CN105932350A - Recycling method for waste lead-acid storage battery lead plaster desulphurization byproduct - Google Patents
Recycling method for waste lead-acid storage battery lead plaster desulphurization byproduct Download PDFInfo
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- CN105932350A CN105932350A CN201610317562.8A CN201610317562A CN105932350A CN 105932350 A CN105932350 A CN 105932350A CN 201610317562 A CN201610317562 A CN 201610317562A CN 105932350 A CN105932350 A CN 105932350A
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- filter liquor
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- 239000011505 plaster Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002253 acid Substances 0.000 title claims abstract description 29
- 239000002699 waste material Substances 0.000 title claims abstract description 29
- 239000006227 byproduct Substances 0.000 title claims abstract description 23
- 238000004064 recycling Methods 0.000 title abstract description 6
- 238000003860 storage Methods 0.000 title abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000011084 recovery Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 13
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 11
- 239000013078 crystal Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000012216 screening Methods 0.000 claims abstract description 4
- 239000000706 filtrate Substances 0.000 claims description 57
- 238000006477 desulfuration reaction Methods 0.000 claims description 46
- 230000023556 desulfurization Effects 0.000 claims description 45
- 230000003009 desulfurizing effect Effects 0.000 claims description 19
- 239000006071 cream Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000004061 bleaching Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 abstract description 21
- 238000005342 ion exchange Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 235000011152 sodium sulphate Nutrition 0.000 abstract 2
- 238000006386 neutralization reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000011347 resin Substances 0.000 description 19
- 229920005989 resin Polymers 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 17
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 238000004042 decolorization Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 206010042674 Swelling Diseases 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000009428 plumbing Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RLLPVAHGXHCWKJ-IEBWSBKVSA-N (3-phenoxyphenyl)methyl (1s,3s)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(Cl)Cl)[C@@H]1C(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 RLLPVAHGXHCWKJ-IEBWSBKVSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052924 anglesite Inorganic materials 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000005323 carbonate salts Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002611 lead compounds Chemical class 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/18—Dehydration
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention relates to a recycling method for a waste lead-acid storage battery lead plaster desulphurization byproduct. The recovery method comprises the following steps: (1) pretreating waste sulfuric acid obtained through decomposition of lead-acid storage batteries, then adding the pretreated waste sulfuric acid into a desulphurization lead plaster filter liquor, and controlling the pH value of the filter liquor to be 6-7; (2) removing heavy metal ions in the desulphurization lead plaster filter liquor by using cation exchange resin; and (3) adding activated carbon into the desulphurization lead plaster filter liquor and carrying out decoloration at the temperature of 50-90 DEG C, and finally carrying out evaporative crystallization, solid-liquid separation, drying and screening to obtain anhydrous Na2SO4 crystal. The purpose of recycling the anhydrous Na2SO4 from the desulphurization lead plaster filter liquor is achieved through the steps of filter liquor collection and neutralization, heavy metal removal with an ion exchange method, activated carbon decoloration, evaporative crystallization and the like, and the grade of the obtained sulfate byproduct exceeds national secondary standard, so that the recycling method is simple in technology and low in cost and has good application prospect.
Description
Technical field
The invention belongs to lead-acid accumulator and recycle field, particularly to a kind of waste lead acid battery lead cream desulfurizing byproduct
Recovery method.
Background technology
In recent years, along with climbing up and up of lead-acid accumulator consumption figure, its learies increases the most accordingly.China's lead acid storage battery at present
The consumption lead amount in pond occupies about the 70% of total value, but recycling waste lead batteries rate is less than 90%, and developed country's general warranty
100%；Lead recovery during China's secondary lead smelting is generally about 80%, and Foreign Advanced Lerel is up to more than 98%.
Therefore annual China there are about the waste lead accumulator of about 30,000 tons and fails to be recycled utilization, simultaneously because the response rate is low causes China
The lead and the lead compound that there are about about 4.5 ten thousand tons every year are flowed in air, soil and water body, cause the serious wasting of resources and
Environmental pollution.Therefore the research direct relation carrying out pollution-free or light pollution lead regenerative process the development of China's plumbing.
