separation method. The cadmium content in the waste electrolyte treated by the device is less than 0.1mg/L, the nickel content is less than 1.00mg/L, and even lower, thereby meeting the national emission standard.
On the basis of the above embodiment, the number of the connecting rod bodies 14 in each group is two or three, the number of the sliding grooves on the upper surface of each heavy metal separation plate body 17 is the same as the number of the connecting rod bodies 14 in each group, and the sliding grooves are uniformly distributed, and the sliding grooves on the upper surface of each heavy metal separation plate body 17 are arranged in the direction extending from the center of the heavy metal separation plate body 17 to the edge of the heavy metal separation plate body.
On the basis of the above embodiment, the positioning block 31 is disposed on the second chute 15 on the upper surface of the heavy metal separation plate 17, so as to control the sliding distance between the lower end slider of the connecting rod 14 and the central position of the heavy metal separation plate 17, so as to control the compression distance of the telescopic filter, and the setting position of the positioning block 31 can be selected according to the compression requirement.
On the basis of the embodiment, the shell is of a cylindrical or rectangular box structure, the telescopic device 19 is arranged at the top of the shell, and the telescopic end of the telescopic device 19 is connected with the cover plate 22; a plurality of first sliding grooves 29 extending longitudinally are arranged on the inner wall of the shell, and a plurality of first sliding blocks 12 corresponding to the plurality of first sliding grooves 29 are arranged on the periphery of the heavy metal separation plate body 17 and the cover plate 22 and used for longitudinally linking and stretching the heavy metal separation plate body 17 and the cover plate 22 in the shell; the upper end hinge point 16 of each group of connecting rod bodies 14 is arranged on the first sliding block 12, and the sliding groove on the upper surface of the heavy metal separation plate body 17 does not pass through the first sliding block 12, so that the connecting rod bodies 14 are arranged in an upward inclined manner, and the longitudinal linkage expansion and contraction of the heavy metal separation plate bodies 17 and the cover plate 22 in the shell are facilitated.
In addition to the above embodiment, as shown in fig. 4, the heavy metal separation plate 17 includes:
a hard round or square outer frame 30, wherein the first sliding block 12 is arranged on the outer periphery of the outer frame 30, and a second sliding groove 15 is arranged on the upper end surface of the outer frame 30;
the dialysis bag is of a double-bag structure, a plurality of cavities are formed in each layer of bag at intervals along the filtering direction, the cavities between the two layers of bags are staggered, and graphene oxide colloid is arranged in each cavity.
Although embodiments of the invention have been disclosed above, they are not limited to the use listed in the specification and embodiments. It can be applied to various fields suitable for the present invention. Additional modifications will readily occur to those skilled in the art.
Claims (5)
1. The waste electrolyte treatment device for the cadmium-nickel storage battery is characterized by comprising the following components: a precipitation tank, a filtering device and a heavy metal separator;
the precipitation tank is a tank body with an opening at the upper part and is used for intensively precipitating waste electrolyte taken out from the waste cadmium-nickel storage battery;
the filtering device comprises a coarse filter, a precise filter and a first charging bucket, wherein the sedimentation tank is communicated with the coarse filter through a telescopic pipeline, then the coarse filter is sequentially communicated with the precise filter and the first charging bucket, and the first charging bucket is used for storing waste electrolyte to be treated after being filtered by the precise filter;
the heavy metal separator comprises a shell, a telescopic filter element and a second charging bucket;
the shell is a sealed container with an upper opening, a sampling port is arranged on the side wall of the shell, a liquid inlet, a liquid outlet and a collecting port are arranged at the bottom end of the shell, and switching valves are respectively arranged on the liquid inlet, the liquid outlet, the collecting port and the sampling port;
the telescopic filter piece is arranged in the shell, a filter medium is arranged on the telescopic filter piece and used for separating or adsorbing heavy metals in waste electrolyte to be treated, and the filter medium is a nanofiltration membrane, an ultrafiltration membrane or graphene oxide colloid;
the second charging bucket is used for storing cleaning liquid to clean and regenerate the filter medium in the shell, the cleaning liquid is acid solution with concentration of more than 0.2mol/L, and a second liquid supply pipe for supplying liquid to the shell is arranged on the second charging bucket;
the heavy metal separator comprises a first charging tank, a second charging tank, a valve, a pump body, a first liquid supply pipe, a second liquid supply pipe, a return pipe and a valve, wherein the first charging tank is provided with the first liquid supply pipe and the return pipe which are communicated with a liquid inlet of the heavy metal separator; one end of the return pipe is communicated with the upper end of the first charging bucket, and the other end of the return pipe is communicated with the liquid inlet through a valve;
wherein the telescoping filter comprises:
