CN102092874A - Equipment for recycling stainless steel neutral salt waste electrolyte - Google Patents
Equipment for recycling stainless steel neutral salt waste electrolyte Download PDFInfo
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- CN102092874A CN102092874A CN2009102585396A CN200910258539A CN102092874A CN 102092874 A CN102092874 A CN 102092874A CN 2009102585396 A CN2009102585396 A CN 2009102585396A CN 200910258539 A CN200910258539 A CN 200910258539A CN 102092874 A CN102092874 A CN 102092874A
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Abstract
The invention relates to equipment for recycling stainless steel neutral salt waste electrolyte. The waste electrolyte comprises a part or all of nickel ions, ferrous ions, ferric ions and chromium ions, and sodium sulfate. In the equipment, the waste electrolyte delivered from an electrolyte storage tank is subjected to an oxidation operation in an oxidation reaction tank, so that the ferrous ions in the waste electrolyte are oxidized into ferric ions, wherein the oxidation operation does not introduce new ions into the waste electrolyte. The pH value of the waste electrolyte is regulated to a preset value of between 4.8 and 5.2 by using a pH value regulating device. Sediment formed by the ferric ions and the chromium ions in the waste electrolyte subjected to pH value regulation is separated from clear liquid by using a solid-liquid separation device. Finally, the separated clear liquid is subjected to ion exchange in an ion exchange device to extract nickel therein, and the liquid discharged after the ion exchange is returned to the electrolyte storage tank. Therefore, the equipment can simultaneously reclaim the nickel metal and the waste electrolyte in a simple mode.
Description
Technical field
The present invention relates to environmental technology and resource and reclaim the field, especially relate to a kind of equipment that is used to recycle stainless steel neutral salt electrolysis waste solution.
Background technology
Stainless steel is described as the elaboration in the steel products, with its superior solidity to corrosion, unique surface and excellent processing characteristics, develops very rapidly, and Application Areas is more and more wide.The pickling of stainless steel strip is a crucial procedure during cold-rolling stainless steel is produced, and has conclusive effect to guaranteeing product surface quality.Acid cleaning process also develops into present chemical pickling and electrolytic pickling process combined by the pure chemistry pickling in the 60 to 70's.In acid-washing stainless steel generation can produce comprise heavy metal nickel, chromium waste water.Traditionally, these direct discharging of waste water, severe contamination environment.
In order to tackle serious environmental problem day by day, industry is just addressing the pollution problem of waste water.Adopt the method for some chemical precipitations can make the waste water reclamation utilization, but the processing of the sludge containing heavy metal that precipitation produces remain a problem.Since the rise of metal price in recent years, some metals resources, and for example the recovery of nickel, chromium may produce economic benefit.Therefore the technology of precious metal appearred extracting from heavy metal-containing waste water or mud.But present stainless steel acid-washing waste liquid recovery technology, on waste water reclamation and metal recovery, consider respectively, consequently in some technologies, can only select recycle-water and metal one of them, the perhaps comprehensive recovery of water and the metal by realizing the containing metal waste liquid in two the separate technology.This has increased the expending of aspect such as time, resource of whole recovery process undoubtedly.
For instance, mainly contain metal ions such as iron, nickel, chromium in the spent pickle liquor that stainless steel neutral salt electrolysis process produces.Discharging causes serious environment pollution in order to avoid directly, and general at present the employing adds alkali and metal ion is carried out sedimentary method handle, and the effluent reuse of post precipitation is to electrolyzer.Though this method can reclaim electrolytic solution, but to produce the mud of the mixture that comprises three kinds of metal hydroxidess, this has produced extra sludge treatment cost, and the utility value of mud is also relatively low, especially can't reclaim the nickel ion with higher economic worth.
Therefore, expect to have a kind of more effectively equipment and can reclaim nickel ion on the one hand,, also can reduce the disposal costs of mud on the other hand to obtain the certain economic interests to recycling in the stainless steel neutral salt electrolysis waste solution.