The most according to the literature, according to the current reserve-production ratio having verified lead ore resource, lead ore is the most enough exploited 25～30 years.Along with
The exhaustion day by day of lead ore resource, the recycling and reuse of lead metal has become the only way realizing plumbing sustainable development.
Lead metal mainly consumes in the production of accumulator at present, and therefore the regenerative process of lead is mainly the lead plaster in lead-acid accumulator
Slag mud carries out reduction and converts to obtain lead and the process of metal.The difficult point of this process is the smelting of lead plaster, and its method at present may be used
It is divided into pyrogenic process, wet method and dry and wet combination method.It is low that pyrometallurgical smelting also exists metal recovery rate, and energy consumption is high and seriously polluted three big problems.
Dry and wet combination method typically takes wet desulphurization, pyrometallurgical smelting, i.e. waste lead accumulator is carried out cracking and sorting, synthetical recovery, lead plaster
After desulfurization conversion, then carry out melting with rotary kiln or reverberatory furnace.The purer pyrometallurgical smelting of this method, significantly reduces SO2
Discharge capacity, but later stage melting still have employed high-temperature service, therefore cannot can cause lead dust pollution with avoiding.Waste lead accumulator
Wet treatment can be divided three classes: (1) lead plaster desulfurization conversion leach electrodeposition method；(2) lead plaster directly leaches electricity
Area method；(3) lead plaster direct electrowinning method.
The lead plaster that lead-acid accumulator obtains after cracking and sorting is the hybrid solid of lead-containing compounds, main component substantially:
PbSO425%～30%, PbO215%～20%, Pb 2%～3%.The desulfurization conversion of lead plaster is i.e. by PbSO therein4Convert
For being easier to the process of other compound form of reduction treatment.At present this technique mainly use soluble carbonate salt as desulfurizing agent,
Such as Na2CO3、NH4HCO3Deng.And desulfurizing agent mainly consumes PbSO in lead plaster4Conversion on, the PbO in lead plaster2With
Pb is not involved in reaction.
At present, for the by-product such as Na produced after desulfurization2SO4The research how to recycle is less.
Summary of the invention
The technical problem to be solved is to provide the recovery method of a kind of waste lead acid battery lead cream desulfurizing byproduct, the party
Method is by collecting, neutralizing filtrate；Ion exchange goes heavy metal；Activated carbon decolorizing；The steps such as evaporative crystallization achieve from lead plaster
Desulfurization filtrate is reclaimed anhydrous Na2SO4Purpose, exceed national grade ii standard through analyzing the grade of sulfate by-products obtained,
Technique is simple, and low cost has a good application prospect.
A kind of recovery method of the waste lead acid battery lead cream desulfurizing byproduct of the present invention, including:
(1) being decomposed by lead-acid accumulator after the Waste Sulfuric Acid of gained carries out pretreatment adds in desulfurization lead plaster filter liquor, controls filtrate pH value and exists
6～7；
(2) cation exchange resin is used to remove the heavy metal ion in desulfurization lead plaster filter liquor；Wherein, the flow of desulfurization lead plaster filter liquor is
0.5～5ml/min, treatment temperature is 20 DEG C～45 DEG C；
(3) use activated carbon to add in desulfurization lead plaster filter liquor by liquid-solid ratio 10～20ml/g to decolour in 50 DEG C～90 DEG C, final evaporation
Crystallization, solid-liquid separation, it is dried screening, obtains anhydrous Na2SO4Crystal.
Pretreatment in described step (1) is Air Exposure, removes oils therein, float etc..
Desulfurization lead plaster filter liquor proportion in described step (1) < 1.2, then it is back to lead plaster pretreatment desulfurizing step cycle and utilizes；Ratio
Weight >=1.2, then add Waste Sulfuric Acid.
The model of the cation exchange resin in described step (2) is 732, D113 or D850 (all originates from Shanghai traditional Chinese medicines group
Chemical reagent company limited)；Use front preprocessed.
The cation exchange resin process time in described step (2) is 2.5～100min.
The particle diameter of the activated carbon in described step (3) is 250 μm～400 μm.
Bleaching time in described step (3) is 30～60min.