the heavy metal separation plates are net plates or frame bodies through which water molecules can pass, the filter medium is uniformly covered on each heavy metal separation plate body, the heavy metal separation plates are arranged in the shell at intervals along the longitudinal direction of the shell to divide the shell into a plurality of cavities, the heavy metal separation plate body positioned at the bottommost part of the shell is fixedly connected with the shell, and the other heavy metal separation plate bodies can be connected in a sliding way along the longitudinal direction of the shell;
the cover plate can be connected in the shell in a sliding manner along the longitudinal direction of the shell, the cover plate is positioned above the heavy metal separation plate bodies, a first air vent communicated with outside air and a liquid level sensor for detecting the liquid level in the shell are arranged on the cover plate, and an electric switch valve is arranged on the first air vent;
the plurality of groups of connecting rod bodies are used for enabling the plurality of heavy metal separation plate bodies and the cover plate to be in linkage close to the heavy metal separation plate body at the bottommost part of the shell and enabling the plurality of heavy metal separation plate bodies and the cover plate to be in linkage far away from the heavy metal separation plate body at the bottommost part of the shell when the cover plate is driven by an external telescopic device to move along the longitudinal direction of the shell; the connection relation between the plurality of groups of connecting rod bodies and the plurality of heavy metal separation plate bodies and the cover plate is specifically as follows: the upper end of one group of connecting rod bodies is hinged with the bottom of the cover plate, the lower end of each connecting rod body is provided with a sliding block, and the sliding blocks are in sliding connection with sliding grooves on the upper surfaces of the adjacent heavy metal separation plate bodies; the upper end of each group of other multi-group connecting rod bodies is hinged with the bottoms of the heavy metal separation bodies in sequence, and the sliding blocks at the lower ends of the connecting rod bodies are in sliding connection with the sliding grooves on the upper surfaces of the next adjacent heavy metal separation plate bodies; the shell is of a cylindrical or rectangular box structure, the telescopic device is arranged at the top of the shell, and the telescopic end of the telescopic device is connected with the cover plate; the heavy metal separation plate body and the cover plate are longitudinally linked and telescopic in the shell; the upper end hinge point of each group of connecting rod bodies is arranged on the first sliding block, and the sliding groove on the upper surface of the heavy metal separation plate body does not pass through the first sliding block;
and the controller is electrically connected with the liquid level sensor, the electric switch valve, the pump body and the telescopic device.
2. The device for treating waste electrolyte of a cadmium-nickel storage battery according to claim 1, wherein two circulating pipelines are arranged on the side wall of the shell, one end of each pipeline is communicated with the upper part of the shell, and the other end of each pipeline is communicated with the lower part of the shell; one end of the other pipeline is communicated with the middle part of the shell, and the other end of the other pipeline is communicated with the lower part of the shell; each pipeline is provided with a pump body and a valve for controlling the opening and closing of the circulating pipeline.
3. The device for treating waste electrolyte of cadmium-nickel storage battery according to claim 1, wherein each group of connecting rods is two or three, the number of the sliding grooves on the upper surface of each heavy metal separation plate body is the same as that of each group of connecting rods, the sliding grooves are uniformly distributed, and the sliding grooves on the upper surface of each heavy metal separation plate body are arranged in a direction extending from the center of the heavy metal separation plate body to the edge of the heavy metal separation plate body.
4. The apparatus for treating waste electrolyte of cadmium-nickel storage battery as claimed in claim 3, wherein a positioning block is provided on a chute on the upper surface of the heavy metal separation plate body for controlling a distance of sliding approach of a lower slider of the connection rod body to the central position of the heavy metal separation plate body so as to control a compression distance of the telescopic filter.
5. A method for treating waste electrolyte of a cadmium-nickel storage battery, characterized in that it comprises the steps of:
step one, concentrating waste electrolyte in a waste cadmium-nickel storage battery into a precipitation tank for precipitation;
step two, the precipitated waste electrolyte is concentrated into a first charging bucket for storage after primary filtration and secondary filtration in sequence;
step three, separating or adsorbing heavy metals contained in the waste electrolyte to be treated in the first charging bucket through heavy metal separation treatment;
step four, sampling the waste electrolyte subjected to the heavy metal separation treatment for a specified time, and carrying out a censoring test or field detection;
fifthly, discharging when the concentration of the detected heavy metals reaches the standard, otherwise, repeatedly carrying out heavy metal separation treatment on the waste electrolyte;
wherein, the primary filtration, the secondary filtration and the heavy metal separation are respectively processed by a coarse filter, a precise filter and a heavy metal separator; the fifth step further includes: when the concentration of the heavy metals does not reach the standard in the assay or detection, the heavy metal separator is cleaned and reused, and the cleaned cleaning liquid is discharged and collected.
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| CN202210004543.5A CN114314884B (en) | 2022-01-04 | 2022-01-04 | Method and device for treating waste electrolyte of cadmium-nickel storage battery |
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