Summary of the invention
Technical problem to be solved by this invention provides a kind of equipment that is used to recycle stainless steel neutral salt electrolysis waste solution, can extract nickel ion from waste liquid, considers the reuse of electrolysis waste solution simultaneously, does not introduce new impurity in this equipment running process.
The present invention is that to solve the problems of the technologies described above the technical scheme that adopts be to propose a kind of equipment that is used to recycle stainless steel neutral salt electrolysis waste solution, this electrolysis waste solution comprises nickel ion, in ferrous ion, iron ion, the chromium ion partly or entirely, and sodium sulfate, this equipment comprises oxidizing reaction pond, pH value adjusting device, equipment for separating liquid from solid and ion exchange unit.This electrolysis waste solution is imported from an electrolytic solution storage tank in the oxidizing reaction pond, in this reaction tank this electrolysis waste solution is carried out an oxidation operation, makes the ferrous ion in this electrolysis waste solution be oxidized to iron ion, and wherein this oxidation operation is not introduced new ion to this waste liquid.The pH value adjusting device is regulated pH value to a preset value of this electrolysis waste solution, and this preset value is between 4.8-5.2.The electrolysis waste solution that the equipment for separating liquid from solid input is regulated through the pH value separates with the precipitation that chromium ion forms the iron ion in the electrolysis waste solution with clear liquid.The isolated clear liquid of ion exchange unit input equipment for separating liquid from solid extracts nickel wherein to carry out ion-exchange, and the liquid of exporting after the ion-exchange is fed back to the electrolytic solution storage tank.
Recycle the equipment of stainless steel neutral salt electrolysis waste solution in above-mentioned being used for, the oxygenant of this oxidation operation is oxygen or hydrogen peroxide.
Recycle the equipment of stainless steel neutral salt electrolysis waste solution in above-mentioned being used for, when this oxygenant was oxygen, this equipment also comprised aerating apparatus, by aeration oxygen was sneaked in this waste liquid.
Recycle the equipment of stainless steel neutral salt electrolysis waste solution in above-mentioned being used for, this pH value adjusting device is regulated the pH value of this waste liquid by sodium hydroxide.
Recycle the equipment of stainless steel neutral salt electrolysis waste solution in above-mentioned being used for, also comprise accurate filter, be connected between equipment for separating liquid from solid and the ion exchange unit.
Recycle the equipment of stainless steel neutral salt electrolysis waste solution in above-mentioned being used for, the ion exchange resin in this ion exchange unit is sodium type weakly acidic cation-exchange resin.
The present invention makes it compared with prior art owing to adopt above technical scheme, and combination and simple operation by a small amount of device can realize the recovery of nickel ion and electrolytic solution, and spent resource are lower.
Description of drawings
For above-mentioned purpose of the present invention, feature and advantage can be become apparent, below in conjunction with accompanying drawing the specific embodiment of the present invention is elaborated, wherein:
Fig. 1 illustrates the recycling equipment of the stainless steel neutral salt electrolysis waste solution of one embodiment of the invention.
Fig. 2 illustrates the recycling equipment process flow sheet of the stainless steel neutral salt electrolysis waste solution of one embodiment of the invention.
Embodiment
The invention provides a kind of recycling equipment of stainless steel neutral salt electrolysis waste solution, an aspect of this equipment extracts nickel ion from waste liquid, to reach the purpose of recovery, for reaching this point, needs to get rid of earlier the interference of other metal ion in the waste liquid.On the other hand, because waste liquid (mainly be meant and comprise electrolytical solution) needs reuse, guarantee not introduce new impurity in the operational process of equipment.