Evaporative crystallization temperature in described step (3) is 70 DEG C～80 DEG C.
The liquid content after solid-liquid separation in described step (3) is less than 3%.
Baking temperature in described step (3) is 100～140 DEG C, and drying time is 4～8h.
Beneficial effect
The present invention is by collecting, neutralizing filtrate；Ion exchange goes heavy metal；Activated carbon decolorizing；The steps such as evaporative crystallization realize
Reclaim anhydrous Na from the lead plaster desulfurization filtrate2SO4Purpose, exceed country two through analyzing the grade of sulfate by-products obtained
Grade standard, technique is simple, and low cost has a good application prospect.
Accompanying drawing explanation
Fig. 1 is the ion exchange column structure chart that the present invention uses；
Fig. 2 is the water inlet pH value impact on ion remaval efficiency；
Fig. 3 is the filtrate water inlet flow velocity impact on ion remaval efficiency；
Fig. 4 is the treatment temperature impact on ion remaval efficiency；
Fig. 5 is lead plaster desulfurization filtrate decolouring index sign trend.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and not
For limiting the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, those skilled in the art can
To make various changes or modifications the present invention, these equivalent form of values fall within the application appended claims limited range equally.
Utilize the metal element content such as Fe, Pb, Sb in WFX 120 atomic absorption spectrophotometer detection lead plaster desulfurization filtrate
Instrument controlling condition as shown in table 1:
Table 1 Atomic Absorption Spectrometry condition
The expression formula of the clearance Q of metal ion is:
Q=[1-(C2/C1)] * 100%
In formula: C1、C2The respectively corresponding content of each metallic element, % in filtrate before and after cation-adsorption exchange column.
Embodiment 1
(1) desulfurization lead plaster filter liquor is collected: if the proportion of filtrate < 1.2, return it to lead plaster pretreatment desulfurizing step cycle and utilize；If
Filtrate proportion >=1.2, then enter next step, to Na when this step ensure that filtrate evaporative crystallization2SO4The demand of concentration；By lead
The Waste Sulfuric Acid of acid accumulator decomposition gained adds after carrying out pretreatment in desulfurization lead plaster filter liquor to neutralize excess Na in filtrate2CO3, control
Filtrate pH value processed is 6～7；Containing Fe in Waste Sulfuric Acid3+、Pb2+、Sb3+Deng many kinds of metal ions and impurity, therefore need
Remove.
(2) heavy metal ion in employing cation exchange resin removal desulfurization lead plaster filter liquor:
1. the pretreatment of resin:
In untreated resin, mix some inorganic impurities, unreacted monomer, the low polymer in its structure, decompose
Products etc., can gradually be dissolved in the water in use, and therefore sold resin must can use after pretreatment.
Repeatedly resin is rinsed until after the transparent no longer colour developing of washing liquid, soaking more than 20h with clear water with warm water.Outwell clear water, then
With more than soak with ethanol 20h and stir for several times to remove wherein alcohol dissolubility impurity.After cleaning up, with the soak with hydrochloric acid 20h of 8
Above and stir for several times to remove wherein acid soluble impurities.Clean after being neutrality to washing liquid, then soak by the NaOH solution of 5
About 4h also stirs for several times to remove wherein alkali solubility impurity.Clean again to washing liquid be neutrality, with sucking filtration machine sucking filtration resin and with filter
Paper blots surface moisture, obtains pretreated ion exchange resin sample.
2. ion exchange column is prepared
Experiment 50mL acid buret makees ion exchange column, and inside is filled with the amberlite lipid layer of 10cm.Exchange column
Upper and lower absorbent cotton is inside had to fix resin bed, it is ensured that it will not loosen in ion exchange process.For guaranteeing that the Inlet and outlet water water yield is uniform,
The upper and lower two ends of exchange column are provided with the water-locator with gauze parcel that circular steel disc with holes is made, and water inlet pipe and water outlet pipe passes through rubber closure and the mouth of pipe
Being connected, its structure is shown in Fig. 1.