The analyzing and testing result of stainless steel neutral salt electrolysis waste solution shows: the major metal ion is Fe in the stainless steel neutral salt electrolysis waste solution
2+, Fe
3+, Ni
2+, Cr
3+, all the other are ionogen (Na
2SO
4).The pH value of electrolysis waste solution changes greatly, generally speaking in 2～6 scope.Because the difference of pH value, metal ion content also is very different, and wherein nickel ion is not very big with the variable effect of pH value, can reach 1200mg/L when concentration is higher, generally all more than 200mg/L.And iron ion (referring to trivalent ion in this manual), ferrous ion (referring to divalent ion in this manual) and chromium ion are along with the variation of pH value is just very obvious.Reach at 5 o'clock in the pH value, the concentration of iron ion and chromium ion is very low, and all below 1mg/L, and the pH value is when low, and iron ion and chromium ion concentration all are improved largely, and the highest 1050mg/l that can reach of iron concentration wherein is on average about 600mg/l; Chromium concn is the highest can to reach 160mg/l, on average about 60mg/l.
The solubility product data sheet of further looking into compound is as can be known: Fe (OH)
2Solubility product be 8.0 * 10
-16, Fe (OH)
3Solubility product be 4.0 * 10
-38, Ni (OH)
2Solubility product be 2.0 * 10
-15, Cr (OH)
3Solubility product be 6.3 * 10
-31Can calculate according to the solubility product data, when the Ni ionic concn maintains the 2000mg/L left and right sides, pH greatly about about 7, under this pH condition, Fe
3+And Cr
3+Ionic concn can drop to 2.78 * 10 respectively
-4Mg/L and 1.61 * 10
-3Below the mg/L, and Fe
2+Concentration does not have obvious variation.Consider that iron ion can produce coprecipitation phenomena in conjunction with a part of nickel ion in precipitation process, cause the rate of recovery of nickel obviously to reduce, take all factors into consideration the retention rate of siderochrome ionic clearance and nickel, therefore the pH value of selecting in one embodiment is preset value 4.8-5.2.
The recycling equipment of the stainless steel neutral salt electrolysis waste solution of one embodiment of the invention comprises oxidizing reaction pond 10, pressure filter 20, pump 30, accurate filter 40, ion exchange unit 50 with reference to shown in Figure 2.The input aperture in oxidizing reaction pond 10 connects an electrolytic solution storage tank 60, and the delivery port of ion exchange unit 50 connects two electrolytic solution storage tanks 60,70.Two electrolytic solution storage tanks 60,70 were communicated with by communicating pipe.Oxidizing reaction pond 10, pressure filter 20, pump 30, accurate filter 40, ion exchange unit 50 connect according to technical process preface successively.Wherein carry out oxidation operation in the oxidizing reaction pond 10, oxidation operation can be to sneak into oxygen by aerating apparatus in waste liquid, also can be to add other oxygenant.Regulate by can in oxidizing reaction pond 10, realizing the pH value for oxidizing reaction pond 10 configurations one pH value adjusting devices (figure does not show).But being understood that easily that the pH value is regulated can finish with other isolated system.The pH value adjusting device comprises the controller of medicating mechanism, control dosing and usually in order to detect the pH regulator result and to feed back to the pH transmitter of controller.
Fig. 2 illustrates the recoverying and utilizing method schema of the stainless steel neutral salt electrolysis waste solution of one embodiment of the invention.Operation workflow below with reference to description equipment shown in Figure 2.
When electrolysis waste solution when electrolytic solution storage tank 60 enters oxidizing reaction pond 10, at step S1, this waste liquid is carried out an oxidation step, make the ferrous ion (Fe in the waste liquid
2+) be oxidized to iron ion (Fe
3+).As previously mentioned, iron ion just can most of precipitate through pH regulator in follow-up flow process, thereby reaches separating metal ionic purpose.Fe
2+Very easily be oxidized to Fe
3+, because electrolytic solution needs fully recovering to the electrolytic solution storage tank, therefore the oxygenant that adds in oxidation step can not be introduced new ion to waste liquid.In an embodiment of the present invention, can select oxygen and hydrogen peroxide as Fe
2+Oxygenant, oxygen and hydrogen peroxide oxidation ferrous ion can not introduced new impurity.Reaction equation is as follows:
2Fe
2++2H
++O
2→2Fe
3++2H
2O
2Fe
2++H
2O
2+2H
+→2Fe
3++2H
2O
When oxygenant is oxygen, even only need just can in solution, sneak into oxygen by aeration.