3. the selection of cation exchange resin
Choose 732, tri-kinds of cation exchange resiies of D113, D850 are respectively charged into ion exchange column after pretreatment.By lead plaster
In desulfurization filtrate Waste Sulfuric Acid and after, take 50mL from top add exchange column make it flow downwardly through ion exchange layer.Experiment condition
Control is: flow of filtrate 1.0mL/min, pH value 6 of intaking, temperature 20 DEG C.Gather effluent, use atomic absorption spectrophotometry light
Fe in filtrate before and after the process of degree method mensuration3+、Pb2+、Sb3+Deng the concentration of metal ion, calculate its clearance.Each metal ion goes
Except rate and the swelling situation of different resins are shown in Table 2.
Table 2 removal of heavy metal ions result
Result shows, three kinds of selected resins are at room temperature, and acid-base value is close under conditions of neutrality, in lead plaster desulfurization filtrate
Heavy metal ion has a highest clearance, all more than 98% and be more or less the same.But 732 type resin swellings are excessive to be caused
Its service life shortens, and should not select；And D850 type resin either clearance or swelling ratio to metal ion is the most inferior
In D113 type resin.Therefore select D113 type cation exchange resin as the absorption of heavy metal ion in lead plaster desulfurization filtrate
Agent.
4. the removing experimental study of heavy metal ion in lead plaster desulfurization filtrate
A. the impact of filtrate water inlet pH value heavy metal ion remaval efficiency:
D113 type resin is loaded ion exchange column, at a temperature of 20 DEG C, adjusts respectively with dilute sulfuric acid filtrate intake pH value
To 2,3,4,5,6,7, controlling flow of filtrate 1.0mL/min, the alignment processing time is 50min.Collect out flow liquid, point
Do not measure Fe3+、Pb2+、Sb3+Concentration, calculates removal efficiency.Its result is as shown in Figure 2.
From Figure 2 it can be seen that D113 type resin absorption, displacement Pb2+、Sb3+Ability affected relatively big by filtrate water inlet pH value,
And Fe3+Absorption displacement the most impacted less.Along with filtrate water inlet pH value increase, the removal efficiency of three metal ion species in
Ascendant trend, this is because D113 type resin itself belongs to weak-acid cation-exchange resin, in highly acid solution environmental
That first replace is H+, followed by Fe3+、Pb2+、Sb3+, thus cause the metal ion that script adsorbs on resin also
It is resolved in solution, reduces its adsorbance.
And along with the rising of pH value, Fe3+、Pb2+、Sb3+Exchange reaction can be sufficiently carried out with the activist of resin, make
In effluent, concentration of metal ions is declined.Therefore under this experiment condition, remove the heavy metal ion in lead plaster desulfurization filtrate, its filter
Liquid water inlet pH value controls 6～7.
B. the impact of filtrate water inlet flow velocity heavy metal ion remaval efficiency:
At a temperature of 20 DEG C, controlling filtrate water inlet pH value is 6, utilizes peristaltic pump to control lead plaster desulfurization flow of filtrate and is respectively
0.5mL/min, 1mL/min, 2mL/min, 5mL/min, 10mL/min, 20mL/min, the alignment processing time divides
Wei 100min, 50min, 25min, 10min, 5min, 2.5min.Collect out flow liquid, measure Fe respectively3+、Pb2+、
Sb3+Concentration, calculates removal efficiency.Its result is as shown in Figure 3.
As seen from Figure 3, when lead plaster desulfurization filtrate water inlet flow velocity is more than 5ml/min, ion remaval efficiency increases rapidly with flow velocity
Decline.This is because flow velocity increases, the filtrate time of staying in ion exchange column shortens, part metals therein ion future
Obtain and be diffused into effective molecule generation metathesis of active position and resin, just flow out exchange column.When filtrate water inlet flow velocity exists
Time within 5ml/min, metal ion can sufficiently swap effect with resin, has preferable removal effect.Therefore event is originally
Embodiment removes the heavy metal ion in lead plaster desulfurization filtrate, and filtrate water inlet flow speed control is below 5ml/min.
C. the impact of temperature heavy metal ion remaval efficiency
Controlling filtrate water inlet pH value is 6, and lead plaster desulfurization flow of filtrate 1mL/min, the alignment processing time is 50min, in temperature
Be respectively 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, collect out flow liquid under the reaction condition of 45 DEG C, measure Fe respectively3+、Pb2+、
Sb3+Concentration, calculates removal efficiency.Its result is as shown in Figure 4.
From fig. 4, it can be seen that within the temperature range of 20 DEG C～45 DEG C, lead plaster desulfurization filtrate heavy metal ion is gone by D113 type resin
Except the change of efficiency is not clearly.This is because, temperature raise can promote ion exchange resin heavy metal ion absorption,
Displacement efficiency, but also accelerate the parsing speed of adion, both maintain a kind of dynamic equilibrium.Therefore, this adsorbed
Journey is at room temperature carried out.
Result of study shows, lead plaster desulfurization filtrate after twice exchange column heavy-metal ion removal step, Fe therein3+、
Pb2+、Sb3+Clearance is up to more than 99%.
(3) use activated carbon to add in desulfurization lead plaster filter liquor to decolour:
1. by filtrate collection, Study On The Activated Carbon is to its decolorization:
The conical flask of 250ml is carried out, the lead plaster desulfurization filtrate after 100ml heavy-metal ion removal is placed wherein, so
After the activated carbon of particle diameter 250 μm～400 μm added in flask and seal.Set the temperature of water bath with thermostatic control bed, flask is put
In wherein so that it is the reaction appointment time.After completion of the reaction, utilize the absorbance before and after the decolouring of spectrophotometric determination filtrate, inhale
Receive wavelength and be set to 410nm.Being calculated as follows of percent of decolourization:
Absorbance × 100% before percent of decolourization (%)=(absorbance after absorbance-decolouring before decolouring)/decolouring
Experiment uses Orthogonal Method, investigates bleaching temperature, action time, liquid-solid ratio, four factors of filtrate pH value to decolorizing efficiency
Impact.Experiment control factor and level are as shown in table 3, according to four factor three water-glass L9(34) test.
Table 3 lead plaster desulfurization filtrate decolorization experiment factor and level
2. data analysis:
With activated carbon, lead plaster desulfurization filtrate being carried out desolventing technology, experimental result is as shown in table 4 with analysis:
Table 4 lead plaster desulfurization filtrate decolouring result and analysis
According to extreme difference size, it is known that with activated carbon, lead plaster desulfurization filtrate being carried out desolventing technology, each governing factor is to decolorizing efficiency shadow
The reduction order of the degree of sound is arranged as: reaction liquid-solid ratio > reaction temperature > filtrate pH value > response time.
According to the height of factor average horizontal value each in experimental result, as can be seen from the table, in the case of not considering reciprocal action,
Processing lead plaster desulfurization filtrate using activated carbon as decolorising agent, preferred version should be: reaction liquid-solid ratio 10ml/g, reaction temperature 70 DEG C,
Filtrate pH value 5, response time 60min.Testing according to this preferred version condition, the percent of decolourization obtaining lead plaster filter liquor is
78.52%, result 71.16% of most preferably decolouring higher than orthogonal test.
3. activated carbon decolorizing index trend
With activated carbon under the conditions of each governing factor, the meansigma methods of lead plaster desulfurization filtrate decolorizing efficiency is drawn broken line for vertical coordinate respectively
Figure, i.e. decolouring index sign trend is shown in Fig. 5.
It can be seen that when temperature is less than 70 DEG C, the lifting of temperature can promote the carrying out of decoloring reaction, when temperature continues
Height of continuing rising, molecular thermalmotion aggravates, and the absorption of activated carbon is corresponding to analytic function to be accelerated, and analytic function has exceeded adsorption,
It is unfavorable for the carrying out of decoloring reaction on the contrary.Decolorizing efficiency increases with the increase in response time, and in 45min, speedup is very fast, 45min
Rear speedup slows down.The dosage of the activated carbon that the increase of reaction liquid-solid ratio is equivalent to the desulfurization filtrate interpolation of unit volume reduces, therefore
It is unfavorable for the carrying out of decoloring reaction.When solution pH value is in 5～7, the change of percent of decolourization is little, and pH value ＞ 7, percent of decolourization is fast
Speed declines.