At step S2, regulate the preset value of the pH value to about 5 (4.8-5.2) of waste liquid with the pH regulator device, iron ion and chromium ion are separated out with precipitation mode.In one embodiment, the employed reagent of pH value of regulating waste liquid is sodium hydroxide (NaOH), to guarantee can not introduce new ion in waste liquid.Be much higher than 5 waste liquid for the pH value, the pH value is regulated may be not necessarily.
Reaction equation is as follows:
[Fe
3+][OH
-]
3＝4.0×10
-38
Then, at step S3, after reaction, waste liquid can form precipitation in as the pressure filter 20 of equipment for separating liquid from solid, and the precipitation part forms mud and transports after pressure filter is handled, and supernatant liquor proceeds to next flow process through pump 30.Electrolysis waste solution is after peroxidation and precipitation process, and only remaining nickel ion of positively charged ion and sodium ion also have utmost point low levels foreign metal ion (concentration of iron ion and chromium ion all is lower than 1mg/l) in the solution.
Alternatively, in step S4, waste liquid enters accurate filter 40 and filters, and enters next flow process afterwards.
In step S5, nickel ion is extracted by the mode of ion exchange unit 50 with ion-exchange.Because the sodium ions content in the electrolytic solution is higher, so preferably adopt sodium type weakly acidic cation-exchange resin absorbed Ni ion.When nickel ion is present in the liquid with unbound state, when following ion exchange reaction takes place when containing the resin layer of exchangable ion:
2RNa+Ni
2+→R
2Ni+2Na
+
The efficient of ion exchange resin absorption metallic nickel ions is very high, and the absorption rate of recovery of general nickel can reach more than 99%, and the water outlet nickel ion is less than 1mg/l.After the saturated resin of nickel absorption can be regenerated, the high concentration of nickel solution of acquisition can be used as the raw material of producing the nickel product.
At last, in step S6, can feed back to electrolytic solution storage tank 60,70 through the electrolytic solution after the ion-exchange and carry out reuse.
In above-mentioned whole process, the reagent that is added is oxygen (or hydrogen peroxide), sodium hydroxide, and amount of reagent is simple, does not introduce new impurity, reclaims when this helps realizing nickel and electrolytic solution.And,, can reduce the processing costs of mud owing to from the mixture of script, extracted nickel as the multiple metal hydroxides of sludge treatment.On economic benefit, the income that the metallic nickel of extraction produces and the sludge treatment expense of minimizing can surpass the income that retrieving arrangement brought.
Though be in the foregoing description to comprise Fe
2+, Fe
3+, Ni
2+, Cr
3+, Na
2SO
4Electrolysis waste solution be that example is described, but understand easily.Embodiments of the invention are also applicable to containing Fe
2+, Fe
3+, Cr
3+In a part of ionic electrolysis waste solution or other similar waste liquid.
Though the present invention discloses as above with preferred embodiment; right its is not in order to qualification the present invention, any those skilled in the art, without departing from the spirit and scope of the present invention; when can doing a little modification and perfect, so protection scope of the present invention is when with being as the criterion that claims were defined.