It is demonstrated experimentally that lead plaster desulfurization filtrate is after twice activated carbon decolorizing processes, with spectrophotometer detect its light transmittance up to
More than 99%, therefore may be regarded as water white transparency shape solution.
(4) evaporative crystallization, solid-liquid separation, it is dried screening, obtains anhydrous Na2SO4Crystal.
Lead plaster desulfurization filtrate, after ion exchange resin goes heavy metal, activated carbon decolorizing step, can obtain containing Na2SO4Concentration
Mother solution more than 30%.It is known from literature that when water temperature is more than 32.38 DEG C, Na2SO4Dissolubility reduce on the contrary.According to right
Na2SO4The method of saturated solution crystallisation by cooling can not get anhydrous Na2SO4Crystal, can only separate out Natrii Sulfas (Na2SO4·10H2O),
Therefore evaporative crystallization method must be used.
1. evaporative crystallization:
Using water bath heating to control between 70～80 DEG C to lead plaster desulfurization filtrate evaporative crystallization, temperature, the water yield of evaporation is how many
According to Na2SO4Depending on the purity requirement of product.The water yield of evaporation is few, then the purity of product is high, but the mother solution of unit volume obtains
The product quality arrived is also few, and vice versa.In order to ensure crystal mass, recovery Na the most as much as possible2SO4By-product, real
Test by mother liquid evaporation to impurity will saturated but still undecomposed degree.
2. solid-liquid separation is screened with being dried:
Utilize Suction filtration device crystallization to be separated with mother solution after evaporative crystallization so that it is liquid content is less than 3% as far as possible.With appropriate distillation
Water washing crystal is to remove residual mother liquor further.After washing, crystal is as thermostatic drying chamber, is dried in the environment of 120 DEG C
About 6h so that it is water content is less than 0.1%, then sieves, crossing 60 mesh sieves is primes, and crossing 42 mesh sieves is seconds,
Remaining is three level Four.
3. crystal analysis:
Lead plaster desulfurization filtrate, after above step, obtains by-product anhydrous Na2SO4Crystal, its analysis result is shown in national standard
Table 5 below.
Table 5 reclaims crystal analysis result and national standard
As can be seen here, the by-product anhydrous Na reclaimed from lead plaster desulfurization filtrate2SO4Substantially conform to national standard
(GB6009 85) technology requirement to seconds and above grade thereof.
Claims (10)
1. a recovery method for waste lead acid battery lead cream desulfurizing byproduct, including:
(1) being decomposed by lead-acid accumulator after the Waste Sulfuric Acid of gained carries out pretreatment adds in desulfurization lead plaster filter liquor, controls filtrate pH value and exists
6～7；
(2) cation exchange resin is used to remove the heavy metal ion in desulfurization lead plaster filter liquor；Wherein, the flow of desulfurization lead plaster filter liquor is
0.5～5ml/min, treatment temperature is 20 DEG C～45 DEG C；
(3) use activated carbon to add in desulfurization lead plaster filter liquor by liquid-solid ratio 10～20ml/g to decolour in 50 DEG C～90 DEG C, final evaporation
Crystallization, solid-liquid separation, it is dried screening, obtains anhydrous Na2SO4Crystal.
The recovery method of a kind of waste lead acid battery lead cream desulfurizing byproduct the most according to claim 1, it is characterised in that: described
Pretreatment in step (1) is Air Exposure.
The recovery method of a kind of waste lead acid battery lead cream desulfurizing byproduct the most according to claim 1, it is characterised in that: described
Desulfurization lead plaster filter liquor proportion in step (1) < 1.2, then it is back to lead plaster pretreatment desulfurizing step cycle and utilizes；Proportion >=1.2,
Then add Waste Sulfuric Acid.
The recovery method of a kind of waste lead acid battery lead cream desulfurizing byproduct the most according to claim 1, it is characterised in that: described
The model of the cation exchange resin in step (2) is 732, D113 or D850；Use front preprocessed.
The recovery method of a kind of waste lead acid battery lead cream desulfurizing byproduct the most according to claim 1, it is characterised in that: described
The cation exchange resin process time in step (2) is 2.5～100min.