Claims (6)
1. equipment that is used to recycle stainless steel neutral salt electrolysis waste solution, this electrolysis waste solution comprises nickel ion, in ferrous ion, iron ion, the chromium ion partly or entirely, and sodium sulfate, this equipment comprises:
This electrolysis waste solution is imported from an electrolytic solution storage tank in the oxidizing reaction pond, in this reaction tank this electrolysis waste solution is carried out an oxidation operation, makes the ferrous ion in this electrolysis waste solution be oxidized to iron ion, and wherein this oxidation operation is not introduced new ion to this electrolysis waste solution;
The pH value adjusting device is regulated pH value to a preset value of this electrolysis waste solution, and this preset value is between 4.8-5.2;
Equipment for separating liquid from solid, the electrolysis waste solution that input is regulated through the pH value separates with the precipitation that chromium ion forms the iron ion in the electrolysis waste solution with clear liquid;
Ion exchange unit, the isolated clear liquid of input equipment for separating liquid from solid extracts nickel wherein to carry out ion-exchange, and the liquid of exporting after the ion-exchange is fed back to this electrolytic solution storage tank.
2. the equipment that is used to recycle stainless steel neutral salt electrolysis waste solution as claimed in claim 1 is characterized in that, the oxygenant of this oxidation operation is oxygen or hydrogen peroxide.
3. the equipment that is used to recycle stainless steel neutral salt electrolysis waste solution as claimed in claim 1 is characterized in that, when this oxygenant was oxygen, this equipment also comprised aerating apparatus, by aeration oxygen is sneaked in this waste liquid.
4. the equipment that is used to recycle stainless steel neutral salt electrolysis waste solution as claimed in claim 1 is characterized in that, this pH value adjusting device is regulated the pH value of this waste liquid by sodium hydroxide.
5. the equipment that is used to recycle stainless steel neutral salt electrolysis waste solution as claimed in claim 1 is characterized in that, also comprises accurate filter, is connected between equipment for separating liquid from solid and the ion exchange unit.
6. the equipment that is used to recycle stainless steel neutral salt electrolysis waste solution as claimed in claim 1 is characterized in that, the ion exchange resin in this ion exchange unit is sodium type weakly acidic cation-exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102585396A CN102092874A (en) | 2009-12-09 | 2009-12-09 | Equipment for recycling stainless steel neutral salt waste electrolyte |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102585396A CN102092874A (en) | 2009-12-09 | 2009-12-09 | Equipment for recycling stainless steel neutral salt waste electrolyte |
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| Publication Number | Publication Date |
|---|---|
| CN102092874A true CN102092874A (en) | 2011-06-15 |
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ID=44126165
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| Application Number | Title | Priority Date | Filing Date |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106498171A (en) * | 2016-12-05 | 2017-03-15 | 张圆圆 | The recoverying and utilizing method of nickel and chromium in a kind of stainless steel |
| CN106630268A (en) * | 2016-12-05 | 2017-05-10 | 张圆圆 | Recycling method of nickel in stainless steel |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123345A (en) * | 1994-07-28 | 1996-05-29 | 株式会社日立制作所 | Method and apparatus for processing neutral salt electolysing liquid |
| JP2008183526A (en) * | 2007-01-31 | 2008-08-14 | Jfe Steel Kk | Method for treating acid waste liquid and alkali waste liquid |
| CN201729722U (en) * | 2009-12-09 | 2011-02-02 | 上海轻工业研究所有限公司 | Device for recycling stainless steel neutral salt waste electrolyte liquor |
-
2009
- 2009-12-09 CN CN2009102585396A patent/CN102092874A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123345A (en) * | 1994-07-28 | 1996-05-29 | 株式会社日立制作所 | Method and apparatus for processing neutral salt electolysing liquid |
| JP2008183526A (en) * | 2007-01-31 | 2008-08-14 | Jfe Steel Kk | Method for treating acid waste liquid and alkali waste liquid |
| CN201729722U (en) * | 2009-12-09 | 2011-02-02 | 上海轻工业研究所有限公司 | Device for recycling stainless steel neutral salt waste electrolyte liquor |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106498171A (en) * | 2016-12-05 | 2017-03-15 | 张圆圆 | The recoverying and utilizing method of nickel and chromium in a kind of stainless steel |
| CN106630268A (en) * | 2016-12-05 | 2017-05-10 | 张圆圆 | Recycling method of nickel in stainless steel |
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Application publication date: 20110615 |