The recovery method of a kind of waste lead acid battery lead cream desulfurizing byproduct the most according to claim 1, it is characterised in that: described
The particle diameter of the activated carbon in step (3) is 250 μm～400 μm.
The recovery method of a kind of waste lead acid battery lead cream desulfurizing byproduct the most according to claim 1, it is characterised in that: described
Bleaching time in step (3) is 30～60min.
The recovery method of a kind of waste lead acid battery lead cream desulfurizing byproduct the most according to claim 1, it is characterised in that: described
Evaporative crystallization temperature in step (3) is 70 DEG C～80 DEG C.
The recovery method of a kind of waste lead acid battery lead cream desulfurizing byproduct the most according to claim 1, it is characterised in that: described
The liquid content after solid-liquid separation in step (3) is less than 3%.
The recovery method of a kind of waste lead acid battery lead cream desulfurizing byproduct the most according to claim 1, it is characterised in that: institute
Stating the baking temperature in step (3) is 100～140 DEG C, and drying time is 4～8h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108950235A (en) * | 2018-07-19 | 2018-12-07 | 芜湖青悠静谧环保科技有限公司 | A kind of recovery method of the pre- desulphurization mother solution of lead plaster |
| CN110042247A (en) * | 2019-04-26 | 2019-07-23 | 南京工程学院 | The recycle device and method of scrap lead cream in a kind of lead-acid accumulator |
| CN115824287A (en) * | 2023-02-24 | 2023-03-21 | 西安泰瑞环保技术有限公司 | Method, device, equipment and medium for analyzing effect of copper foil passivation solution wastewater recovery |
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| US4769116A (en) * | 1986-01-09 | 1988-09-06 | Engitec Impianti S.P.A. | Hydrometallurgical process for an overall recovery of the components of exhausted lead-acid batteries |
| CN101244831A (en) * | 2008-03-18 | 2008-08-20 | 华中科技大学 | Method and device for recycling anhydrous sodium sulfate from desulfurization lead plaster filter liquor |
| CN103771459A (en) * | 2014-01-16 | 2014-05-07 | 北京化工大学 | Method of recovering sodium sulfate from lead-bearing desulfurized waste liquid |
| CN104724730A (en) * | 2015-04-02 | 2015-06-24 | 湘潭大学 | Method and device for crystallizing lead plaster desulphurization by-product sodium sulfate based on localized cooling and rapid crystal precipitation |
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| US4769116A (en) * | 1986-01-09 | 1988-09-06 | Engitec Impianti S.P.A. | Hydrometallurgical process for an overall recovery of the components of exhausted lead-acid batteries |
| CN101244831A (en) * | 2008-03-18 | 2008-08-20 | 华中科技大学 | Method and device for recycling anhydrous sodium sulfate from desulfurization lead plaster filter liquor |
| CN103771459A (en) * | 2014-01-16 | 2014-05-07 | 北京化工大学 | Method of recovering sodium sulfate from lead-bearing desulfurized waste liquid |
| CN104724730A (en) * | 2015-04-02 | 2015-06-24 | 湘潭大学 | Method and device for crystallizing lead plaster desulphurization by-product sodium sulfate based on localized cooling and rapid crystal precipitation |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108950235A (en) * | 2018-07-19 | 2018-12-07 | 芜湖青悠静谧环保科技有限公司 | A kind of recovery method of the pre- desulphurization mother solution of lead plaster |
| CN110042247A (en) * | 2019-04-26 | 2019-07-23 | 南京工程学院 | The recycle device and method of scrap lead cream in a kind of lead-acid accumulator |
| CN110042247B (en) * | 2019-04-26 | 2020-08-04 | 南京工程学院 | Device and method for recycling waste lead paste in waste lead-acid battery |
| CN115824287A (en) * | 2023-02-24 | 2023-03-21 | 西安泰瑞环保技术有限公司 | Method, device, equipment and medium for analyzing effect of copper foil passivation solution wastewater recovery |
| CN115824287B (en) * | 2023-02-24 | 2023-09-15 | 西安泰瑞环保技术有限公司 | Method, device, equipment and medium for analyzing effect of recycling copper foil passivation solution wastewater |
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